Late-stage chemoselective functional-group manipulation of bioactive natural products with super-electrophilic silylium ions

NASA Astrophysics Data System (ADS)

Bender, Trandon A.; Payne, Philippa R.; Gagné, Michel R.

2018-01-01

The selective (and controllable) modification of complex molecules with disparate functional groups (for example, natural products) is a long-standing challenge that has been addressed using catalysts tuned to perform singular transformations (for example, C-H hydroxylation). A method whereby reactions with diverse functional groups within a single natural product are feasible depending on which catalyst or reagent is chosen would widen the possible structures one could obtain. Fluoroarylborane catalysts can heterolytically split Si-H bonds to yield an oxophilic silylium (R3Si+) equivalent along with a reducing (H-) equivalent. Together, these reactive intermediates enable the reduction of multiple functional groups. Exogenous phosphine Lewis bases further modify the catalyst speciation and attenuate aggressive silylium ions for the selective modification of complex natural products. Manipulation of the catalyst, silane reagent and the reaction conditions provides experimental control over which site is modified (and how). Applying this catalytic method to complex bioactive compounds (natural products or drugs) provides a powerful tool for studying structure-activity relationships.

A modified preparation procedure for carbon nanotube-confined Nd/Na heterobimetallic catalyst for anti-selective catalytic asymmetric nitroaldol reactions.

PubMed

Sureshkumar, Devarajulu; Hashimoto, Kazuki; Kumagai, Naoya; Shibasaki, Masakatsu

2013-11-15

A recyclable asymmetric metal-based catalyst is a rare entity among the vast collection of asymmetric catalysts developed so far. Recently we found that the combination of a self-assembling metal-based asymmetric catalyst and multiwalled carbon nanotubes (MWNTs) produced a highly active and recyclable catalyst in which the catalytically active metal complex was dispersed in the MWNT network. Herein we describe an improved preparation procedure and full details of a Nd/Na heterobimetallic complex confined in MWNTs. Facilitated self-assembly of the catalyst with MWNTs avoided the sacrificial use of excess chiral ligand for the formation of the heterobimetallic complex, improving the loading ratio of the catalyst components. Eighty-five percent of the catalyst components were incorporated onto MWNTs to produce the confined catalyst, which was a highly efficient and recyclable catalyst for the anti-selective asymmetric nitroaldol reaction. The requisite precautions for the catalyst preparation to elicit reproducible catalytic performance are summarized. Superior catalytic profiles over the prototype catalyst without MWNTs were revealed in the synthesis of optically active 1,2-nitroalkanols, which are key intermediates for the synthesis of therapeutics.

The capacity of modified nickel catalysts derived from discharged catalyst of fertilizer plants for NOx treatment

NASA Astrophysics Data System (ADS)

Ha, T. M. P.; Luong, N. T.; Le, P. N.

2016-11-01

In Vietnam for recent years, a large amount of hazardous waste containing nickel (Ni) derived from discharged catalyst of fertilizer plants has caused environmental problems in landfill overloading and the risk of soil or surface water sources pollution. Taking advantage of discharged catalyst, recycling Ni components and then synthesizing new catalysts apply for mono-nitrogen oxides (NOx) treatments is an approach to bring about both economic and environmental benefits. This study was carried out with the main objective: Evaluate the performance of modified catalysts (using recovered Ni from the discharged RKS-2-7H catalyst of Phu My Fertilizer Plant) on NOx treatment. The catalysts was synthesized and modified with active phases consist of recovered Ni and commercial Barium oxide (BaO), Manganese dioxide (MnO2) / Cerium (IV) oxide (CeO2) on the support Aluminium oxide (γ-Al2O3). The results show that the modified catalysts with Ni, Ba, Ce was not more beneficial for NOx removal than which with Ni, Ba, Mn. 98% NOx removal at 350°C with the start temperature at 115°C and the T60 value at 307°C can be obtained with 10Ni10Ba10Mn/Al catalyst.

CuO based catalysts on modified acidic silica supports tested in the de-NOx reduction.

PubMed

Bennici, Simona; Gervasini, Antonella; Lazzarin, Marta; Ragaini, Vittorio

2005-03-01

A series of dispersed CuO catalysts supported on modified silica supports with Al2O3 (SA), TiO2 (ST), and ZrO2 (SZ) were prepared optimising the adsorption method of copper deposition assisted by ultrasound treatment, already reported in a previous paper (S. Bennici, A. Gervasini, V. Ragaini, Ultrason. Sonochem. 10 (2003) 61). The obtained catalysts were characterized in their bulk (atomic absorption, X-ray diffraction, temperature programmed reduction) and surface (N2 adsorption, X-ray photoelectron spectroscopy, scanning electron microscopy) properties. The morphology of the finished materials was not deeply modified compared with that of the relevant supports. The employed complemented techniques evidenced a well dispersed CuO phase with a copper-support interaction on the most acidic supports (SA and SZ). The catalyst performances were studied in the reaction of selective catalytic reduction of NOx with ethene in oxidizing atmosphere in a flow apparatus under variable times (0.360-0.072 s) and temperatures (200-450 degrees C). The catalysts prepared on the most acidic supports (SA and SZ) were the most active and selective towards N2 formation. They showed a particular interesting activity in the reaction of NO2 reduction besides that of NO reduction.

DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Branko N. Popov

2009-03-03

The objective of this project is to develop novel non-precious metal electrocatalysts for oxygen reduction reaction (ORR), and demonstrate the potential of the catalysts to perform at least as good as conventional Pt catalysts currently in use in polymer electrolyte membrane fuel cell (PEMFC) with a cost at least 50 % less than a target of 0.2 g (Pt loading)/peak kW and with durability > 2,000 h operation with less than 10 % power degradation. A novel nitrogen-modified carbon-based catalyst was obtained by modifying carbon black with nitrogen-containing organic precursor in the absence of transition metal precursor. The catalyst showsmore » the onset potential of approximately 0.76 V (NHE) for ORR and the amount of H2O2 of approximately 3% at 0.5 V (NHE). Furthermore, a carbon composite catalyst was achieved through the high-temperature pyrolysis of the precursors of transition metal (Co and Fe) and nitrogen supported on the nitrogen-modified carbon-based catalyst, followed by chemical post-treatment. This catalyst showed an onset potential for ORR as high as 0.87 V (NHE), and generated less than 1 % of H2O2. The PEM fuel cell exhibited a current density of 2.3 A cm-2 at 0.2 V for a catalyst loading of 6.0 mg cm-2. No significant performance degradation was observed for 480 h continuous operation. The characterization studies indicated that the metal-nitrogen chelate complexes decompose at the temperatures above 800 oC. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface modified with nitrogen is active for ORR. In order to elucidate the role of transition metal precursor played in the formation of active sites in the non-precious metal catalysts, a novel ruthenium-based chelate (RuNx) catalyst was synthesized by using RuCl3 and propylene diammine as the Ru and N precursors, respectively, followed by high-temperature pyrolysis. This catalyst exhibited comparable catalytic activity and selectivity for ORR as the Pt catalyst. A theoretical analysis is made of the four-electron reduction reaction of oxygen to water over the mixed anion and cation (202) surface of pentlandite structure Co9Se8, one of several selenide phases. Reversible potentials for forming adsorbed reaction intermediates in acid are predicted using adsorption energies calculated with the Vienna ab initio simulation program (VASP) and the known bulk solution values together in a linear Gibbs energy relationship. The effect of hydrophobic and structural properties of a single/dual-layer cathode gas diffusion layer on mass transport in PEM fuel cells was studied using an analytical expression. The simulations indicated that liquid water transport at the cathode is controlled by the fraction of hydrophilic surface and the average pore diameter in the cathode gas diffusion layer. The optimized hydrophobicity and pore geometry in a dual-layer cathode GDL leads to an effective water management, and enhances the oxygen diffusion kinetics.« less

DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Branko N. Popov

2009-02-20

The objective of this project is to develop novel non-precious metal electrocatalysts for oxygen reduction reaction (ORR), and demonstrate the potential of the catalysts to perform at least as good as conventional Pt catalysts currently in use in polymer electrolyte membrane fuel cell (PEMFC) with a cost at least 50 % less than a target of 0.2 g (Pt loading)/peak kW and with durability > 2,000 h operation with less than 10 % power degradation. A novel nitrogen-modified carbon-based catalyst was obtained by modifying carbon black with nitrogen-containing organic precursor in the absence of transition metal precursor. The catalyst showsmore » the onset potential of approximately 0.76 V (NHE) for ORR and the amount of H2O2 of approximately 3% at 0.5 V (NHE). Furthermore, a carbon composite catalyst was achieved through the high-temperature pyrolysis of the precursors of transition metal (Co and Fe) and nitrogen supported on the nitrogen-modified carbon-based catalyst, followed by chemical post-treatment. This catalyst showed an onset potential for ORR as high as 0.87 V (NHE), and generated less than 1 % of H2O2. The PEM fuel cell exhibited a current density of 2.3 A cm-2 at 0.2 V for a catalyst loading of 6.0 mg cm-2. No significant performance degradation was observed for 480 h continuous operation. The characterization studies indicated that the metal-nitrogen chelate complexes decompose at the temperatures above 800 oC. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface modified with nitrogen is active for ORR. In order to elucidate the role of transition metal precursor played in the formation of active sites in the non-precious metal catalysts, a novel ruthenium-based chelate (RuNx) catalyst was synthesized by using RuCl3 and propylene diammine as the Ru and N precursors, respectively, followed by high-temperature pyrolysis. This catalyst exhibited comparable catalytic activity and selectivity for ORR as the Pt catalyst. A theoretical analysis is made of the four-electron reduction reaction of oxygen to water over the mixed anion and cation (202) surface of pentlandite structure Co9Se8, one of several selenide phases. Reversible potentials for forming adsorbed reaction intermediates in acid are predicted using adsorption energies calculated with the Vienna ab initio simulation program (VASP) and the known bulk solution values together in a linear Gibbs energy relationship. The effect of hydrophobic and structural properties of a single/dual-layer cathode gas diffusion layer on mass transport in PEM fuel cells was studied using an analytical expression. The simulations indicated that liquid water transport at the cathode is controlled by the fraction of hydrophilic surface and the average pore diameter in the cathode gas diffusion layer. The optimized hydrophobicity and pore geometry in a dual-layer cathode GDL leads to an effective water management, and enhances the oxygen diffusion kinetics.« less

Development of Carbon-Based Solid Acid Catalysts Using a Lipid-Extracted Alga, Dunaliella tertiolecta, for Esterification.

PubMed

Ryu, Young-Jin; Kim, Z-Hun; Lee, Seul Gi; Yang, Ji-Hyun; Shin, Hee-Yong; Lee, Choul-Gyun

2018-05-28

Novel carbon-based solid acid catalysts were synthesized through a sustainable route from lipid-extracted microalgal residue of Dunaliella tertiolecta , for biodiesel production. Two carbon-based solid acid catalysts were prepared by surface modification of bio-char with sulfuric acid (H₂SO₄) and sulfuryl chloride (SO₂Cl₂), respectively. The treated catalysts were characterized and their catalytic activities were evaluated by esterification of oleic acid. The esterification catalytic activity of the SO₂Cl₂-treated bio-char was higher (11.5 mmol Prod.∙h⁻¹∙g Cat. ⁻¹) than that of commercial catalyst silica-supported Nafion SAC-13 (2.3 mmol Prod.∙h⁻¹∙g Cat. ⁻¹) and H₂SO₄-treated bio-char (5.7 mmol Prod.∙h⁻¹∙g Cat. ⁻¹). Reusability of the catalysts was examined. The catalytic activity of the SO₂Cl₂-modified catalyst was sustained from the second run after the initial activity dropped after the first run and kept the same activity until the fifth run. It was higher than that of first-used Nafion. These experimental results demonstrate that catalysts from lipid-extracted algae have great potential for the economic and environment-friendly production of biodiesel.

Highly Selective Deoxydehydration of Tartaric Acid over Supported and Unsupported Rhenium Catalysts with Modified Acidities.

PubMed

Li, Xiukai; Zhang, Yugen

2016-10-06

The deoxydehydration (DODH) of sugar acids to industrially important carboxylic acids is a very attractive topic. Oxorhenium complexes are the most-often employed DODH catalysts. Because of the acidity of the rhenium catalysts, the DODH products of sugar acids were usually in the form of mixture of free carboxylic acids and esters. Herein, we demonstrate strategies for the selective DODH of sugar acids to free carboxylic acids by tuning the Lewis acidity or the Brønsted acidity of the rhenium-based catalysts. Starting from tartaric acid, up to 97 % yield of free maleic acid was achieved. Based on our strategies, functional polymer immobilized heterogeneous rhenium catalysts were also developed for the selective DODH conversion of sugar acids. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

SnO2 promoted by alkali metal oxides for soot combustion: The effects of surface oxygen mobility and abundance on the activity

NASA Astrophysics Data System (ADS)

Rao, Cheng; Shen, Jiating; Wang, Fumin; Peng, Honggen; Xu, Xianglan; Zhan, Hangping; Fang, Xiuzhong; Liu, Jianjun; Liu, Wenming; Wang, Xiang

2018-03-01

In this study, SnO2-based catalysts promoted by different alkali metal oxides with a Sn/M (M = Li, Na, K, Cs) molar ratio of 9/1 have been prepared for soot combustion. In comparison with the un-modified SnO2 support, the activity of the modified catalysts has been evidently enhanced, following the sequence of CsSn1-9 > KSn1-9 > NaSn1-9 > LiSn1-9 > SnO2. As testified by Raman, H2-TPR, soot-TPR-MS, XPS and O2-TPD results, the incorporation of various alkali metal oxides can induce the formation of more abundant and mobile oxygen species on the surface of the catalysts. Moreover, quantified results have proved that the amount of the surface active oxygen species is nearly proportional to the activity of the catalysts. CsSn1-9, the catalyst promoted by cesium oxide, owns the largest amount of surface mobile oxygen species, thus having the highest activity among all the studied catalysts. It is concluded that the amount of surface active and mobile oxygen species is the major factor determining the activity of the catalysts for soot combustion.

Modifying ceria (111) with a TiO2 nanocluster for enhanced reactivity.

PubMed

Nolan, Michael

2013-11-14

Modification of ceria catalysts is of great interest for oxidation reactions such as oxidative dehydrogenation of alcohols. Improving the reactivity of ceria based catalysts for these reactions means that they can be run at lower temperatures and density functional theory (DFT) simulations of new structures and compositions are proving valuable in the development of these catalysts. In this paper, we have used DFT+U (DFT corrected for on-site Coulomb interactions) to examine the reactivity of a novel modification of ceria, namely, modifying with TiO2, using the example of a Ti2O4 species adsorbed on the ceria (111) surface. The oxygen vacancy formation energy in the Ti2O4-CeO2 system is significantly reduced over the bare ceria surfaces, which together with previous work on ceria-titania indicates that the presence of the interface favours oxygen vacancy formation. The energy gain upon hydrogenation of the catalyst, which is the rate determining step in oxidative dehydrogenation, further points to the improved oxidation power of this catalyst structure.

Promoted Iron Nanocrystals Obtained via Ligand Exchange as Active and Selective Catalysts for Synthesis Gas Conversion

PubMed Central

2017-01-01

Colloidal synthesis routes have been recently used to fabricate heterogeneous catalysts with more controllable and homogeneous properties. Herein a method was developed to modify the surface composition of colloidal nanocrystal catalysts and to purposely introduce specific atoms via ligands and change the catalyst reactivity. Organic ligands adsorbed on the surface of iron oxide catalysts were exchanged with inorganic species such as Na2S, not only to provide an active surface but also to introduce controlled amounts of Na and S acting as promoters for the catalytic process. The catalyst composition was optimized for the Fischer–Tropsch direct conversion of synthesis gas into lower olefins. At industrially relevant conditions, these nanocrystal-based catalysts with controlled composition were more active, selective, and stable than catalysts with similar composition but synthesized using conventional methods, possibly due to their homogeneity of properties and synergic interaction of iron and promoters. PMID:28824820

The enhancement of CuO modified V2O5-WO3/TiO2 based SCR catalyst for Hg° oxidation in simulated flue gas

NASA Astrophysics Data System (ADS)

Chen, Chuanmin; Jia, Wenbo; Liu, Songtao; Cao, Yue

2018-04-01

CuO modified V2O5-WO3/TiO2 based SCR catalysts prepared by improved impregnation method were investigated to evaluate the catalytic activity for elemental mercury (Hg°) oxidation in simulated flue gas at 150-400 °C. Nitrogen adsorption, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to characterize the catalysts. It was found that V0.8WTi-Cu3 catalyst exhibited the superior Hg° oxidation activity and wide operating temperature window at the gas hourly space velocity (GHSV) of 3 × 105 h-1. The BET and XRD results showed that CuO was well loaded and highly dispersed on the catalysts surface. The XPS results suggested that the addition of CuO generated abundant chemisorbed oxygen, which was due to the synergistic effect between CuO and V2O5. The existence of the redox cycle of V4+ + Cu2+ ↔ V5+ + Cu+ in V0.8WTi-Cu3 catalyst enhanced Hg° oxidation activity. The effects of flue gas components (O2, NO, SO2 and H2O) on Hg° oxidation over V0.8WTi-Cu3 catalyst were also explored. Moreover, the co-presence of NO and NH3 remarkably inhibited Hg° oxidation, which was due to the competitive adsorption and reduction effect of NH3 at SCR condition. Fortunately, this inhibiting effect was gradually scavenged with the decrease of GHSV. The mechanism of Hg° oxidation was also investigated.

The black rock series supported SCR catalyst for NO x removal.

PubMed

Xie, Bin; Luo, Hang; Tang, Qing; Du, Jun; Liu, Zuohua; Tao, Changyuan

2017-09-01

Black rock series (BRS) is of great potential for their plenty of valued oxides which include vanadium, iron, alumina and silica oxides, etc. BRS was used for directly preparing of selective catalytic reduction (SCR) catalyst by modifying its surface texture with SiO 2 -TiO 2 sols and regulating its catalytic active constituents with V 2 O 5 and MoO 3 . Consequently, 90% NO removal ratio was obtained within 300-400 °C over the BRS-based catalyst. The structure and properties of the BRS-based catalyst were characterized by the techniques of N 2 adsorption-desorption, X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), H 2 -temperature programmed reduction (H 2 -TPR), and NH 3 -temperature programmed desorption (NH 3 -TPD). The results revealed that the BRS-based catalyst possesses favorable properties for NO x removal, including highly dispersed active components, abundant surface-adsorbed oxygen O α , well redox property, and numerous Brønsted acid sites. Particularly, the BRS-based catalyst exhibited considerable anti-poisoning performance compared with commercial TiO 2 -based catalyst. The former catalyst shows a NO conversion surpassing 80% from 300 to 400 °C for potassium poisoning, and a durability of SO 2 and H 2 O exceeding 85% at temperatures from 300 to 450 °C.

Modified Fe3O4- hydroxyapatite nanocomposites as heterogeneous catalysts in three UV, Vis and Fenton like degradation systems

NASA Astrophysics Data System (ADS)

Valizadeh, S.; Rasoulifard, M. H.; Dorraji, M. S. Seyed

2014-11-01

The magnetite-hydroxyapatite (M-HAP) nanocomposites were prepared by a chemical co- precipitation procedure and characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and diffuse reflectance spectra (DRS). The ability of the synthesized catalyst for photocatalytic degradation of Acid Blue 25 (AB25), as an organic dye, under UV irradiation was studied. The catalyst was modified employing transition metals (Mn, Fe, Co, Ni, Cu and Zn) trying to improve the catalytic performance of HAP in absence of UV irradiation and in the presence of hydrogen peroxide i.e. a Fenton like reaction. The best results obtained for Cu and Co modified M-HAPs and the effect of operational parameters such pH, amount of catalyst and hydrogen peroxide concentration was studied. In order to investigate the performance of HAP based photocatalyst in visible light region, M-HAP was modified with silver ions. At the end, Langmuir-Hinshelwood kinetic expression used to evaluate and compare the catalytic systems. The strongest degradation activity was observed for Ag-M-HAP/Vis system because of Ag3PO4 formation. Apparent reaction rate constant (Kapp) by Ag-M-HAP/Vis was 63, 36 and 19 times faster than Cu-M-HAP(II)/H2O2, Co-M-HAP(II)/H2O2 and M-HAP (I)/UV systems, respectively.

Activities of Combined TiO2 Semiconductor Nanocatalysts Under Solar Light on the Reduction of CO2.

PubMed

Liu, Hongfang; Dao, Anh Quang; Fu, Chaoyang

2016-04-01

The materials based on TiO2 semiconductors are a promising option for electro-photocatalytic systems working as solar energy low-carbon fuels exchanger. These materials' structures are modified by doping metals and metal oxides, by metal sulfides sensitization, or by graphene supported membrane, enhancing their catalytic activity. The basic phenomenon of CO2 reduction to CH4 on Pd modified TiO2 under UV irradiation could be enhanced by Pd, or RuO2 co-doped TiO2. Sensitization with metal sulfide QDs is effective by moving of photo-excited electron from QDs to TiO2 particles. Based on characteristics of the catalysts various combinations of catalysts are proposed in order to creat catalyst systems with good CO2 reduction efficiency. From this critical review of the CO2 reduction to organic compounds by converting solar light and CO2 to storable fuels it is clear that more studies are still attractive and needed.

Autothermal reforming of propane over Mg-Al hydrotalcite-like catalysts.

PubMed

Lim, You-Soon; Park, Nam-Cook; Shin, Jae-Soon; Kim, Jong-Ho; Moon, Dong-Ju; Kim, Young-Chul

2008-10-01

The performance of hydrotalcite-like catalysts in propane autothermal reforming for hydrogen production was studied in fixed-bed flow reactor. Hydrotalcite-like catalysts were synthesized by coprecipitation and modified co-precipitation by the impregnation method and those were promoted by the addition of noble metals. Reaction test results indicated that hydrotalcite-like catalysts of modified method were showed higher H2-yield than co-precipitation method because surface Ni particles of catalysts by modified method were more abundant. When added noble metals, the activity was enhanced because the size of nickel particles was decreased and degree of dispersion was increased. Also the carbon deposit is low after the reaction. When solvent of solution was changed, activity was increased. It is because degree of dispersion was increased.

Support effects on adsorption and catalytic activation of O2 in single atom iron catalysts with graphene-based substrates.

PubMed

Gao, Zheng-Yang; Yang, Wei-Jie; Ding, Xun-Lei; Lv, Gang; Yan, Wei-Ping

2018-03-07

The adsorption and catalytic activation of O 2 on single atom iron catalysts with graphene-based substrates were investigated systematically by density functional theory calculation. It is found that the support effects of graphene-based substrates have a significant influence on the stability of the single atom catalysts, the adsorption configuration, the electron transfer mechanism, the adsorption energy and the energy barrier. The differences in the stable adsorption configuration of O 2 on single atom iron catalysts with different graphene-based substrates can be well understood by the symmetrical matching principle based on frontier molecular orbital analysis. There are two different mechanisms of electron transfer, in which the Fe atom acts as the electron donor in single vacancy graphene-based substrates while the Fe atom mainly acts as the bridge for electron transfer in double vacancy graphene-based substrates. The Fermi softness and work function are good descriptors of the adsorption energy and they can well reveal the relationship between electronic structure and adsorption energy. This single atom iron catalyst with single vacancy graphene modified by three nitrogen atoms is a promising non-noble metal single atom catalyst in the adsorption and catalytic oxidation of O 2 . Furthermore, the findings can lay the foundation for the further study of graphene-based support effects and provide a guideline for the development and design of new non-noble-metal single atom catalysts.

Microgravity Effects on Chronoamperometric Ammonia Oxidation Reaction at Platinum Nanoparticles on Modified Mesoporous Carbon Supports

NASA Astrophysics Data System (ADS)

Poventud-Estrada, Carlos M.; Acevedo, Raúl; Morales, Camila; Betancourt, Luis; Diaz, Diana C.; Rodriguez, Manuel A.; Larios, Eduardo; José-Yacaman, Miguel; Nicolau, Eduardo; Flynn, Michael; Cabrera, Carlos R.

2017-10-01

The effect of microgravity on the electrochemical oxidation of ammonia at platinum nanoparticles supported on modified mesoporous carbons (MPC) with three different pore diameters (64, 100, and 137 Å) was studied via the chronoamperometric technique in a half-cell. The catalysts were prepared by a H2 reductive process of PtCl6^{4-} in presence of the mesoporous carbon support materials. A microgravity environment was obtained with an average gravity of less than 0.02 g created aboard an airplane performing parabolic maneuvers. Results show the chronoamperommetry of the ammonia oxidation reaction in 1.0 M NH4OH at 0.60 V vs. RHE under microgravity conditions. The current density, in all three catalysts, decreased while in microgravity conditions when compared to ground based experiments. Under microgravity, all three catalysts yielded a decrease in ammonia oxidation reaction current density between 25 to 63% versus terrestrial experimental results, in time scales between 1 and 15 s. The Pt catalyst prepared with mesoporous carbon of 137 Å porous showed the smallest changes, between 25 to 48%. Nanostructuring catalyst materials have an effect on the level of current density decrease under microgravity conditions.

PES Surface Modification Using Green Chemistry: New Generation of Antifouling Membranes.

PubMed

Nady, Norhan

2016-04-18

A major limitation in using membrane-based separation processes is the loss of performance due to membrane fouling. This drawback can be addressed thanks to surface modification treatments. A new and promising surface modification using green chemistry has been recently investigated. This modification is carried out at room temperature and in aqueous medium using green catalyst (enzyme) and nontoxic modifier, which can be safely labelled "green surface modification". This modification can be considered as a nucleus of new generation of antifouling membranes and surfaces. In the current research, ferulic acid modifier and laccase bio-catalyst were used to make poly(ethersulfone) (PES) membrane less vulnerable to protein adsorption. The blank and modified PES membranes are evaluated based on e.g., their flux and protein repellence. Both the blank and the modified PES membranes (or laminated PES on silicon dioxide surface) are characterized using many techniques e.g., SEM, EDX, XPS and SPM, etc. The pure water flux of the most modified membranes was reduced by 10% on average relative to the blank membrane, and around a 94% reduction in protein adsorption was determined. In the conclusions section, a comparison between three modifiers-ferulic acid, and two other previously used modifiers (4-hydroxybenzoic acid and gallic acid)-is presented.

Effect of valence state and particle size on NO oxidation in fresh and aged Pt-based diesel oxidation catalysts

NASA Astrophysics Data System (ADS)

Liang, Yanli; Ding, Xinmei; Zhao, Ming; Wang, Jianli; Chen, Yaoqiang

2018-06-01

To stabilize Pt, Magnesium-modified SiO2-Al2O3 materials was used to impregnate with Pt, which could strengthen the bonding effect between Pt and Mg. Before and after aging, both showed a higher dispersion. High valence state of Pt in fresh modified catalyst was unfavorable of NO oxidation, indicating that the valence state of Pt was the leader factor in fresh catalytic performance. While for the aged Mg-modified sample, its reaction temperature of 30% NO conversion lowered by around 30 °C. The Pt stabilization via interacting with Mg derives a relation that the variation of Pt valence state and its exposed sites played a significant role in fresh and aged catalytic NO activity, respectively.

Pd nanoparticles Supported on Cellulose as a catalyst for vanillin conversion in aqueous media.

PubMed

Li, Dan-Dan; Zhang, Jia-Wei; Cai, Chun

2018-05-17

Palladium nanoparticles were firstly anchored on modified biopolymer as an efficient catalyst for biofuel upgradation. Fluorinated compounds was grafted onto cellulose to obtain amphiphilic supports for on water reactions. Pd catalyst was prepared by straightforward deposition of metal nanoparticles on modified cellulose. The catalyst exhibited excellent catalytic activity and selectivity in hydrodeoxygenation of vanillin (a typical model compound of lignin) to 2-methoxy-4-methylphenol under atmospheric hydrogen pressure in neat water without any other additives under mild conditions.

Graphene Derivative in Magnetically Recoverable Catalyst Determines Catalytic Properties in Transfer Hydrogenation of Nitroarenes to Anilines with 2-Propanol.

PubMed

Das, Vijay Kumar; Mazhar, Sumaira; Gregor, Lennon; Stein, Barry D; Morgan, David Gene; Maciulis, Nicholas A; Pink, Maren; Losovyj, Yaroslav; Bronstein, Lyudmila M

2018-06-14

Here, we report transfer hydrogenation of nitroarenes to aminoarenes using 2-propanol as a hydrogen source and Ag-containing magnetically recoverable catalysts based on partially reduced graphene oxide (pRGO) sheets. X-ray diffraction and X-ray photoelectron spectroscopy data demonstrated that, during the one-pot catalyst synthesis, formation of magnetite nanoparticles (NPs) is accompanied by the reduction of graphene oxide (GO) to pRGO. The formation of Ag 0 NPs on top of magnetite nanoparticles does not change the pRGO structure. At the same time, the catalyst structure is further modified during the transfer hydrogenation, leading to a noticeable increase of sp 2 carbons. These carbons are responsible for the adsorption of substrate and intermediates, facilitating a hydrogen transfer from Ag NPs and creating synergy between the components of the catalyst. The nitroarenes with electron withdrawing and electron donating substituents allow for excellent yields of aniline derivatives with high regio and chemoselectivity, indicating that the reaction is not disfavored by these functionalities. The versatility of the catalyst synthetic protocol was demonstrated by a synthesis of an Ru-containing graphene derivative based catalyst, also allowing for efficient transfer hydrogenation. Easy magnetic separation and stable catalyst performance in the transfer hydrogenation make this catalyst promising for future applications.

One-step electrochemical deposition of Schiff base cobalt complex as effective water oxidation catalyst

NASA Astrophysics Data System (ADS)

Huang, Binbin; Wang, Yan; Zhan, Shuzhong; Ye, Jianshan

2017-02-01

Schiff base metal complexes have been applied in many fields, especially, a potential homogeneous catalyst for water splitting. However, the high overpotential, time consumed synthesis process and complicated working condition largely limit their application. In the present work, a one-step approach to fabricate Schiff base cobalt complex modified electrode is developed. Microrod clusters (MRC) and rough spherical particles (RSP) can be obtained on the ITO electrode through different electrochemical deposition condition. Both of the MRC and RSP present favorable activity for oxygen evolution reaction (OER) compared to the commercial Co3O4, taking an overpotential of 650 mV and 450 mV to drive appreciable catalytic current respectively. The highly active and stable RSP shows a Tafel plot of 84 mV dec-1 and negligible decrease of the current density for 12 h bulk electrolysis. The synthesis strategy of effective and stable catalyst in this work provide a simple method to fabricate heterogeneous OER catalyst with Schiff base metal complex.

Phenol hydroxylation on Al-Fe modified-bentonite: Effect of Fe loading, temperature and reaction time

NASA Astrophysics Data System (ADS)

Widi, R. K.; Budhyantoro, A.; Christianto, A.

2017-11-01

The present work reflects the study of the phenol hydroxylation reactions to synthesize hydroquinone and catechol on Al-Fe modified-bentonite. This study started with synthesizes the catalyst material based on the modified bentonite. Natural bentonite from Pacitan, Indonesia was intercalated with Cetyl-TetramethylammoniumBromida (CTMA-Br) followed by pillarization using Alumina. The pillared bentonite was then impregnated with Fe solution (0.01 M, 0.05 M, and 0.1 M). The solid material obtained was calcined at 723 K for 4 hours. All the materials were characterized using BET N2 adsorption. Their catalytic activity and selectivity were studied for phenol hydroxylation using H2O2 (30%). The reaction conditions of this reaction were as follows: ratio of phenol/H2O2 = 1:1 (molar ratio), concentration of phenol = 1 M and ratio of catalyst/phenol was 1:10. Reaction temperatures were varied at 333, 343 and 353 K. The reaction time was also varied at 3, 4 and 5 hours. The result shows that the materials have potential catalyst activity.

Poisoning of a silica supported cobalt catalyst due to the presence of sulfur impurities in syngas during Fischer-Tropsch synthesis: Effect of chelating agent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bambal, A.S.; Gardner, T.H.; Kugler, E.L.

2012-01-01

Sulfur compounds that are generally found in syngas derived from coal and biomass are a poison to Fischer-Tropsch (FT) catalysts. The presence of sulfur impurities in the ppm range can limit the life of a FT catalyst to a few hours or a few days. In this study, FT synthesis was carried out in a fixed-bed reactor at 230 °C, 20 bar, and 13,500 Ncm3/h/gcat for 72 h using syngas with H2/CO = 2.0. Cobalt-based catalysts were subjected to poisoning by 10 and 50 ppm sulfur in the syngas. The performance of FT catalyst was compared in context of syngasmore » conversion, product selectivities and yields, during the poisoning as well as post-poisoning stages. At both the impurity concentrations, the sulfur was noted to cause permanent loss in the activity, possibly by adsorbing irreversibly on the surface. The sulfur poison affects the hydrogenation and the chain-propagation ability of the catalysts, and shifts the product selectivity towards short-chain hydrocarbons with higher percentages of olefins. Additional diffusion limitations caused due to sulfur poisoning are thought to alter the product selectivity. The shifts in product selectivities suggest that the sulfur decreases the ability of the catalyst to form C-C bonds to produce longer-chain hydrocarbons. The selective blocking of sulfur is thought to affect the hydrogenation ability on the catalyst, resulting in more olefins in the product after sulfur poisoning. The sulfur poisoning on the cobalt catalyst is expected to cause an increase in the number of sites responsible for WGS or to influence the Boudouard reaction, resulting in a higher CO2 selectivity. Both the sites responsible for CO adsorptions as well as the sites for chain growth are poisoned during the poisoning. Additionally, the performance of a base-case cobalt catalyst is compared with that of catalysts modified by chelating agents (CAs). The superior performance of CA-modified catalysts during sulfur poisoning is attributed to the presence of smaller crystallite sizes and higher dispersions of cobalt on the support. Finally, the sulfur deactivation data is modeled by a simple kinetic expression to determine the deactivation constant, deactivation rates and half-life of the FT catalyst.« less

Heterogeneous electro-Fenton using modified iron-carbon as catalyst for 2,4-dichlorophenol degradation: influence factors, mechanism and degradation pathway.

PubMed

Zhang, Chao; Zhou, Minghua; Ren, Gengbo; Yu, Xinmin; Ma, Liang; Yang, Jie; Yu, Fangke

2015-03-01

Modified iron-carbon with polytetrafluoroethylene (PTFE) was firstly investigated as heterogeneous electro-Fenton (EF) catalyst for 2,4-dichlorophenol (2,4-DCP) degradation in near neutral pH condition. The catalyst was characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), and the effects of some important operating parameters such as current intensity and pH on the 2,4-DCP degradation were investigated. After the catalyst modification with 20% PTFE, the degradation performance maintained well with much lower iron leaching, and at current intensity 100 mA, initial pH 6.7, catalyst loading 6 g/L, the degradation efficiency of 2,4-DCP could exceed 95% within 120 min treatment. Two-stage pseudo first-order kinetics of 2,4-DCP degradation was observed, including a slow anodic oxidation stage (first-stage) and much faster heterogeneous EF oxidation (second-stage), in which the automatic drop of pH in the first-stage initiated the Fe(2+) release from micro-electrolysis and thus benefited to the subsequent EF reaction. Aromatic intermediates such as 3,5-dichlorocatechol, 4,6-dichlororesorcinol and 2-chlorohydroquinone were detected by GC-MS. Oxalic acid, acetic acid, formic acid and Cl(-) were quantified by ion chromatograph. Based on these analysis as well as the detection of H₂O₂ and OH, a possible mechanism and degradation pathway for 2,4-DCP were proposed. This work demonstrated that such a heterogeneous EF using cheap modified Fe-C catalyst was promising for organic wastewater treatment in initial neutral pH condition. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effect of catalyst type on field emission properties of nanostructured carbon films grown by a modified hot-filament chemical vapor deposition technique

NASA Astrophysics Data System (ADS)

Kang, Sukill; Lowndes, Douglas H.; Ellis, Darren

2001-03-01

Nanostructured carbon films have been grown on uncatalysed n-type Si using a modified HF-CVD process and catalytic decomposition of ethylene (C_2H_4). Various metal catalyst wires such as Ni, Co, Fe and a NiFe composite were placed within the windings of a tungsten filament and the assembly was placed in close proximity ( ~7 mm) to the unheated substrate. Radiative heating of the substrate by the filament results in a substrate temperature of ~ 500^oC after 7 min. Films grown using the Ni catalyst showed a field emission turn-on field that varied from 9 to 15 V/μm and was stable for 30-50 hours (1-10 A/cm^2 emission current density), a result that is comparable to carbon nanotube- and carbon nanofiber-based structures. In this contribution, we present results from field emission scanning electron microscopy, transmission electron microscopy, and electron field emission measurements that elucidate the relationship between field emission properties, film morphology, and type of catalyst.

Phosphorene Co-catalyst Advancing Highly Efficient Visible-Light Photocatalytic Hydrogen Production.

PubMed

Ran, Jingrun; Zhu, Bicheng; Qiao, Shi-Zhang

2017-08-21

Transitional metals are widely used as co-catalysts boosting photocatalytic H 2 production. However, metal-based co-catalysts suffer from high cost, limited abundance and detrimental environment impact. To date, metal-free co-catalyst is rarely reported. Here we for the first time utilized density functional calculations to guide the application of phosphorene as a high-efficiency metal-free co-catalyst for CdS, Zn 0.8 Cd 0.2 S or ZnS. Particularly, phosphorene modified CdS shows a high apparent quantum yield of 34.7 % at 420 nm. This outstanding activity arises from the strong electronic coupling between phosphorene and CdS, as well as the favorable band structure, high charge mobility and massive active sites of phosphorene, supported by computations and advanced characterizations, for example, synchrotron-based X-ray absorption near edge spectroscopy. This work brings new opportunities to prepare highly-active, cheap and green photocatalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

PES Surface Modification Using Green Chemistry: New Generation of Antifouling Membranes

PubMed Central

Nady, Norhan

2016-01-01

A major limitation in using membrane-based separation processes is the loss of performance due to membrane fouling. This drawback can be addressed thanks to surface modification treatments. A new and promising surface modification using green chemistry has been recently investigated. This modification is carried out at room temperature and in aqueous medium using green catalyst (enzyme) and nontoxic modifier, which can be safely labelled “green surface modification”. This modification can be considered as a nucleus of new generation of antifouling membranes and surfaces. In the current research, ferulic acid modifier and laccase bio-catalyst were used to make poly(ethersulfone) (PES) membrane less vulnerable to protein adsorption. The blank and modified PES membranes are evaluated based on e.g., their flux and protein repellence. Both the blank and the modified PES membranes (or laminated PES on silicon dioxide surface) are characterized using many techniques e.g., SEM, EDX, XPS and SPM, etc. The pure water flux of the most modified membranes was reduced by 10% on average relative to the blank membrane, and around a 94% reduction in protein adsorption was determined. In the conclusions section, a comparison between three modifiers—ferulic acid, and two other previously used modifiers (4-hydroxybenzoic acid and gallic acid)—is presented. PMID:27096873

An empirical study on the preparation of the modified coke and its catalytic oxidation properties

NASA Astrophysics Data System (ADS)

Liu, Hao; Jiang, Wenqiang

2017-05-01

T As a methyl acrylic ester fungicide, pyraclostrobin has the advantages of high activity, wide sterilization spectrum and high safety level comparing with the traditional fungicide. Due to less toxicity and side effects on human and environment, the use of pyraclostrobin and its mixture in agriculture is increasing. The heavy use of pyraclostrobin will inevitably cause pollution to the biological and abiotic environment. Therefore, it is of great significance to do the research on the degradation of pyraclostrobin. In this study, coke, as matrix, was modified by chemical modification. The modified coke was used as the catalyst and the pyraclostrobin was used as the degradation object. The degradation experiment of pyraclostrobin was carried out by using catalytic oxidation. The catalytic oxidation performance of modified coke was studied. The result showed that in the catalytic oxidation system of using modified coke as catalyst and H2O2 as oxidant, the best reaction condition is as following: The modified coke which is modified by using 70% concentration nitric acid is used as catalyst; The dosage of the catalyst is10g; The dosage of H2O2 is 0.6ml; The reaction time is 6 hours.

Anchoring of Cu(II) onto surface of porous metal-organic framework through post-synthesis modification for the synthesis of benzimidazoles and benzothiazoles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kardanpour, Reihaneh; Tangestaninejad, Shahram, E-mail: stanges@sci.ui.ac.ir; Mirkhani, Valiollah, E-mail: mirkhani@sci.ui.ac.ir

2016-03-15

Efficient synthesis of various benzimidazoles and benzothiazoles under mild conditions catalyzed by Cu(II) anchored onto UiO-66–NH{sub 2} metal organic framework is reported. In this manner, first, the aminated UiO-66 was modified with thiophene-2-carbaldehyde and then the prepared Schiff base was reacted with CuCl{sub 2}. The prepared catalyst was characterized by FT-IR, UV–vis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N{sub 2} adsorption, inductively coupled plasma atomic emission spectroscopy (ICP-AES) and field emission scanning electron microscopy (FE-SEM). The UiO-66–NH{sub 2}–TC–Cu was applied as a highly efficient catalyst for synthesis of benzimidazole and benzothiazole derivatives by the reaction of aldehydes with 1,2-diaminobenzenemore » or 2-aminothiophenol. The Cu(II)-containing MOF was reused several times without any appreciable loss of its efficiency. - Graphical abstract: Efficient synthesis of benzimidazoles and benzothiazoles catalyzed by Cu(II) anchored onto UiO-66–NH{sub 2} metal organic framework is reported. - Highlights: • A copper Schiff base was immobilized on UiO-66 via postsynthetic modification. • The modified MOFs were fully characterized by a variety of methods. • The catalyst was used for the preparation of benzimidazoles and benzothiazoles. • In comparison of other catalysts, our catalyst was more efficient and forceful.« less

Aromatic hydrocarbon production via eucalyptus urophylla pyrolysis over several metal modified ZSM-5 catalysts – an analysis by py-GC/MS

USDA-ARS?s Scientific Manuscript database

Metal modified HZSM-5 catalysts were prepared by ion exchange of NH4ZSM-5 (SIO2/Al2O3 = 23) using gallium, molybdenum, nickel and zinc, and their combinations thereof. The prepared catalysts were used to evaluate catalytic pyrolysis for the conversion of Eucalyptus urophylla to fuels and chemicals, ...

Protic ionic liquid modified electrocatalyst enables robust anode under cell reversal condition

NASA Astrophysics Data System (ADS)

Zhu, Zhengyu; Yan, Xiaocong; Tang, Haolin; Cai, Haopeng; Pan, Mu; Zhang, Haining; Luo, Jiangshui

2017-05-01

Pt/C has been commercially used as anode electrocatalyst for fuel cells but generally exhibits limited durability under conditions of fuel starvation and subsequent cell reversal. Herein we report an improved scaffold concept to simultaneously stabilize the catalyst against particle growth and reduce the adverse effects of cell reversal by modifying Pt/C with suitable protic ionic liquids (PILs). The modified Pt/C catalysts show enhanced cell reversal tolerance because of their high activity towards oxygen evolution reaction (OER), up to 300 mV lower overpotential compared to the unmodified Pt/C. Moreover, the PIL modified catalysts show better resistance to the loss of electrochemical surface area (ECSA) under simulated cell reversal conditions. The results indicate that modification of Pt/C catalysts with PILs is a promising strategy to enhance the stability and durability of electrocatalysts in fuel cell applications with the risk of frequent fuel starvation events, such as automotive fuel cells.

Oxidation of methane over palladium catalysts: effect of the support.

PubMed

Escandón, Lara S; Ordóñez, Salvador; Vega, Aurelio; Díez, Fernando V

2005-01-01

This work is focused on the deep catalytic oxidation of methane over supported palladium catalysts. The influences of the metal loading, oxidation state of palladium, nature of supports, presence of promoters in the supports (for zirconia-based supports), and thermal stability have been studied experimentally. Catalysts were prepared by incipient wetness of commercially available supports with aqueous solutions of palladium nitrate. For gamma-alumina support, it was observed that the optimal amount of palladium is between 0.5% and 2%, with higher amounts leading to a loss in specific activity. Concerning the oxidation state of the catalyst, it is concluded that for all the supports tested in the present work, a reduction of the catalyst is not needed, yielding the same conversion at steady state catalysts reduced and oxidised. The thermal stability of various supported catalysts were also studied, zirconia supports being the most active. These supports, specially Y-modified zirconia support, do not suffer appreciable deactivation below 500 degrees C.

In Situ FTIR and NMR Spectroscopic Investigations on Ruthenium-Based Catalysts for Alkene Hydroformylation.

PubMed

Kubis, Christoph; Profir, Irina; Fleischer, Ivana; Baumann, Wolfgang; Selent, Detlef; Fischer, Christine; Spannenberg, Anke; Ludwig, Ralf; Hess, Dieter; Franke, Robert; Börner, Armin

2016-02-18

Homogeneous ruthenium complexes modified by imidazole-substituted monophosphines as catalysts for various highly efficient hydroformylation reactions were characterized by in situ IR spectroscopy under reaction conditions and NMR spectroscopy. A proper protocol for the preformation reaction from [Ru3 (CO)12] is decisive to prevent the formation of inactive ligand-modified polynuclear complexes. During catalysis, ligand-modified mononuclear ruthenium(0) carbonyls were detected as resting states. Changes in the ligand structure have a crucial impact on the coordination behavior of the ligand and consequently on the catalytic performance. The substitution of CO by a nitrogen atom of the imidazolyl moiety in the ligand is not a general feature, but it takes place when structural prerequisites of the ligand are fulfilled. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced development of a catalyst chamber for the decomposition of up to 1.0 kg/s hydrogen peroxide

NASA Astrophysics Data System (ADS)

Božić, Ognjan; Porrmann, Dennis; Lancelle, Daniel; May, Stefan

2016-06-01

A new innovative hybrid rocket engine concept is developed within the AHRES program of the German Aerospace Center (DLR). This rocket engine based on hydroxyl-terminated polybutadiene (HTPB) with metallic additives as solid fuel and high test peroxide (HTP) as liquid oxidizer. Instead of a conventional ignition system, a catalyst chamber with a silver mesh catalyst is designed to decompose the HTP. The newly modified catalyst chamber is able to decompose up to 1.0 kg/s of 87.5 wt% HTP. Used as a monopropellant thruster, this equals an average thrust of 1600 N. The catalyst chamber is designed using the self-developed software tool SHAKIRA. The applied kinetic law, which determines catalytic decomposition of HTP within the catalyst chamber, is given and commented. Several calculations are carried out to determine the appropriate geometry for complete decomposition with a minimum of catalyst material. A number of tests under steady state conditions are carried out, using 87.5 wt% HTP with different flow rates and a constant amount of catalyst material. To verify the decomposition, the temperature is measured and compared with the theoretical prediction. The experimental results show good agreement with the results generated by the design tool. The developed catalyst chamber provides a simple, reliable ignition system for hybrid rocket propulsion systems based on hydrogen peroxide as oxidizer. This system is capable for multiple reignition. The developed hardware and software can be used to design full scale monopropellant thrusters based on HTP and catalyst chambers for hybrid rocket engines.

Synthesis and reactivity of ultra-fine coal liquefaction catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Linehan, J.C.; Matson, D.W.; Fulton, J.L.

1992-10-01

The Pacific Northwest Laboratory is currently developing ultra-fine iron-based coal liquefaction catalysts using two new particle production technologies: (1) modified reverse micelles (MRM) and (2) rapid thermal decomposition of solutes (RTDS). These methodologies have been shown to allow control over both particle size (from 1 nm to 60 nm) and composition when used to produce ultra-fine iron-based materials. Powders produced using these methods are found to be selective catalysts for carbon-carbon bond scission using the naphthyl bibenzylmethane model compound, and to promote the production of THF soluble coal products during liquefaction studies. This report describes the materials produced by bothmore » MRM and the RTDS methods and summarizes the results of preliminary catalysis studies using these materials.« less

Removal of free fatty acid in Azadirachta indica (Neem) seed oil using phosphoric acid modified mordenite for biodiesel production.

PubMed

SathyaSelvabala, Vasanthakumar; Varathachary, Thiruvengadaravi Kadathur; Selvaraj, Dinesh Kirupha; Ponnusamy, Vijayalakshmi; Subramanian, Sivanesan

2010-08-01

In this study free fatty acids present in Azadirachta indica (Neem) oil were esterified with our synthesized phosphoric acid modified catalyst. During the esterification, the acid value was reduced from 24.4 to 1.8 mg KOH/g oil. Synthesized catalyst was characterized by NH(3) TPD, XRD, SEM, FTIR and TGA analysis. During phosphoric acid modification hydrophobic character and weak acid sites of the mordenite were increased, which lead to better esterification when compared to H-mordenite. A kinetic study demonstrates that the esterification reaction followed pseudo-first order kinetics. Thermodynamic studies were also done based on the Arrhenius model. (c) 2010 Elsevier Ltd. All rights reserved.

Selective dehydration of bio-ethanol to ethylene catalyzed by lanthanum-phosphorous-modified HZSM-5: influence of the fusel.

PubMed

Hu, Yaochi; Zhan, Nina; Dou, Chang; Huang, He; Han, Yuwang; Yu, Dinghua; Hu, Yi

2010-11-01

Bio-ethanol dehydration to ethylene is an attractive alternative to oil-based ethylene. The influence of fusel, main byproducts in the fermentation process of bio-ethanol production, on the bio-ethanol dehydration should not be ignored. We studied the catalytic dehydration of bio-ethanol to ethylene over parent and modified HZSM-5 at 250°C, with weight hourly space velocity (WHSV) equal to 2.0/h. The influences of a series of fusel, such as isopropanol, isobutanol and isopentanol, on the ethanol dehydration over the catalysts were investigated. The 0.5%La-2%PHZSM-5 catalyst exhibited higher ethanol conversion (100%), ethylene selectivity (99%), and especially enhanced stability (more than 70 h) than the parent and other modified HZSM-5. We demonstrated that the introduction of lanthanum and phosphorous to HZSM-5 could weaken the negative influence of fusel on the formation of ethylene. The physicochemical properties of the catalysts were characterized by ammonia temperature-programmed desorption (NH(3)-TPD), nitrogen adsorption and thermogravimetry (TG)/differential thermogravimetry (DTG)/differential thermal analysis (DTA) (TG/DTG/DTA) techniques. The results indicated that the introduction of lanthanum and phosphorous to HZSM-5 could inhibit the formation of coking during the ethanol dehydration to ethylene in the presence of fusel. The development of an efficient catalyst is one of the key technologies for the industrialization of bio-ethylene.

Enhancement of biodiesel synthesis from soybean oil by potassium fluoride modification of a calcium magnesium oxides catalyst.

PubMed

Fan, Mingming; Zhang, Pingbo; Ma, Qinke

2012-01-01

Transesterification of soybean oil with methanol was carried out in the presence of CaO-MgO and KF-modified CaO-MgO catalysts at atmospheric pressure. While the methyl ester yield for the CaO-MgO catalyst with a ratio of 8:2 (CaO:MgO) was 63.6%, it was 97.9% for the KF-modified catalyst at a 2% catalyst to the reactants (methanol/oil mixture) weight ratio, a temperature of 65 °C, a methanol-soybean oil ratio of 9:1 and a reaction time of 2.5 h. The KF/CaO-MgO catalyst still yielded 86.7% after four successive uses. The catalytic performance of the KF/CaO-MgO catalyst was attributed to the formation of active KCaF(3) and K(2)MgF(4) centers. Copyright © 2011 Elsevier Ltd. All rights reserved.

Efficiency of bimetallic PtPd on polydopamine modified on various carbon supports for alcohol oxidations

NASA Astrophysics Data System (ADS)

Pinithchaisakula, A.; Ounnunkad, K.; Themsirimongkon, S.; Promsawan, N.; Waenkaew, P.; Saipanya, S.

2017-02-01

In this work, the preparation, characterization, and electrocatalytic analysis of the catalysts on various carbon substrates for direct alcohol fuel cells were studied. Selected carbons were modified with/without polydopamine (labelled as PDA-C and C) and further metal electrodeposited incorporated onto the glassy carbon (labelled as 5Pt1Pd/PDA-C and 5Pt1Pd/C). Four various carbon materials were used e.g. graphite (G), carbon nanotube (CNT), graphene (GP) and graphene oxide (GO) and the carbons were modified with PDA denoted as PDA-G, PDA-CNT, PDA-GP and PDA-GO, respectively. The transmission electron microscopy (TEM) and scanning electron microscopy (SEM) experimental observation showed narrow size distribution of metal anchored on the PDA-C and C materials. Chemical compositions and oxidation states of the catalysts were determined by X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDX). The catalytic performances for small organic electro-oxidation (e.g. methanol and ethanol) were measured by cyclic voltammetry (CV). Among different PDA-C and C catalysts, monometallic Pt showed less activity than the bimetallic catalysts. Among catalysts with PDA, the 5Pt1Pd/PDA-GO catalyst facilitated methanol and ethanol oxidations with high oxidation currents and If/Ib value and stability with low potentials while among catalysts without PDA, the 5Pt1Pd/CNT provides highest activity and stability. It was found that the catalysts with PDA provided high activity and stability than the catalysts without PDA. The improved catalytic performance of the prepared catalysts could be related to the higher active surface area from polymer modification and bimetallic catalyst system in the catalyst composites.

Platinum and palladium nano-structured catalysts for polymer electrolyte fuel cells and direct methanol fuel cells.

PubMed

Long, Nguyen Viet; Thi, Cao Minh; Yong, Yang; Nogami, Masayuki; Ohtaki, Michitaka

2013-07-01

In this review, we present the synthesis and characterization of Pt, Pd, Pt based bimetallic and multi-metallic nanoparticles with mixture, alloy and core-shell structure for nano-catalysis, energy conversion, and fuel cells. Here, Pt and Pd nanoparticles with modified nanostructures can be controllably synthesized via chemistry and physics for their uses as electro-catalysts. The cheap base metal catalysts can be studied in the relationship of crystal structure, size, morphology, shape, and composition for new catalysts with low cost. Thus, Pt based alloy and core-shell catalysts can be prepared with the thin Pt and Pt-Pd shell, which are proposed in low and high temperature proton exchange membrane fuel cells (PEMFCs), and direct methanol fuel cells (DMFCs). We also present the survey of the preparation of Pt and Pd based catalysts for the better catalytic activity, high durability, and stability. The structural transformations, quantum-size effects, and characterization of Pt and Pd based catalysts in the size ranges of 30 nm (1-30 nm) are presented in electro-catalysis. In the size range of 10 nm (1-10 nm), the pure Pt catalyst shows very large surface area for electro-catalysis. To achieve homogeneous size distribution, the shaped synthesis of the polyhedral Pt nanoparticles is presented. The new concept of shaping specific shapes and morphologies in the entire nano-scale from nano to micro, such as polyhedral, cube, octahedra, tetrahedra, bar, rod, and others of the nanoparticles is proposed, especially for noble and cheap metals. The uniform Pt based nanosystems of surface structure, internal structure, shape, and morphology in the nanosized ranges are very crucial to next fuel cells. Finally, the modifications of Pt and Pd based catalysts of alloy, core-shell, and mixture structures lead to find high catalytic activity, durability, and stability for nano-catalysis, energy conversion, fuel cells, especially the next large-scale commercialization of next PEMFCs, and DMFCs.

Enhanced hydrothermal stability of Cu-ZSM-5 catalyst via surface modification in the selective catalytic reduction of NO with NH3

NASA Astrophysics Data System (ADS)

Zhang, Tao; Shi, Juan; Liu, Jian; Wang, Daxi; Zhao, Zhen; Cheng, Kai; Li, Jianmei

2016-07-01

The surface of Cu-ZSM-5 catalyst was modified by chemical liquid deposition (CLD) of tetraethoxysilane (TEOS) for enhancing its hydrothermal stability in the selective catalytic reduction of NO with NH3. After hydrothermal aging at 750 °C for 13 h, the catalytic performance of Cu-ZSM-5-Aged catalyst was significantly reduced for NO reduction in the entire temperature range, while that of Cu-ZSM-5-CLD-Aged catalyst was affected very little. The characterization results indicated that an inert silica layer was deposited on the surface of Cu-ZSM-5 and formed a protective layer, which prevents the detachment of Cu2+ from ZSM-5 ion-exchange positions and the dealumination of zeolite during the hydrothermal aging process. Based on the data it is hypothesized to be the primary reason for the high hydrothermal stability of Cu-ZSM-5-CLD catalyst.

Acid treatment and formation of MnWO4 belts for NH3-SCR performance of MnWOx/TiO2 catalysts

NASA Astrophysics Data System (ADS)

Zhang, Zekai; Lu, Weizhe; Zhang, Xinying; Liu, Huayan; Lu, Hanfeng

2018-06-01

NH3-SCR is an important technology to remove NOx, and non-V based catalysts development is still a hot topic in the field. To improve N2 selectivity, acid treatment was carried out to modify the properties of a MnWOx/TiO2 catalyst. Influences of acid concentration, time and temperature on the catalyst were investigated. The TEM results showed that the acid treatment removed more MnO2 species than Mn2O3 and MnWO4 and disclosed more crystal faces of the active species. The active species even formed hollow structures by Ostwald ripening mechanism, which was then corroded by acid to form the nanobelts on the surface. The working temperature window of the MnWOx/TiO2 catalyst was thereby moved to the high temperature attitude and the N2 selectivity is clearly improved.

New catalysts for coal liquefaction and new nanocrystalline catalysts synthesis methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Linehan, J.C.; Matson, D.W.; Darab, J.G.

1994-09-01

The use of coal as a source of transportation fuel is currently economically unfavorable due to an abundant world petroleum supply and the relatively high cost of coal liquefaction. Consequently, a reduction in the cost of coal liquefaction, for example by using less and/or less costly catalysts or lower liquefaction temperatures, must be accomplished if coal is to play an significant role as a source of liquid feedstock for the petrochemical industry. The authors and others have investigated the applicability of using inexpensive iron-based catalysts in place of more costly and environmentally hazardous metal catalysts for direct coal liquefaction. Iron-basedmore » catalysts can be effective in liquefying coal and in promoting carbon-carbon bond cleavage in model compounds. The authors have been involved in an ongoing effort to develop and optimize iron-based powders for use in coal liquefaction and related petrochemical applications. Research efforts in this area have been directed at three general areas. The authors have explored ways to optimize the effectiveness of catalyst precursor species through use of nanocrystalline materials and/or finely divided powders. In this effort, the authors have developed two new nanophase material production techniques, Modified Reverse Micelle (MRM) and the Rapid Thermal Decomposition of precursors in Solution (RTDS). A second effort has been aimed at optimizing the effectiveness of catalysts by variations in other factors. To this, the authors have investigated the effect that the crystalline phase has on the capacity of iron-based oxide and oxyhydroxide powders to be effectively converted to an active catalyst phase under liquefaction conditions. And finally, the authors have developed methods to produce active catalyst precursor powders in quantities sufficient for pilot-scale testing. Major results in these three areas are summarized.« less

Origin of Multiple Peaks in the Potentiodynamic Oxidation of CO Adlayers on Pt and Ru-Modified Pt Electrodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Hongsen; Abruña, Héctor D.

2015-05-21

The study of the electrooxidation mechanism of COad on Pt based catalysts is very important for designing more effective CO-tolerant electrocatalysts for fuel cells. We have studied the origin of multiple peaks in the cyclic voltammograms of CO stripping from polycrystalline Pt and Ru modified polycrystalline Pt (Pt/Ru) surfaces in both acidic and alkaline media by differential electrochemical mass spectrometry (DEMS), DFT calculations, and kinetic Monte Carlo (KMC) simulations. A new COad electrooxidation kinetic model on heterogeneous Pt and Pt/Ru catalysts is proposed to account for the multiple peaks experimentally observed. In this model, OH species prefer to adsorb atmore » low-coordination sites or Ru sites and, thus, suppress CO repopulation from high-coordination sites onto these sites. Therefore, COad oxidation occurs on different facets or regions, leading to multiplicity of CO stripping peaks. This work provides a new insight into the CO electrooxidation mechanism and kinetics on heterogeneous catalysts.« less

Synthesis and characterization of mangenese(III) porphyrin supported on imidazole modified chloromethylated MIL-101(Cr): A heterogeneous and reusable catalyst for oxidation of hydrocarbons with sodium periodate

NASA Astrophysics Data System (ADS)

Zadehahmadi, Farnaz; Tangestaninejad, Shahram; Moghadam, Majid; Mirkhani, Valiollah; Mohammadpoor-Baltork, Iraj; Khosropour, Ahmad R.; Kardanpour, Reihaneh

2014-10-01

In the present work, chloromethylated MIL-101(Cr) modified with imidazole, Im-MIL-101, was applied as a support for immobilizing of tetraphenylporphyrinatomangenese(III) chloride. The imidazole-bound MIL-101, Im-MIL-101, not only used as support for immobilization of manganese porphyrin but also applied as a heterogeneous axial base. The Mn(TPP)Cl@Im-MIL-101 catalyst was characterized by UV-vis, FT-IR, X-ray diffraction (XRD), N2 adsorption, field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray (EDX), elemental analysis and inductively coupled plasma (ICP) methods. The catalytic activity of this new catalytic system was investigated in the alkene epoxidation and alkane hydroxylation using NaIO4 as an oxidant in CH3CN/H2O at room temperature. This heterogeneous catalyst is highly efficient, stable and reusable in the oxidation of hydrocarbons.

Biodiesel production from rice bran oil by transesterification using heterogeneous catalyst natural zeolite modified with K2CO3

NASA Astrophysics Data System (ADS)

Taslim; Iriany; Bani, O.; Parinduri, S. Z. D. M.; Ningsih, P. R. W.

2018-02-01

In the present study, an effort had been made to use natural zeolite from Tapanuli Utara, North Sumatera as a potential catalyst for biodiesel production. Biodiesel production is usuallythrough transesterification, and a catalyst is employed to improve reaction rate and yield. In this research rice bran oil (RBO) was used as feedstock. The objective of this work was to discover the effectiveness of natural zeolite modified by K2CO3 as catalysts in biodiesel production from RBO. K2CO3/natural zeolite catalyst modification was by impregnation method at various K2CO3 concentrations followed by drying and calcination. Transesterification was conducted at 65°C and 500 rpm. Effect of process variables such as the amount of catalyst, reaction time, and the molar ratio of methanol to RBO was investigated.The maximum yield of 98.18% biodiesel was obtained by using 10:1 molar ratio of methanol to RBO at a reaction time of 3 hours in the presence of 4 w% catalyst. The obtained biodiesel was then characterized by its density, viscosity and ester content. The biodiesel properties met the Indonesia standard (SNI).The results showed that natural zeolite modified by K2CO3 was suitable as a catalyst in the synthesis of biodiesel through transesterification from RBO.

DeNOx Abatement over Sonically Prepared Iron-Substituted Y, USY and MFI Zeolite Catalysts in Lean Exhaust Gas Conditions

PubMed Central

Stachurska, Patrycja; Kuterasiński, Łukasz; Dziedzicka, Anna; Górecka, Sylwia; Chmielarz, Lucjan; Łojewska, Joanna; Sitarz, Maciej

2018-01-01

Iron-substituted MFI, Y and USY zeolites prepared by two preparation routes—classical ion exchange and the ultrasound modified ion-exchange method—were characterised by micro-Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and ultraviolet (UV)/visible diffuse reflectance spectroscopy (UV/Vis DRS). Ultrasound irradiation, a new technique for the preparation of the metal salt suspension before incorporation to the zeolite structure, was employed. An experimental study of selective catalytic reduction (SCR) of NO with NH3 on both iron-substituted reference zeolite catalysts and those prepared through the application of ultrasound conducted during an ion-exchange process is presented. The prepared zeolite catalysts show high activity and selectivity in SCR deNOx abatement. The MFI-based iron catalysts, especially those prepared via the sonochemical method, revealed superior activity in the deNOx process, with almost 100% selectivity towards N2. The hydrothermal stability test confirmed high stability and activity of MFI-based catalysts in water-rich conditions during the deNOx reaction at 450 °C. PMID:29301370

Investigating the effects of alkali metal Na addition on catalytic activity of HZSM-5 for methyl mercaptan elimination

NASA Astrophysics Data System (ADS)

Yu, Jie; He, Dedong; Chen, Dingkai; Liu, Jiangping; Lu, Jichang; Liu, Feng; Liu, Pan; Zhao, Yutong; Xu, Zhizhi; Luo, Yongming

2017-10-01

Na-modified HZSM-5 catalysts with different Na loading amounts were prepared by incipient-wetness impregnation method and their catalytic activities for methyl mercaptan catalytic elimination were analyzed. XRD, N2 adsorption-desorption, NH3-TPD, CO2-TPD and FT-IR measurements were carried out to investigate the effects of modification of alkali metal Na on the physicochemical properties of the HZSM-5 zeolite catalyst. Research results illustrated that the introduction of alkali metal Na can improve catalytic activity for CH3SH catalytic elimination. CH3SH can be almost completely converted over 3%-Na/HZSM-5 at 450 °C compared to pure HZSM-5 at 600 °C based on our experimental results and the results from previous research. The improved catalytic activity could be attributed to the regulated acid-base properties of the HZSM-5 catalysts by doping with alkali metal Na. High alkali concentration treatment, however, may destroy the framework structure of the catalyst sample, thus causing the poor stability performance of the obtained catalyst.

DOE Office of Scientific and Technical Information (OSTI.GOV)

James K. Neathery; Gary Jacobs; Burtron H. Davis

In this reporting period, a fundamental filtration study was started to investigate the separation of Fischer-Tropsch Synthesis (FTS) liquids from iron-based catalyst particles. Slurry-phase FTS in slurry bubble column reactor systems is the preferred mode of production since the reaction is highly exothermic. Consequently, heavy wax products must be separated from catalyst particles before being removed from the reactor system. Achieving an efficient wax product separation from iron-based catalysts is one of the most challenging technical problems associated with slurry-phase FTS. The separation problem is further compounded by catalyst particle attrition and the formation of ultra-fine iron carbide and/or carbonmore » particles. Existing pilot-scale equipment was modified to include a filtration test apparatus. After undergoing an extensive plant shakedown period, filtration tests with cross-flow filter modules using simulant FTS wax slurry were conducted. The focus of these early tests was to find adequate mixtures of polyethylene wax to simulate FTS wax. Catalyst particle size analysis techniques were also developed. Initial analyses of the slurry and filter permeate particles will be used by the research team to design improved filter media and cleaning strategies.« less

Effects of Activated Carbon Surface Property on Structure and Activity of Ru/AC Catalysts

NASA Astrophysics Data System (ADS)

Xu, S. K.; Li, L. M.; Guo, N. N.

2018-05-01

The activated carbon (AC) was modified by supercritical (SC) methanol, HNO3 oxidation, or HNO3 oxidation plus SC methanol, respectively. Then, the original and the modified AC were used as supports for Ru/AC catalysts prepared via the impregnation method. The results showed that the SC methanol modification decreased the content of surface acidic groups of AC. While HNO3 oxidation displayed the opposite behavior. Furthermore, the dispersion of ruthenium and the activity of catalysts were highly dependent on the content of surface acidic groups, and the SC methanol modified sample exhibited the highest activity for hydrogenation of glucose.

Enhanced activity and stability of copper oxide/γ-alumina catalyst in catalytic wet-air oxidation: Critical roles of cerium incorporation

NASA Astrophysics Data System (ADS)

Zhang, Yongli; Zhou, Yanbo; Peng, Chao; Shi, Junjun; Wang, Qingyu; He, Lingfeng; Shi, Liang

2018-04-01

By successive impregnation method, the Ce-modified Cu-O/γ-Al2O3 catalyst was prepared and characterized using nitrogen adsorption-desorption, scanning electron microscopy energy dispersive X-ray analysis (SEM-EDS), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman, and H2-Temperature programming reduction (H2-TPR). In catalytic wet-air oxidation (CWAO) process for the printing and dyeing wastewater (PDW), the effects of Ce addition on performance, mechanism and kinetics of the catalyst were investigated. The Ce addition increases the Brunauer-Emmett-Teller (BET) surface area and pore volume of the catalyst and makes the active components uniformly distributed on the catalyst surface. Formation of a stable CuAl2O4 solid solution by anchoring Cu onto the γ-Al2O3 crystal lattice leads to a significant decrease in metal leaching of the Ce-modified catalyst. The proportion of lattice oxygen in the catalyst substantially increases and the apparent activation energy of Cu-O/γ-Al2O3 catalyst decreases owing to Ce addition. Therefore, the catalytic activity and stability of the Ce-modified catalyst are considerably improved. The scavengers experiments identify the active species existed in the CWAO reaction system, with the order of reactivity: h+ > O2•- > H2O2 > HO•. This novel Cu-Ce-O/γ-Al2O3 catalyst has great potential in applications for treatment of concentrated organic wastewater due to its superior catalytic activity and improved stability.

Methanol electro-oxidation on platinum modified tungsten carbides in direct methanol fuel cells: a DFT study.

PubMed

Sheng, Tian; Lin, Xiao; Chen, Zhao-Yang; Hu, P; Sun, Shi-Gang; Chu, You-Qun; Ma, Chun-An; Lin, Wen-Feng

2015-10-14

In exploration of low-cost electrocatalysts for direct methanol fuel cells (DMFCs), Pt modified tungsten carbide (WC) materials are found to be great potential candidates for decreasing Pt usage whilst exhibiting satisfactory reactivity. In this work, the mechanisms, onset potentials and activity for electrooxidation of methanol were studied on a series of Pt-modified WC catalysts where the bare W-terminated WC(0001) substrate was employed. In the surface energy calculations of a series of Pt-modified WC models, we found that the feasible structures are mono- and bi-layer Pt-modified WCs. The tri-layer Pt-modified WC model is not thermodynamically stable where the top layer Pt atoms tend to accumulate and form particles or clusters rather than being dispersed as a layer. We further calculated the mechanisms of methanol oxidation on the feasible models via methanol dehydrogenation to CO involving C-H and O-H bonds dissociating subsequently, and further CO oxidation with the C-O bond association. The onset potentials for the oxidation reactions over the Pt-modified WC catalysts were determined thermodynamically by water dissociation to surface OH* species. The activities of these Pt-modified WC catalysts were estimated from the calculated kinetic data. It has been found that the bi-layer Pt-modified WC catalysts may provide a good reactivity and an onset oxidation potential comparable to pure Pt and serve as promising electrocatalysts for DMFCs with a significant decrease in Pt usage.

In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60 Fullerenes.

PubMed

Martínez, Juan Pablo; Vummaleti, Sai Vikrama Chaitanya; Falivene, Laura; Nolan, Steven P; Cavallo, Luigi; Solà, Miquel; Poater, Albert

2016-05-04

Density functional theory calculations have been used to explore the potential of Ru-based complexes with 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) ligand backbone (A) being modified in silico by the insertion of a C60 molecule (B and C), as olefin metathesis catalysts. To this end, we investigated the olefin metathesis reaction catalyzed by complexes A, B, and C using ethylene as the substrate, focusing mainly on the thermodynamic stability of all possible reaction intermediates. Our results suggest that complex B bearing an electron-withdrawing N-heterocyclic carbene improves the performance of unannulated complex A. The efficiency of complex B is only surpassed by complex A when the backbone of the N-heterocyclic carbene of complex A is substituted by two amino groups. The particular performance of complexes B and C has to be attributed to electronic factors, that is, the electronic-donating capacity of modified SIMes ligand rather than steric effects, because the latter are predicted to be almost identical for complexes B and C when compared to those of A. Overall, this study indicates that such Ru-based complexes B and C might have the potential to be effective olefin metathesis catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modified chiral triazolium salts for enantioselective benzoin cyclization of enolizable keto-aldehydes: synthesis of (+)-sappanone B.

PubMed

Takikawa, Hiroshi; Suzuki, Keisuke

2007-07-05

Asymmetric synthesis of (+)-sappanone B (1), a natural product with a 3-hydroxy chromanone structure, was achieved via enantioselective benzoin cyclization by using a modified Rovis catalyst and triethylamine. This catalyst enabled the successful benzoin cyclization of readily enolizable keto-aldehydes.

Photoelectrochemical Performance of the Ag(III)-Based Oxygen-Evolving Catalyst.

PubMed

Sordello, Fabrizio; Ghibaudo, Manuel; Minero, Claudio

2017-07-19

We report the electrosynthesis of a water oxidation catalyst based on Ag oxides (AgCat). The deposited AgCat is composed of mixed valence crystalline Ag oxides with the presence of particle aggregates whose size is ∼1 μm. This catalyst, coupled with TiO 2 and hematite, and under photoelectrochemical conditions, substantially increases photocurrents in a wide range of applied potentials compared with bare and Co-Pi-modified photocatalysts. AgCat can sustain current densities comparable with other water oxidation catalysts. Dark bulk electrolysis demonstrated that AgCat is stable and can sustain high turnover number in operative conditions. Oxygen evolution from water occurs in mild conditions: pH = 2-13, room temperature and pressure, and moderate overpotentials (600 mV) compatible with the coupling with semiconducting oxides as sensitizers. Using hematite in sustained electrolysis O 2 production is significant, both in the dark and under irradiation, after an initial slow induction time in which modification of surface species occurs.

Relevance of the Interaction between the M-Phthalocyanines and Carbon Nanotubes in the Electroactivity toward ORR.

PubMed

González-Gaitán, Carolina; Ruiz-Rosas, Ramiro; Morallón, Emilia; Cazorla-Amorós, Diego

2017-10-31

In this work, the influence of the interaction between the iron and cobalt-phthalocyanines (FePc and CoPc) and carbon nanotubes (CNTs) used as support in the electroactivity toward oxygen reduction reaction (ORR) in alkaline media has been investigated. A series of thermal treatments were performed on these materials in order to modify the interaction between the CNTs and the phthalocyanines. The FePc-based catalysts showed the highest activity, with comparable performance to the state-of-the-art Pt-Vulcan catalyst. A heat treatment at 400 °C improved the activity of FePc-based catalysts, while the use of higher temperatures or oxidative atmosphere rendered the decomposition of the macrocyclic compound and consequently the loss of the electrochemical activity of the complex. CoPc-based catalysts performance was negatively affected for all of the tested treatments. Thermogravimetric analyses demonstrated that the FePc was stabilized when loaded onto CNTs, while CoPc did not show such a feature, pointing to a better interaction of the FePc instead of the CoPc. Interestingly, electrochemical measurements demonstrated an improvement of the electron transfer rate in thermally treated FePc-based catalysts. They also allowed us to assess that only 15% of the iron in the catalyst was available for direct electron transfer. This is the same iron amount that remains on the catalyst after a strong acid washing with concentrated HCl (ca. 0.3 wt %), which is enough to deliver a comparable ORR activity. Durability tests confirmed that the catalysts deactivation occurs at a slower rate in those catalysts where FePc is strongly attached to the CNT surface. Thus, the highest ORR activity seems to be provided by those FePc molecules that are strongly attached to the CNT surface, pointing out the relevance of the interaction between the support and the FePc in these catalysts.

Advanced cathode materials for polymer electrolyte fuel cells based on pt/ metal oxides: from model electrodes to catalyst systems.

PubMed

Fabbri, Emiliana; Pătru, Alexandra; Rabis, Annett; Kötz, Rüdiger; Schmidt, Thomas J

2014-01-01

The development of stable catalyst systems for application at the cathode side of polymer electrolyte fuel cells (PEFCs) requires the substitution of the state-of-the-art carbon supports with materials showing high corrosion resistance in a strongly oxidizing environment. Metal oxides in their highest oxidation state can represent viable support materials for the next generation PEFC cathodes. In the present work a multilevel approach has been adopted to investigate the kinetics and the activity of Pt nanoparticles supported on SnO2-based metal oxides. Particularly, model electrodes made of SnO2 thin films supporting Pt nanoparticles, and porous catalyst systems made of Pt nanoparticles supported on Sb-doped SnO2 high surface area powders have been investigated. The present results indicate that SnO2-based supports do not modify the oxygen reduction reaction mechanism on the Pt nanoparticle surface, but rather lead to catalysts with enhanced specific activity compared to Pt/carbon systems. Different reasons for the enhancement in the specific activity are considered and discussed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chu, C.C.

A process is described of dehydrogenating para-ethyltoluene to selectively form para-methylstyrene comprising contacting to para-ethyltoluene under dehydrogenation reaction conditions with a catalyst composition comprising: (a) from about 30% to 60% by weight of iron oxide, calculated as ferric oxide; (b) from about 13% to 48% by weight of a potassium compound, calculated as potassium oxide; and (c) from about 0% to 5% by weight of a chromium compound, calculated as chromic oxide. The improvement is described comprising dehydrogenating the para-ethyltoluene with a catalyst composition comprising, in addition to the components (a), (b) and (c), a modifying component (d) capable ofmore » rendering the para-methylstyrene-containing dehydrogenation reaction effluent especially resistant to the subsequent formation of popcorn polymers when the dehydrogenation of para-ethyltoluene is conducted over the modified catalyst, the modifying component (d) being a bismuth compound present to the extent of from about 1% to 20% by weight of the catalyst composition, calculated as bismuth trioxide.« less

Engineering the internal surfaces of three-dimensional nanoporous catalysts by surfactant-modified dealloying.

PubMed

Wang, Zhili; Liu, Pan; Han, Jiuhui; Cheng, Chun; Ning, Shoucong; Hirata, Akihiko; Fujita, Takeshi; Chen, Mingwei

2017-10-20

Tuning surface structures by bottom-up synthesis has been demonstrated as an effective strategy to improve the catalytic performances of nanoparticle catalysts. Nevertheless, the surface modification of three-dimensional nanoporous metals, fabricated by a top-down dealloying approach, has not been achieved despite great efforts devoted to improving the catalytic performance of three-dimensional nanoporous catalysts. Here we report a surfactant-modified dealloying method to tailor the surface structure of nanoporous gold for amplified electrocatalysis toward methanol oxidation and oxygen reduction reactions. With the assistance of surfactants, {111} or {100} faceted internal surfaces of nanoporous gold can be realized in a controllable manner by optimizing dealloying conditions. The surface modified nanoporous gold exhibits significantly enhanced electrocatalytic activities in comparison with conventional nanoporous gold. This study paves the way to develop high-performance three-dimensional nanoporous catalysts with a tunable surface structure by top-down dealloying for efficient chemical and electrochemical reactions.

Catalyst recycling via specific non-covalent adsorption on modified silicas.

PubMed

Kluwer, Alexander M; Simons, Chretien; Knijnenburg, Quinten; van der Vlugt, Jarl Ivar; de Bruin, Bas; Reek, Joost N H

2013-03-14

This article describes a new strategy for the recycling of a homogeneous hydroformylation catalyst, by selective adsorption of the catalyst to tailor-made supports after a batchwise reaction. The separation of the catalyst from the product mixture is based on selective non-covalent supramolecular interactions between a ligand and the support. Changing the solvent releases the active catalyst back into the reactor and allows a subsequent batch reaction with the recycled active catalyst. For this purpose, the bidentate NixantPhos ligand has been equipped with a pyridine group. The corresponding rhodium pre-catalyst [Rh(Nix-py)(acac)] (acac = acetylacetonate) forms a very selective, active and highly stable catalyst, and able to reach a turnover number (TON) of 170 000 in a single run (reaction performed in nearly neat 1-octene, S/C ratio of 200 000, at 140 °C, 20 bars syngas pressure). Various commercially available supports have been explored in binding studies and recycling experiments. The end-capped silica-alumina performs the best so far with respect to ligand-adsorbing properties for the current purpose. Although this system has not been fully optimized, four recycling runs could be performed successfully.

Visible light-driven water oxidation promoted by host-guest interaction between photosensitizer and catalyst with a high quantum efficiency.

PubMed

Li, Hua; Li, Fei; Zhang, Biaobiao; Zhou, Xu; Yu, Fengshou; Sun, Licheng

2015-04-08

A highly active supramolecular system for visible light-driven water oxidation was developed with cyclodextrin-modified ruthenium complex as the photosensitizer, phenyl-modified ruthenium complexes as the catalysts, and sodium persulfate as the sacrificial electron acceptor. The catalysts were found to form 1:1 host-guest adducts with the photosensitizer. Stopped-flow measurement revealed the host-guest interaction is essential to facilitate the electron transfer from catalyst to sensitizer. As a result, a remarkable quantum efficiency of 84% was determined under visible light irradiation in neutral aqueous phosphate buffer. This value is nearly 1 order of magnitude higher than that of noninteraction system, indicating that the noncovalent incorporation of sensitizer and catalyst is an appealing approach for efficient conversion of solar energy into fuels.

Catalytic performance of strong acid catalyst: Methyl modified SBA-15 loaded perfluorinated sulfonic acid obtained by the waste perfluorinated sulfonic acid ion exchange membrane

NASA Astrophysics Data System (ADS)

Jiang, Tingshun; Huang, Qiuyan; Li, Yingying; Fang, Minglan; Zhao, Qian

2018-02-01

Mesoporous molecular sieve (SBA-15) was modified using the trimethylchlorosilane as functional agent and the silylation SBA-15 mesoporous material was prepared in this work. The alcohol solution of perfluorinated sulfonic acid dissolved from the waste perfluorinated sulfonic acid ion exchange membrane (PFSIEM) was loaded onto the resulting mesoporous material by the impregnation method and their physicochemical properties were characterized by FT-IR, N2-physisorption, XRD, TG-DSC and TEM. The catalytic activities of these synthesized solid acid catalysts were evaluated by alkylation of phenol with tert-butyl alcohol. The influence of reaction temperature, weight hour space velocity (WHSV) and reaction time on the phenol conversion and product selectivity were assessed by means of a series of experiments. The results showed that with the increase of the active component of the catalyst, these catalysts still remained good mesoporous structure, but the mesoporous ordering decreased to some extent. These catalysts exhibited good catalytic performance for the alkylation of phenol with tert-butanol. The maximum phenol conversion of 89.3% with 70.9% selectivity to 4-t-butyl phenol (4-TBP) was achieved at 120 °C and the WHSV is 4 h-1. The methyl group was loaded on the surface of the catalyst by trimethylchlorosilane. This is beneficial to retard the deactivation of the catalyst. In this work, the alkylation of phenol with tert-butyl alcohol were carried out using the methyl modified SBA-15 mesoporous materials loaded perfluorinated sulfonic acid as catalysts. The results show that the resulting catalyst exhibited high catalytic activity.

Solid catalyzed isoparaffin alkylation at supercritical fluid and near-supercritical fluid conditions

DOEpatents

Ginosar, Daniel M.; Fox, Robert V.; Kong, Peter C.

2000-01-01

This invention relates to an improved method for the alkylation reaction of isoparaffins with olefins over solid catalysts including contacting a mixture of an isoparaffin, an olefin and a phase-modifying material with a solid acid catalyst member under alkylation conversion conditions at either supercritical fluid, or near-supercritical fluid conditions, at a temperature and a pressure relative to the critical temperature(T.sub.c) and the critical pressure(P.sub.c) of the reaction mixture. The phase-modifying phase-modifying material is employed to promote the reaction's achievement of either a supercritical fluid state or a near-supercritical state while simultaneously allowing for decreased reaction temperature and longer catalyst life.

Indirect Liquefaction of Coal-Biomass Mixture for Production of Jet Fuel with High Productivity and Selectivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gangwal, Santosh K; McCabe, Kevin

Coal to liquids (CTL) and coal-biomass to liquids (CBTL) processes were advanced by testing and demonstrating Southern Research’s sulfur tolerant nickel-based reforming catalyst and Chevron’s highly selective and active cobalt-zeolite hybrid Fischer-Tropsch (FT) catalyst to clean, upgrade and convert syngas predominantly to jet fuel range hydrocarbon liquids, thereby minimizing expensive cleanup and wax upgrading operations. The National Carbon Capture Center (NCCC) operated by Southern Company (SC) at Wilsonville, Alabama served as the host site for the gasifier slip-stream and simulated syngas testing/demonstration. Reformer testing was performed to (1) reform tar and light hydrocarbons, (2) decompose ammonia in the presence H2S,more » and (3) deliver the required H2 to CO ratio for FT synthesis. FT Testing was performed to produce a product primarily containing C5-C20 liquid hydrocarbons and no C21+ waxy hydrocarbons with productivity greater than 0.7 gC5+/g catalyst/h, and at least 70% diesel and jet fuel range (C8-C20) hydrocarbon selectivity in the liquid product. A novel heat-exchange reactor system was employed to enable the use of the highly active FT catalyst and larger diameter reactors that results in cost reduction for commercial systems. Following laboratory development and testing, SR’s laboratory reformer was modified to operate in a Class 1 Div. 2 environment, installed at NCCC, and successfully tested for 125 hours using raw syngas. The catalyst demonstrated near equilibrium reforming (~90%) of methane and complete reforming/decomposition of tar and ammonia in the presence of up to 380 ppm H2S. For FT synthesis, SR modified and utilized a bench scale skid mounted FT reactor system (SR-CBTL test rig) that was fully integrated with a slip stream from SC/NCCC’s transport gasifier (TRIG). The test-rig developed in a previous project (DE-FE0010231) was modified to receive up to 7.5 lb/h raw syngas augmented with bottled syngas to adjust the H2/CO molar ratio to 2, clean it to cobalt FT catalyst specifications, and produce liquid FT products at the design capacity of up to 6 L/day. Promising Chevron catalyst candidates in the size range from 70-200 μm were loaded onto SR’s 2-inch ID and 4-inch ID bench-scale reactors utilizing IntraMicron’s micro-fiber entrapped catalyst (MFEC) heat exchange reactor technology. During 2 test campaigns, the FT reactors were successfully demonstrated at NCCC using syngas for ~420 hours. The catalyst did not experience deactivation during the tests. SR’s thermo-syphon heat removal system maintained reactor operating temperature along the axis to within ±4 °C. The experiments gave a steady catalyst productivity of 0.7-0.8 g/g catalyst/h, liquid hydrocarbon selectivity of ~75%, and diesel and jet fuel range hydrocarbon selectivity in the liquid product as high as 85% depending on process conditions. A preliminary techno-economic evaluation showed that the SR technology-based 50,000 bpd plant had a 10 % lower total plant cost compared to a conventional slurry reactor based plant. Furthermore, because of the modular nature of the SR technology, it was shown that the total plant cost advantage increases to >35 % as the plant is scaled down to 1000 bpd.« less

Supported organometallic catalysts for hydrogenation and Olefin Polymerization

DOEpatents

Marks, Tobin J.; Ahn, Hongsang

2001-01-01

Novel heterogeneous catalysts for the which hydrogenation of olefins and arenes with high conversion rates under ambient conditions and the polymerization of olefins have been developed. The catalysts are synthesized from Ziegler-type precatalysts by supporting them on sulfate-modified zirconia.

Protein tetrazinylation via diazonium coupling for covalent and catalyst-free bioconjugation.

PubMed

Zhang, Jie; Men, Yuwen; Lv, Shanshan; Yi, Long; Chen, Jian-Feng

2015-12-21

An efficient and bench-stable reagent was synthesized for direct and covalent introduction of tetrazines onto target protein or virus surfaces, which can be further modified based on tetrazine-ene ligation to achieve fluorescence labelling or PEGylation under mild conditions.

Fischer-Tropsch Synthesis: XANES Investigation of Hydrogen Chloride Poisoned Iron and Cobalt-Based Catalysts at the K-Edges of Cl, Fe, and Co

DOE PAGES

Pendyala, Venkat Ramana Rao; Jacobs, Gary; Ma, Wenping; ...

2016-07-23

The effect of co-fed hydrogen chloride (HCl) in syngas on the performance of iron and cobalt-based Fischer-Tropsch (FT) catalysts was investigated in our earlier studies [ACS Catal. 5 (2015) 3124-3136 and DOE final report 2011; Catal. Lett. 144 (2014) 1127-1133]. For an iron catalyst, lower HCl concentrations (< 2.0 ppmw of HCl)) in syngas did not significantly affect the activity, whereas rapid deactivation occurred at higher concentrations (~20 ppmw). With cobalt catalysts, even low concentrations of HCl (100 ppbw) caused catalyst deactivation, and the deactivation rate increased with increasing HCl concentration in the syngas. The deactivation of the catalysts ismore » explained by the chloride being adsorbed on the catalyst surface to (1) block the active sites and/or (2) electronically modify the sites. In this study, XANES spectroscopy was employed to investigate HCl poisoning mechanism on the iron and cobalt catalysts. Cl K-edge normalized XANES results indicate that Cl is indeed present on the catalyst following HCl poisoning and exhibits a structure similar to the family of compounds MCl; two main peaks are formed, with the second peak consisting of a main peak and a higher energy shoulder. At the Co K and Fe K edges, the white line was observed to be slightly increased relative to the same catalyst under clean conditions. There is then the additional possibility that Cl adsorption may act in part to intercept electron density from the FT metallic function (e.g.,cobalt or iron carbide). If so, this would result in less back-donation and therefore hinder the scission of molecules such as CO.« less

Production of biodiesel fuel by transesterification of different vegetable oils with methanol using Al₂O₃ modified MgZnO catalyst.

PubMed

Olutoye, M A; Hameed, B H

2013-03-01

An active heterogeneous Al2O3 modified MgZnO (MgZnAlO) catalyst was prepared and the catalytic activity was investigated for the transesterification of different vegetable oils (refined palm oil, waste cooking palm oil, palm kernel oil and coconut oil) with methanol to produce biodiesel. The catalyst was characterized by using X-ray diffraction, Fourier transform infrared spectra, thermo gravimetric and differential thermal analysis to ascertain its versatility. Effects of important reaction parameters such as methanol to oil molar ratio, catalyst dosage, reaction temperature and reaction time on oil conversion were examined. Within the range of studied variability, the suitable transesterification conditions (methanol/oil ratio 16:1, catalyst loading 3.32 wt.%, reaction time 6h, temperature 182°C), the oil conversion of 98% could be achieved with reference to coconut oil in a single stage. The catalyst can be easily recovered and reused for five cycles without significant deactivation. Copyright © 2013 Elsevier Ltd. All rights reserved.

n-Hexane hydro-isomerization over promoted Pd/HZSM-5 catalysts

NASA Astrophysics Data System (ADS)

Thoa Dao, Thi Kim; Loc Luu, Cam

2015-09-01

A series of Pd/HZSM-5 catalysts modified by various metallic species, including Co, Ni, Fe, Re, and Cu, was prepared by sequential impregnation. Contents of Pd and second metals in modified catalysts were 0.8 and 1.0 wt%, respectively. Physico-chemical characteristics of catalysts were investigated by nitrogen physi-sorption (BET), x-ray diffraction (XRD), transmission electron microscopy (TEM), ammonia temperature programmed desorption (NH3-TPD), temperature programmed reduction (TPR) and hydrogen pulse chemisorption (HPC). Coke formation was studied by the method of thermogravimetric analysis (TGA). The activities of catalysts in n-hexane isomerization were studied in a micro-flow reactor under atmospheric pressure at 250 °C, and molar ratio of H2: n-hexane of 5.92. It was found that Co, Ni, Fe, and Re additives exhibited geometric and electronic effects toward Pd/HZSM-5 catalyst, leading to an enhancement of its activity and stability. On the contrary, Cu additive caused Pd/HZSM-5 to become poorer in activity and stability.

SBA-15 Mesoporous Silica as Catalytic Support for Hydrodesulfurization Catalysts—Review

PubMed Central

Huirache-Acuña, Rafael; Nava, Rufino; Peza-Ledesma, Carmen L.; Lara-Romero, Javier; Alonso-Núñez, Gabriel; Pawelec, Barbara; Rivera-Muñoz, Eric M.

2013-01-01

SBA-15 is an interesting mesoporous silica material having highly ordered nanopores and a large surface area, which is widely employed as catalyst supports, absorbents, drug delivery materials, etc. Since it has a lack of functionality, heteroatoms and organic functional groups have been incorporated by direct or post-synthesis methods in order to modify their functionality. The aim of this article is to review the state-of-the-art related to the use of SBA-15-based mesoporous systems as supports for hydrodesulfurization (HDS) catalysts. PMID:28788323

Direct alcohol fuel cells: Increasing platinum performance by modification with sp-group metals

NASA Astrophysics Data System (ADS)

Figueiredo, Marta C.; Sorsa, Olli; Doan, Nguyet; Pohjalainen, Elina; Hildebrand, Helga; Schmuki, Patrik; Wilson, Benjamin P.; Kallio, Tanja

2015-02-01

By using sp group metals as modifiers, the catalytic properties of Pt can be improved toward alcohols oxidation. In this work we report the performance increase of direct alcohol fuel cells (DAFC) fuelled with ethanol or 2-propanol with platinum based anode electrodes modified with Bi and Sb adatoms. For example, by simply adding Sb to the Pt/C based anode ink during membrane electrode assembly fabrication of a direct ethanol fuel cell (DEFC) its performance is improved three-fold, with more than 100 mV increase in the open circuit potential. For the fuel cell fuelled with 2-propanol high power densities are obtained at very high potentials with these catalyst materials suggesting a great improvement for practical applications. Particularly in the case of Pt/C-Bi, the improvement is such that within 0.6 V (from 0.7 to 0.1 V) the power densities are between 7 and 9 mW/cm2. The results obtained with these catalysts are in the same range as those obtained with other bimetallic catalysts comprising of PtRu and PtSn, which are currently considered to be the best for these type of fuel cells and that are obtained by more complicated (and consequently more expensive) methods.

Polyethyleneimine-modified superparamagnetic Fe3O4 nanoparticles: An efficient, reusable and water tolerance nanocatalyst

NASA Astrophysics Data System (ADS)

Khoobi, Mehdi; Delshad, Tayebeh Modiri; Vosooghi, Mohsen; Alipour, Masoumeh; Hamadi, Hosein; Alipour, Eskandar; Hamedani, Majid Pirali; Sadat ebrahimi, Seyed Esmaeil; Safaei, Zahra; Foroumadi, Alireza; Shafiee, Abbas

2015-02-01

A novel magnetically separable catalyst was prepared based on surface modification of Fe3O4 magnetic nanoparticle (MNPs) with polyethyleneimine (PEI) via covalent bonding. [3-(2,3-Epoxypropoxy)propyl]trimethoxysilane (EPO) was used as cross linker to bond PEI on the surface of MNPs with permanent stability in contrast to PEI coating via electrostatic interactions. The synthesized catalyst was characterized by Fourier transform infrared (FT-IR), thermogravimetric analysis (TGA), X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and vibrating sample magnetometry (VSM). The catalyst show high efficiency for one-pot synthesis of 2-amino-3-cyano-4H-pyran derivatives via multi-component reaction (MCR). This procedure offers the advantages of green reaction media, high yield, short reaction time, easy purification of the products and simple recovery and reuse of the catalyst by simple magnetic decantation without significant loss of catalytic activity.

PET-modified red mud as catalysts for oxidative desulfurization reactions.

PubMed

do Prado, Nayara T; Heitmann, Ana P; Mansur, Herman S; Mansur, Alexandra A; Oliveira, Luiz C A; de Castro, Cinthia S

2017-07-01

This work describes the synthesis of catalysts based on red mud/polyethylene terephthalate (PET) composites and their subsequent heat treatment under N 2 atmosphere. The materials were characterized by scanning electron microscopy (SEM), temperature programmed reduction (TPR), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric (TG) analysis and N 2 adsorption/desorption. The catalysts were evaluated in the oxidative desulfurization reaction of dibenzothiophene (DBT) in a biphasic system. The results indicated that the PET impregnation on red mud increased the affinity of the catalyst with the nonpolar phase (fuel), in which the contaminant was dissolved, allowing a higher conversion (up to 80%) and selectivity to the corresponding dibenzothiophene sulfone. The sulfone compound is more polar than DBT and diffused into the polar solvent as indicated by the data obtained via gas chromatography-mass spectrometry (GC-MS). Copyright © 2017. Published by Elsevier B.V.

Metal-organic frameworks: versatile heterogeneous catalysts for efficient catalytic organic transformations.

PubMed

Chughtai, Adeel H; Ahmad, Nazir; Younus, Hussein A; Laypkov, A; Verpoort, Francis

2015-10-07

Novel catalytic materials are highly demanded to perform a variety of catalytic organic reactions. MOFs combine the benefits of heterogeneous catalysis like easy post reaction separation, catalyst reusability, high stability and homogeneous catalysis such as high efficiency, selectivity, controllability and mild reaction conditions. The possible organization of active centers like metallic nodes, organic linkers, and their chemical synthetic functionalization on the nanoscale shows potential to build up MOFs particularly modified for catalytic challenges. In this review, we have summarized the recent research progress in heterogeneous catalysis by MOFs and their catalytic behavior in various organic reactions, highlighting the key features of MOFs as catalysts based on the active sites in the framework. Examples of their post functionalization, inclusion of active guest species and metal nanoparticles have been discussed. Finally, the use of MOFs as catalysts for asymmetric heterogeneous catalysis and stability of MOFs has been presented as separate sections.

Catalytic dehydrogenation of isobutane in the presence of hydrogen over Cs-modified Ni2P supported on active carbon

NASA Astrophysics Data System (ADS)

Xu, Yanli; Sang, Huanxin; Wang, Kang; Wang, Xitao

2014-10-01

In this article, an environmentally friendly non-noble-metal class of Cs-Ni2P/active carbon (AC) catalyst was prepared and demonstrated to exhibit enhanced catalytic performance in isobutane dehydrogenation. The results of activity tests reveal that Ni/AC catalyst was highly active for isobutane cracking, which led to the formation of abundant methane and coke. After the introduction of phosphorus through impregnation with ammonium di-hydrogen phosphate and H2-temperature programmed reduction, undesired cracking reactions were effectively inhibited, and the selectivity to isobutene and stability of catalyst increased remarkably. The characterization results indicate that, after the addition of phosphorous, the improvement of dehydrogenation selectivity is ascribed to the partial positive charges carried on Ni surface in Ni2P particles, which decreases the strength of Nisbnd C bond between Ni and carbonium-ion intermediates and the possibility of excessive dehydrogenation. In addition, Cs-modified Ni2P/AC catalysts display much higher catalytic performance as compared to Ni2P/AC catalyst. Cs-Ni2P-6.5 catalyst has the highest catalytic performance, and the selectivity to isobutene higher than 93% can be obtained even after 4 h reaction. The enhancement in catalytic performance of the Cs-modified catalysts is mainly attributed to the function of Cs to improve the dispersion of Ni2P particles, transfer electron from Cs to Ni, and decrease acid site number and strength.

Precursor effect on the property and catalytic behavior of Fe-TS-1 in butadiene epoxidation

NASA Astrophysics Data System (ADS)

Wu, Mei; Zhao, Huahua; Yang, Jian; Zhao, Jun; Song, Huanling; Chou, Lingjun

2017-11-01

The effect of iron precursor on the property and catalytic behavior of iron modified titanium silicalite molecular sieve (Fe-TS-1) catalysts in butadiene selective epoxidation has been studied. Three Fe-TS-1 catalysts were prepared, using iron nitrate, iron chloride and iron sulfate as precursors, which played an important role in adjusting the textural properties and chemical states of TS-1. Of the prepared Fe-TS-1 catalysts, those modified by iron nitrate (FN-TS-1) exhibited a significant enhanced performance in butadiene selective epoxidation compared to those derived from iron sulfate (FS-TS-1) or iron chloride (FC-TS-1) precursors. To obtain a deep understanding of their structure-performance relationship, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Temperature programmed desorption of NH3 (NH3-TPD), Diffuse reflectance UV-Vis spectra (DR UV-Vis), Fourier transformed infrared spectra (FT-IR) and thermal gravimetric analysis (TGA) were conducted to characterize Fe-TS-1 catalysts. Experimental results indicated that textural structures and acid sites of modified catalysts as well as the type of Fe species influenced by the precursors were all responsible for the activity and product distribution.

Efficient synthesis of optically active 4-nitro-cyclohexanones via bifunctional thiourea-base catalyzed double-Michael addition of nitromethane to dienones.

PubMed

Wu, Bin; Liu, Guo-Gui; Li, Mei-Qiu; Zhang, Yong; Zhang, Shao-Yun; Qiu, Jun-Ru; Xu, Xiao-Ping; Ji, Shun-Jun; Wang, Xing-Wang

2011-04-07

Thiourea-modified cinchona alkaloids as bifunctional catalysts and a base could catalyze a stepwise [5+1] cyclization of divinyl ketones with nitromethane via double Michael additions, furnishing optically active 4-nitro-cyclohexanones with good yields, excellent diastereoselectivities (>20 : 1) and high enantiomeric ratios (up to 97 : 3).

Ferrocene-modified chitosan as an efficient and green heterogeneous catalyst for sulfate-radical-based advanced oxidation process.

PubMed

Lin, Kun-Yi Andrew; Lin, Jyun-Ting; Yang, Hongta

2017-10-01

While ferrocene (Fc) is a promising heterogeneous catalyst for activating persulfate (PS) to degrade organic contaminants, chemical reagent-grade Fc is nanoscale and direct usage of Fc leads to operational and recovery issues. In this study, chitosan (CS) is selected as a support to immobilize Fc as CS is abundant, and environmental benign fishery waste. The amine group of CS also allows the formation of covalent bond between Fc-based reagent (i.e., Fc-CHO) and CS to form Fc-modified CS (Fc-CS). This Fc-CS can be more advantageous than Fc because of its easier recovery by precipitation and filtration. To evaluate Fc-CS for PS activation, degradation of Amaranth (AMR) dye by PS is selected as a model test. The resulting Fc-CS exhibits a higher catalytic activity than pristine Fc possibly because Fc can be evenly dispersed on CS and CS can also exhibit affinity toward AMR. AMR can be also fully decomposed by Fc-CS activated PS. Through the Electron paramagnetic resonance (EPR) spectroscopic analysis, the AMR degradation can be attributed to both sulfate and hydroxyl radicals. Fc-CS had been also proven to activate PS for AMR degradation over multiple times without loss of catalytic activity. These features indicate that Fc-CS can be a promising catalyst and CS appears to be a naturally available and environmentally friendly waste-derived support for immobilizing Fc. The results and findings in this study are essential for CS-supported metal catalysts in environmental applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

Microwave-assisted maleation of tung oil for bio-based products

USDA-ARS?s Scientific Manuscript database

In this work, a simple, “green” and convenient chemical modification of tung oil for maleinized tung oil (TOMA) was developed via microwave-assisted one-step maleation. This modifying process did not involve any solvent, catalyst, or initiator, but demonstrated the most efficiency of functionalizing...

Photoelectrocatalytic reduction of CO2 into chemicals using Pt-modified reduced graphene oxide combined with Pt-modified TiO2 nanotubes.

PubMed

Cheng, Jun; Zhang, Meng; Wu, Gai; Wang, Xin; Zhou, Junhu; Cen, Kefa

2014-06-17

The photoelectrocatalytic (PEC) reduction of CO2 into high-value chemicals is beneficial in alleviating global warming and advancing a low-carbon economy. In this work, Pt-modified reduced graphene oxide (Pt-RGO) and Pt-modified TiO2 nanotubes (Pt-TNT) were combined as cathode and photoanode catalysts, respectively, to form a PEC reactor for converting CO2 into valuable chemicals. XRD, XPS, TEM, AFM, and SEM were employed to characterize the microstructures of the Pt-RGO and Pt-TNT catalysts. Reduction products, such as C2H5OH and CH3COOH, were obtained from CO2 under band gap illumination and biased voltage. A combined liquid product generation rate (CH3OH, C2H5OH, HCOOH, and CH3COOH) of approximately 600 nmol/(h·cm(2)) was observed. Carbon atom conversion rate reached 1,130 nmol/(h·cm(2)), which were much higher than those achieved using Pt-modified carbon nanotubes and platinum carbon as cathode catalysts.

Use of Hydrogen Chemisorption and Ethylene Hydrogenation as Predictors for Aqueous Phase Reforming of Lactose over Ni@Pt and Co@Pt Bimetallic Overlayer Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lai, Qinghua; Skoglund, Michael D.; Zhang, Chen

Overlayer Pt on Ni (Ni@Pt) or Co (Co@Pt) were synthesized and tested for H2 generation from APR of lactose. H2 chemisorption descriptor showed that Ni@Pt and Co@Pt overlayer catalysts had reduced H2 adsorption strength compared to a Pt only catalyst, which agree with computational predictions. The overlayer catalysts also demonstrated lower activity for ethylene hydrogenation than the Pt only catalyst, which likely resulted from decreased H2 binding strength decreasing the surface coverage of H2. XAS results showed that overlayer catalysts exhibited higher white line intensity than the Pt catalyst, which indicates a negative d-band shift for the Pt overlayer, furthermore » providing evidence for overlayer formation. Lactose APR studies showed that lactose can be used as feedstock to produce H2 and CO under desirable reaction conditions. The Pt active sites of Ni@Pt and Co@Pt overlayer catalysts showed significantly enhanced H2 production selectivity and activity when compared with that of a Pt only catalyst. The single deposition overlayer with the largest d-band shift showed the highest H2 activity. The results suggest that overlayer formation using directed deposition technique could modify the behavior of the surface metal and ultimately modify the APR activity.« less

Pictures of Processes: Automated Graph Rewriting for Monoidal Categories and Applications to Quantum Computing

NASA Astrophysics Data System (ADS)

Kumar, Bhupendra

Light assisted or driven fuel generation by carbon dioxide and proton reduction can be achieved by a p-type semiconductor/liquid junction. There are four different types of schemes which are typically used for carbon dioxide and proton reduction for fuel generation applications. In these systems, the semiconductor can serve the dual role of a catalyst and a light absorber. Specific electrocatalysts (heterogeneous and homogeneous) can be driven by p-type semiconductor where it works only as light absorber in order to achieve better selectivity and faster rates of catalysis. The p-type semiconductor/molecular catalyst junction is primarily explored in this dissertation for CO2 and proton photoelectrochemical reduction. A general principle for the operation of p-type semiconductor/molecular junctions is proposed and validated for several molecular catalysts in contact with p-Si photocathode. It is also shown that the light assisted homogeneous and heterogeneous catalysis can coexist. This principle is extended to achieve direct conversion of CO 2 to methanol on Platinum nanoparticles decorated p-Si in aqueous medium through pyridine/pyridinium system for CO2 reduction. An open circuit voltage higher than 600 mV is achieved for p-Si/Re(bipy-tBu)(CO) 3Cl [where bipy-tBu = 4,4'- tert-butyl-2,2'-bipyridine] (Re-catalyst) junction. The photoelectrochemical conversion of CO2 to CO using a p-Si/Re-catalyst junction is obtained at 100 % Faradaic efficiency. The homogeneous catalytic current density for CO2 by p-Si/Re-catalyst junction under illumination scales linearly with illumination intensity (both polychromatic and monochromatic). This indicates that the homogeneous catalysis is light driven for the p-Si/Re-catalyst junction system up to light intensities approaching one sun. The photoelectrochemical reduction of other active members of Re(bipyridyl)(CO)3Cl molecular catalyst family is also observed on illuminated p-Si photocathode. Effects of surface modification and nanowire morphology of the p-Si photocathode on the homogeneous catalytic reduction of CO2 by using p-Si/Re-catalyst junction are also described in this dissertation. For phenyl ethyl modified p-Si photocathode, the rate of homogeneous catalysis for CO2 reduction by Re-catalyst is three times greater than glassy carbon electrode and six times greater than the hexyl modified and the hydrogen terminated p-Si photocathodes. When hexyl modified p-Si nanowires are used as photocathode, the homogeneous catalytic current density increased by a factor of two compared to planar p-Si (both freshly etched and hexyl modified) photocathode. A successful light assisted generation of syngas (H2:CO = 2:1) from CO2 and water is achieved by using p-Si/Re-catalyst. In this system, water is reduced heterogeneously on p-Si surface and CO2 is reduced homogeneously by Re-catalyst. The same principle is extended to the homogeneous proton reduction by using p-Si/[FeFe] complex junction where [FeFe] complex [Fe2(micro-bdt)(CO) 6] (bdt = benzene-1,2-dithiolate)] is a proton reduction molecular catalyst. A short circuit quantum efficiency of 79 % with 100 % Faradaic efficiency and 600 mV open circuit are achieved by using p-Si/[FeFe] complex for proton reduction with 300 mM perchloric acid as a proton source. Cobalt difluororyl-diglyoximate (Co-catalyst) is a proton reduction catalyst with only 200 mV of overpotential for the hydrogen evolution reaction (HRE). The Co-catalyst is photoelectrochemically reduced with a photovoltage of 470 mV on illuminated p-Si photocathode. For p-Si photocathodes, the overpotential for proton reduction is over 1 V. In principle, p-Si/Co-catalyst junction can reduce proton to hydrogen homogeneously at underpotential. In a concluding effort, a wireless monolithic dual face single photoelectrode (multi junction photovoltaic cell which can generate a voltage higher 1.7 V) based photochemical cell is proposed for direct conversion of solar energy into liquid fuel. In this device, the two faces of the multijunction photoelectrode are serve as an anode and a cathode for water oxidation and fuel generation, respectively, and are separated by proton exchange membrane.

PdCo nanoparticles supported on carbon fibers derived from cotton: Maximum utilization of Pd atoms for efficient reduction of nitroarenes.

PubMed

Yang, Jin; Wang, Wei David; Dong, Zhengping

2018-08-15

In the present work, a facile and environment-friendly route is illustrated for the efficient fabrication of highly dispersed PdCo nanoparticles (NPs) by modified cotton-derived carbon fibers (PdCo/CCF). Firstly, commercial cotton was impregnated with CoCl 2 , followed by pyrolysis under high calcination temperature to obtain the Co NPs modified CCF sample (Co/CCF). Secondly, Co/CCF was treated with Pd(AcO) 2 aqueous solution, wherein, through a spontaneous replacement reaction process, Pd 2+ is reduced to metallic Pd and mostly covered on the surface of the Co NPs. Thus, the PdCo/CCF catalyst was obtained avoiding the use of toxic reductants like NaBH 4 , NH 2 NH 2 and HCHO. The PdCo/CCF catalyst exhibits excellent catalytic activity and recyclability for the reduction of 4-nitrophenol and other nitroarenes compared with Pd/CCF, PdCo NPs and many other noble metals based catalysts. The reasons could be attributed to the uniformly dispersed and accessible PdCo NPs on the surface of the CCF, and the Pd atoms deposited on the Co NPs surface that makes the Pd active sites available for optimum use. The PdCo/CCF catalyst also exhibits potential application for catalytic reduction of nitroarenes in a fixed bed reactor under mild reaction conditions. Furthermore, the PdCo/CCF catalyst can be magnetically recycled and reused for at least ten cycles without either losing catalytic activity or leaching of Pd active sites, thereby confirming its superior stability. Copyright © 2018 Elsevier Inc. All rights reserved.

Effect of plasma-induced surface charging on catalytic processes: application to CO2 activation

NASA Astrophysics Data System (ADS)

Bal, Kristof M.; Huygh, Stijn; Bogaerts, Annemie; Neyts, Erik C.

2018-02-01

Understanding the nature and effect of the multitude of plasma-surface interactions in plasma catalysis is a crucial requirement for further process development and improvement. A particularly intriguing and rather unique property of a plasma-catalytic setup is the ability of the plasma to modify the electronic structure, and hence chemical properties, of the catalyst through charging, i.e. the absorption of excess electrons. In this work, we develop a quantum chemical model based on density functional theory to study excess negative surface charges in a heterogeneous catalyst exposed to a plasma. This method is specifically applied to investigate plasma-catalytic CO2 activation on supported M/Al2O3 (M = Ti, Ni, Cu) single atom catalysts. We find that (1) the presence of a negative surface charge dramatically improves the reductive power of the catalyst, strongly promoting the splitting of CO2 to CO and oxygen, and (2) the relative activity of the investigated transition metals is also changed upon charging, suggesting that controlled surface charging is a powerful additional parameter to tune catalyst activity and selectivity. These results strongly point to plasma-induced surface charging of the catalyst as an important factor contributing to the plasma-catalyst synergistic effects frequently reported for plasma catalysis.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Winter, Lea R.; Gomez, Elaine; Yan, Binhang

CO 2 hydrogenation over Fe-modified Ni/CeO 2 catalysts was investigated in a batch reactor using time-resolved in situ FTIR spectroscopy. Low loading of Ni/CeO 2 was associated with high selectivity to CO over CH 4, while higher Ni loading improved CO 2 hydrogenation activity with a reduced CO selectivity. X-ray absorption near-edge structure (XANES) analysis revealed Ni to be metallic for all catalysts including the CO-selective low loading 0.5% Ni catalyst, suggesting that the selectivity trend is due to structural rather than oxidation state effects. The loading amount of 1.5% Ni was selected for co-impregnation with Fe, based on themore » significant shift in product selectivity towards CH 4 for that loading amount, in order to shift the selectivity towards CO while maintaining high activity. Temperature programmed reduction (TPR) results indicated bimetallic interactions between Ni and Fe, and XANES analysis showed that about 70% of Fe in the bimetallic catalysts was oxidized. The Ni-Fe catalysts demonstrated improved selectivity towards CO without significantly compromising activity, coupling the high activity of Ni catalysts and the high CO selectivity of Fe. The general trends in Ni loading and bimetallic modification should guide efforts to develop non-precious metal catalysts for the selective production of CO by CO 2 hydrogenation.« less

Microwave-assisted maleation of tung oil for bio-based products with versatile applications

USDA-ARS?s Scientific Manuscript database

In this work, a simple, “green” and convenient chemical modification of tung oil for maleinized tung oil (TOMA) was developed via microwave-assisted one-step maleation. This modifying process did not involve any solvent, catalyst, or initiator, but demonstrated the most efficiency of functionalizing...

A novel metal organic framework-derived carbon-based catalyst for oxygen reduction reaction in a microbial fuel cell

NASA Astrophysics Data System (ADS)

Zhang, Lihua; Hu, Yongyou; Chen, Junfeng; Huang, Wantang; Cheng, Jianhua; Chen, Yuancai

2018-04-01

To improve the power generation of microbial fuel cell (MFC), the cathode is modified to increase its oxygen reduction reaction (ORR) activity by using a Cu, N-incorporated carbon-based material as catalyst, which obtained from pyrolyzing ORR active Cu (II)-based metal organic framework (MOF; Cu-bipy-BTC, bipy = 2,2‧-bipyridine, BTC = 1,3,5-tricarboxylate). MOF-800 (the product of pyrolyzing Cu-bipy-BTC at 800 °C) shows porous structure with micropores ranging from 0.5 to 1.3 nm and mesopores ranging from 27 to 46 nm. It also exhibits improved ORR electrocatalytic activity with a higher current density of -3.06 mA cm-2 compared to Cu-bipy-BTC. Moreover, the charge transfer resistance of MOF-800 cathode (1.38 Ω) is much smaller than that of Cu-bipy-BTC cathode (176.8 Ω). A maximum power density of 326 ± 11 mW m-2 is achieved by MOF-800-MFC, which is 2.6 times of that of Cu-bipy-BTC-MFC and comparable with Pt/C-MFC (402 ± 17 mW m-2). The results imply the enhancements of ORR catalytic activity and electrical conductivity of MOF-800 are due to the enhanced porous structure and abundant active sites (C-N, Cu-Nχ), which result in the improved power generation of MFC. This study provides technical and theoretical validation for the MFC performance improvement by ORR active MOF-derived catalysts modified cathodes.

From small molecules to polymeric catalysts in the oscillatory carbonylation reaction: multiple effects of adding HI.

PubMed

Isakova, Anna; Murdoch, Billy J; Novakovic, Katarina

2018-04-04

The oscillatory palladium-catalysed carbonylation reaction opens new horizons for applications in smart materials due to the versatility of its conditions and substrates, as well as the adjustability of amplitude and period of pH oscillations. A variety of viable substrates have been demonstrated, including polymeric alkyne-terminated substrates. However, so far, there have not been any reports of polymer-based palladium catalysts in oscillatory mode. In this paper, we demonstrate pH oscillations in various systems, using commercially available palladium acetate, a triphenylphosphine palladium acetate complex and a polymer-bound palladium catalyst. While palladium acetate was able to generate oscillations under the conditions already established in our previous research on PdI2-catalysed oscillators, the other two catalysts needed the addition of HI to induce oscillations. HI forced an initial pH drop, bringing pH into the range where oscillations generally occur. Addition of HI had a significant effect on all catalysts, modifying the amplitude and period of oscillations, oscillation mode, as well as starting material conversion and product distribution.

An Overview of Recent Development in Composite Catalysts from Porous Materials for Various Reactions and Processes

PubMed Central

Xie, Zaiku; Liu, Zhicheng; Wang, Yangdong; Yang, Qihua; Xu, Longya; Ding, Weiping

2010-01-01

Catalysts are important to the chemical industry and environmental remediation due to their effective conversion of one chemical into another. Among them, composite catalysts have attracted continuous attention during the past decades. Nowadays, composite catalysts are being used more and more to meet the practical catalytic performance requirements in the chemical industry of high activity, high selectivity and good stability. In this paper, we reviewed our recent work on development of composite catalysts, mainly focusing on the composite catalysts obtained from porous materials such as zeolites, mesoporous materials, carbon nanotubes (CNT), etc. Six types of porous composite catalysts are discussed, including amorphous oxide modified zeolite composite catalysts, zeolite composites prepared by co-crystallization or overgrowth, hierarchical porous catalysts, host-guest porous composites, inorganic and organic mesoporous composite catalysts, and polymer/CNT composite catalysts. PMID:20559508

Ethylene polymerization on a SiH4-modified Phillips catalyst: detection of in situ produced α-olefins by operando FT-IR spectroscopy.

PubMed

Barzan, Caterina; Groppo, Elena; Quadrelli, Elsje Alessandra; Monteil, Vincent; Bordiga, Silvia

2012-02-21

Ethylene polymerization on a model Cr(II)/SiO(2) Phillips catalyst modified with gas phase SiH(4) leads to a waxy product containing a bimodal MW distribution of α-olefins (M(w) < 3000 g mol(-1)) and a highly branched polyethylene, LLDPE (M(w) ≈ 10(5) g mol(-1), T(m) = 123 °C), contrary to the unmodified catalyst which gives a linear and more dense PE, HDPE (M(w) = 86,000 g mol(-1) (PDI = 7), T(m) = 134 °C). Pressure and temperature resolved FT-IR spectroscopy under operando conditions (T = 130-230 K) allows us to detect α-olefins, and in particular 1-hexene and 1-butene (characteristic IR absorption bands at 3581-3574, 1638 and 1598 cm(-1)) as intermediate species before their incorporation in the polymer chains. The polymerization rate is estimated, using time resolved FT-IR spectroscopy, to be 7 times higher on the SiH(4)-modified Phillips catalyst with respect to the unmodified one.

Interstitial modification of palladium nanoparticles with boron atoms as a green catalyst for selective hydrogenation

NASA Astrophysics Data System (ADS)

Chan, Chun Wong Aaron; Mahadi, Abdul Hanif; Li, Molly Meng-Jung; Corbos, Elena Cristina; Tang, Chiu; Jones, Glenn; Kuo, Winson Chun Hsin; Cookson, James; Brown, Christopher Michael; Bishop, Peter Trenton; Tsang, Shik Chi Edman

2014-12-01

Lindlar catalysts comprising of palladium/calcium carbonate modified with lead acetate and quinoline are widely employed industrially for the partial hydrogenation of alkynes. However, their use is restricted, particularly for food, cosmetic and drug manufacture, due to the extremely toxic nature of lead, and the risk of its leaching from catalyst surface. In addition, the catalysts also exhibit poor selectivities in a number of cases. Here we report that a non-surface modification of palladium gives rise to the formation of an ultra-selective nanocatalyst. Boron atoms are found to take residence in palladium interstitial lattice sites with good chemical and thermal stability. This is favoured due to a strong host-guest electronic interaction when supported palladium nanoparticles are treated with a borane tetrahydrofuran solution. The adsorptive properties of palladium are modified by the subsurface boron atoms and display ultra-selectivity in a number of challenging alkyne hydrogenation reactions, which outclass the performance of Lindlar catalysts.

Reactivity improvement of cellulolytic enzyme lignin via mild hydrothermal modification.

PubMed

Ma, Zhuoming; Tang, Jiafa; Li, Shujun; Suo, Enxiang

2017-12-01

Isolated by the cellulolytic enzyme lignin (CEL) process, water-alcohol (1:1, v/v) was introduced as co-solvent in the process of the hydrothermal treatment. The modification parameters such as reaction temperature and time, solid-to-liquid ratio, and catalysts (NaOH and NaOAlO 2 ) have been investigated in terms of the specific lignin properties, such as the phenolic hydroxyl content (OH phen ), DPPH free radical scavenging rate, and formaldehyde value. The CELs were also characterized by GPC, FT-IR and 1 H NMR spectroscopy, and Py-GC/MS. The key data are under optimal lignin modification conditions (solid-to-liquid ratio of 1:10 (w/v) and a temperature of 250°C for 60min) are: OH phen content: 2.50mmol/g; half maximal inhibitory concentration (IC 50 ) towards DPPH free radicals: 88.2mg/L; formaldehyde value: 446.9g/kg). Both base catalysts decrease the residue rate, but phenol reactivities of the products were also detracted. Py-GC/MS results revealed that modified lignin had a higher phenolic composition than the CEL did, especially the modified lignin without catalyst (ML), which represented 74.51% phenolic content. Copyright © 2017. Published by Elsevier Inc.

Highly Dispersed and Active ReOx on Alumina-Modified SBA-15 Silica for 2-Butanol Dehydration

DOE Office of Scientific and Technical Information (OSTI.GOV)

She, Xiaoyan; Kwak, Ja Hun; Sun, Junming

2012-05-23

SBA-15 silica supported rhenium catalysts were synthesized using solution-based atomic layer deposition method, and their activity and stability were studied in the acid-catalyzed 2-butanol dehydration. We find that ReOx/SBA-15 exhibited an extremely high initial activity but a fast deactivation for 2-butanol dehydration at 90-105 C. Fast deactivation was likely due to the sintering, sublimation, and reduction of rhenia as confirmed by TEM, elemental analysis, and in situ UV vis (DRS) measurements. To overcome these issues, ReOx/AlOx/SBA-15 catalysts with significantly improved stability were prepared by first modifying the surface identity of SBA-15 with alumina followed by dispersion of rhenia using atomicmore » layer deposition. The AlOx phase stabilizes the dispersion of small and uniform rhenia clusters (<2 nm) as as confirmed by TEM, STEM and UV-vis (DRS) characterizations. Additional 27Al MAS NMR characterization revealed that modification of the SBA-15 surface with alumina introduces a strong interaction between rhenia and alumina, which consequently improves the stability of supported rhenia catalysts by suppressing the sintering, sublimation, and reduction of rhenia albeit at a moderately reduced initial catalytic dehydration activity« less

Enhancement of Glycerol Steam Reforming Activity and Thermal Stability by Incorporating CeO2 and TiO2 in Ni- and Co-MCM-41 Catalysts

NASA Astrophysics Data System (ADS)

Dade, William N.

Hydrogen (H2) has many applications in industry with current focus shifted to production of hydrocarbon fuels and valuable oxygenates using the Fischer-Tropsch technology and direct use in proton exchange membrane fuel cell (PEMFC). Hydrogen is generally produced via steam reforming of natural gas or alcohols like methanol and ethanol. Glycerol, a by-product of biodiesel production process, is currently considered to be one of the most attractive sources of sustainable H2 due to its high H/C ratio and bio-based origin. Ni and Co based catalysts have been reported to be active in glycerol steam reforming (GSR); however, deactivation of the catalysts by carbon deposition and sintering under GSR operating conditions is a major challenge. In this study, a series of catalysts containing Ni and Co nanoparticles incorporated in CeO2 and TiO2 modified high surface area MCM-41 have been synthesized using one-pot method. The catalysts are tested for GSR (at H2O/Glycerol mole ratio of 12 and GHSV of 2200 h-1) to study the effect of support modification and reaction temperature (450 - 700 °C) on the product selectivity and long term stability. GSR results revealed that all the catalysts performed significantly well exhibiting over 85% glycerol conversion at 650 °C except Ni catalysts that showed better low temperature activities. Deactivation studies of the catalysts conducted at 650 °C indicated that the Ni-TiO2-MCM-41 and Ni-CeO 2-MCM-41 were resistant to deactivation with ˜100% glycerol conversion for 40 h. In contrast, Co-TiO2-MCM-41 perform poorly as the catalyst rapidly deactivated after 12 h to yield ˜20% glycerol conversion after 40 h. The WAXRD and TGA-DSC analyses of spent catalysts showed a significant amount of coke deposition that might explain catalysts deactivation. The flattening shape of the original BET type IV isotherm with drastic reduction of catalyst surface area can also be responsible for observed drop in catalysts activities.

An Enzyme-Mediated Methodology for the Site-Specific Radiolabeling of Antibodies Based on Catalyst-Free Click Chemistry

PubMed Central

Zeglis, Brian M.; Davis, Charles B.; Aggeler, Robert; Kang, Hee Chol; Chen, Aimei; Agnew, Brian J.; Lewis, Jason S.

2013-01-01

An enzyme- and click chemistry-mediated methodology for the site-selective radiolabeling of antibodies on the heavy chain glycans has been developed and validated. To this end, a model system based on the prostate specific membrane antigen-targeting antibody J591, the positron-emitting radiometal 89Zr, and the chelator desferrioxamine has been employed. The methodology consists of four steps: (1) the removal of sugars on the heavy chain region of the antibody to expose terminal N-acetylglucosamine residues; (2) the incorporation of azide-modified N-acetylgalactosamine monosaccharides into the glycans of the antibody; (3) the catalyst-free click conjugation of desferrioxamine-modified dibenzocyclooctynes to the azide-bearing sugars; and (4) the radiolabeling of the chelator-modified antibody with 89Zr. The site-selective labeling methodology has proven facile, reproducible, and robust, producing 89Zr-labeled radioimmunoconjguates that display high stability and immunoreactivity in vitro (>95%) in addition to high selective tumor uptake (67.5 ± 5.0 %ID/g) and tumor-to-background contrast in athymic nude mice bearing PSMA-expressing subcutaneous LNCaP xenografts. Ultimately, this strategy could play a critical role in the development of novel well-defined and highly immunoreactive radioimmunoconjugates for both the laboratory and clinic. PMID:23688208

Modified fly ash from municipal solid waste incineration as catalyst support for Mn-Ce composite oxides

NASA Astrophysics Data System (ADS)

Chen, Xiongbo; Liu, Ying; Yang, Ying; Ren, Tingyan; Pan, Lang; Fang, Ping; Chen, Dingsheng; Cen, Chaoping

2017-08-01

Fly ash from municipal solid waste incineration was modified by hydrothermal treatment and used as catalyst support for Mn-Ce composite oxides. The prepared catalyst showed good activity for the selective catalytic reduction (SCR) of NO by NH3. A NO conversion of 93% could be achieved at 300 °C under a GHSV of 32857 h-1. With the help of characterizations including XRD, BET, SEM, TEM, XPS and TPR, it was found that hydrothermal treatment brought a large surface area and abundant mesoporous to the modified fly ash, and Mn-Ce composite oxides were highly dispersed on the surface of the support. These physical and chemical properties were the intrinsic reasons for the good SCR activity. This work transformed fly ash into high value-added products, providing a new approach to the resource utilization and pollution control of fly ash.

Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

DOE PAGES

Getsoian, Andrew "Bean"; Das, Ujjal; Camacho-Bunquin, Jeffrey; ...

2016-06-13

Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order tomore » better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. Furthermore, these findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.« less

Diameter and Geometry Control of Vertically Aligned SWNTs through Catalyst Manipulation

NASA Astrophysics Data System (ADS)

Xiang, Rong; Einarsson, Erik; Okawa, Jun; Murakami, Yoichi; Maruyama, Shigeo

2009-03-01

We present our recent progress on manipulating our liquid-based catalyst loading process, which possesses greater potential than conventional deposition in terms of cost and scalability, to control the diameter and morphology of single-walled carbon nanotubes (SWNTs). We demonstrate that the diameter of aligned SWNTs synthesized by alcohol catalytic CVD can be tailored over a wide range by modifying the catalyst recipe. SWNT arrays with an average diameter as small as 1.2 nm were obtained by this method. Additionally, owing to the alignment of the array, the continuous change of the SWNT diameter during a single CVD process can be clearly observed and quantitatively characterized. We have also developed a versatile wet chemistry method to localize the growth of SWNTs to desired regions via surface modification. By functionalizing the silicon surface using a classic self-assembled monolayer, the catalyst can be selectively dip-coated onto hydrophilic areas of the substrate. This technique was successful in producing both random and aligned SWNTs with various patterns. The precise control of the diameter and morphology of SWNTs, achieved by simple and scalable liquid-based surface chemistry, could greatly facilitate the application of SWNTs as the building blocks of future nano-devices.

Final Project Report: Development of Micro-Structural Mitigation Strategies for PEM Fuel Cells: Morphological Simulations and Experimental Approaches

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wessel, Silvia; Harvey, David

2013-06-28

The durability of PEM fuel cells is a primary requirement for large scale commercialization of these power systems in transportation and stationary market applications that target operational lifetimes of 5,000 hours and 40,000 hours by 2015, respectively. Key degradation modes contributing to fuel cell lifetime limitations have been largely associated with the platinum-based cathode catalyst layer. Furthermore, as fuel cells are driven to low cost materials and lower catalyst loadings in order to meet the cost targets for commercialization, the catalyst durability has become even more important. While over the past few years significant progress has been made in identifyingmore » the underlying causes of fuel cell degradation and key parameters that greatly influence the degradation rates, many gaps with respect to knowledge of the driving mechanisms still exist; in particular, the acceleration of the mechanisms due to different structural compositions and under different fuel cell conditions remains an area not well understood. The focus of this project was to address catalyst durability by using a dual path approach that coupled an extensive range of experimental analysis and testing with a multi-scale modeling approach. With this, the major technical areas/issues of catalyst and catalyst layer performance and durability that were addressed are: 1. Catalyst and catalyst layer degradation mechanisms (Pt dissolution, agglomeration, Pt loss, e.g. Pt in the membrane, carbon oxidation and/or corrosion). a. Driving force for the different degradation mechanisms. b. Relationships between MEA performance, catalyst and catalyst layer degradation and operational conditions, catalyst layer composition, and structure. 2. Materials properties a. Changes in catalyst, catalyst layer, and MEA materials properties due to degradation. 3. Catalyst performance a. Relationships between catalyst structural changes and performance. b. Stability of the three-phase boundary and its effect on performance/catalyst degradation. The key accomplishments of this project are: • The development of a molecular-dynamics based description of the carbon supported-Pt and ionomer system • The development of a composition-based, 1D-statistical Unit Cell Performance model • A modified and improved multi-pathway ORR model • An extension of the existing micro-structural catalyst model to transient operation • The coupling of a Pt Dissolution model to the modified ORR pathway model • The Development A Semi-empirical carbon corrosion model • The integration and release of an open-source forward predictive MEA performance and degradation model • Completion of correlations of BOT (beginning of test) and EOT (end of test) performance loss breakdown with cathode catalyst layer composition, morphology, material properties, and operational conditions • Catalyst layer durability windows and design curves • A design flow path of interactions from materials properties and catalyst layer effective properties to performance loss breakdown for virgin and degraded catalyst layers In order to ensure the best possible user experience we will perform a staged release of the software leading up to the webinar scheduled in October 2013. The release schedule will be as follows (please note that the manual will be released with the beta release as direct support is provided in Stage 1): • Stage 0 - Internal Ballard Release o Cross check of compilation and installation to ensure machine independence o Implement code on portable virtual machine to allow for non-UNIX use (pending) • Stage 1 - Alpha Release o The model code will be made available via a GIT, sourceforge, or other repository (under discussion at Ballard) for download and installation by a small pre-selected group of users o Users will be given three weeks to install, apply, and evaluate features of the code, providing feedback on issues or software bugs that require correction prior to beta release • Stage 2 - Beta Release o The model code repository is opened to the general public on a beta release concept, with a mechanism for bug tracking and feedback from a large user group o Code will be tracked and patched for any discovered bugs or relevant feedback from the user community, upon the completion of three months without a major bug submission the code will be moved to a full version release • Stage 3 - Full Version Release o Code is version to revision 1.0 and that version is frozen in development/patching« less

Recent developments on ultrasound assisted catalyst-free organic synthesis.

PubMed

Banerjee, Bubun

2017-03-01

Mother Nature needs to be protected from ever increasing chemical pollutions associated with synthetic organic processes. The fundamental challenge for today's methodologists is to make their protocols more environmentally benign and sustainable by avoiding the extensive use of hazardous reagents and solvents, harsh reaction conditions, and toxic metal catalysts. However, the people of the twenty-first century are well aware about the side effects of those hazardous substances used and generated by the chemical processes. As a result, the last decade has seen a tremendous outburst in modifying chemical processes to make them 'sustainable' for the betterment of our environment. Catalysts play a crucial role in organic synthesis and thus they find huge applications and uses. Scientists' continuously trying to modify the catalysts to reduce their toxicity level, but the most benign way is to design an organic reaction without catalyst(s), if possible. It is worthy to mention that the involvement of ultrasound in organic synthesis is sometimes fulfilling this goal. In many occasions the applications of ultrasound can avoid the use of catalysts in organic reactions. Such beneficial features as a whole have motivated the organic chemists to apply ultrasonic irradiation in more heights and as a results, in recent past, there were immense applications of ultrasound in organic reactions for the synthesis of diverse organic scaffolds under catalyst-free condition. The present review summarizes the latest developments on ultrasound assisted catalyst-free organic synthesis reported so far. Copyright © 2016 Elsevier B.V. All rights reserved.

Influence of peracetic acid modification on the physicochemical properties of activated carbon and its performance in the ozone-catalytic oxidation of gaseous benzene

NASA Astrophysics Data System (ADS)

Fang, Ruimei; Huang, Haibao; Huang, Wenjun; Ji, Jian; Feng, Qiuyu; Shu, Yajie; Zhan, Yujie; Liu, Gaoyuan; Xie, Ruijie

2017-10-01

Coal based activated carbon (AC) was pretreated by peracetic acid solution and used for supporting Mn catalyst towards oxidation of gaseous benzene by catalytic ozonation. The as-obtained activated carbon was characterized by XPS, BET, SEM, and TG technologies. It indicates that peracetic acid solution modification not only raised the quantity of chemisorbed oxygen or water, and hydroxyl group on activated carbon material surface, but also increased the specific surface area and benzene adsorption capacity of activated carbon. Benzene could be completely removed in 300 min and CO2 selectivity reached to 61.9% over Mn/AC-modified catalyst. A possible catalytic ozonation mechanism of activated carbon which was treated by peracetic acid solution supported Mn catalyst for oxidation of benzene was proposed.

Replacing precious metals with carbide catalysts for hydrogenation reactions

DOE PAGES

Ruijun, Hou; Chen, Jingguang G.; Chang, Kuan; ...

2015-03-03

Molybdenum carbide (Mo₂C and Ni/Mo₂C) catalysts were compared with Pd/SiO₂ for the hydrogenation of several diene molecules, 1,3- butadiene, 1,3- and 1,4-cyclohexadiene (CHD). Compared to Pd/SiO₂, Mo₂C showed similar hydrogenation rate for 1,3-butadiene and 1,3-CHD and even higher rate for 1,4-CHD, but with significant deactivation rate for 1,3-CHD hydrogenation. However, the hydrogenation activity of Mo₂C could be completely regenerated by H₂ treatment at 723 K for the three molecules. The Ni modified Mo₂C catalysts retained similar activity for 1,3-butadiene hydrogenation with significantly enhanced selectivity for 1-butene production. The 1-butene selectivity increased with increasing Ni loading below 15%. Among the Nimore » modified Mo₂C catalysts, 8.6%Ni/Mo₂C showed the highest selectivity to 1-butene, which was even higher selectivity than that over Pd/SiO₂. Compared to Pd/SiO₂, both Mo₂C and Ni/Mo₂C showed combined advantages in hydrogenation activity and catalyst cost reduction, demonstrating the potential to use less expensive carbide catalysts to replace precious metals for hydrogenation reactions.« less

Structural and electrochemical characterization of carbon supported Pt-Pr catalysts for direct ethanol fuel cells prepared using a modified formic acid method in a CO atmosphere.

PubMed

Corradini, Patricia Gon; Antolini, Ermete; Perez, Joelma

2013-07-28

Pt-Pr/C electrocatalysts were prepared using a modified formic acid method, and their activity for carbon monoxide and ethanol oxidation was compared to Pt/C. No appreciable alloy formation was detected by XRD analysis. By TEM measurements it was found that Pt particle size increases with an increasing Pr content in the catalysts and with decreasing metal precursor addition time. XPS measurements indicated Pt segregation on the catalyst surface and the presence of Pr2O3 and PrO2 oxides. The addition of Pr increased the electro-catalytic activity of Pt for both CO and CH3CH2OH oxidation. The enhanced activity of Pt-Pr/C catalysts was ascribed to both an electronic effect, caused by the presence of Pr2O3, and the bi-functional mechanism, caused by the presence of PrO2.

Lithium modified zeolite synthesis for conversion of biodiesel-derived glycerol to polyglycerol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ayoub, Muhammad, E-mail: muhammad.ayoub@petronas.com.my; Abdullah, Ahmad Zuhairi, E-mail: chzuhairi@usm.my; Inayat, Abrar, E-mail: abrar.inayat@petronas.com.my

Basic zeolite has received significant attention in the catalysis community. These zeolites modified with alkaline are the potential replacement for existing zeolite catalysts due to its unique features with added advantages. The present paper covers the preparation of lithium modified zeolite Y (Li-ZeY) and its activity for solvent free conversion of biodiesel-derived glycerol to polyglycerol via etherification process. The modified zeolite was well characterized by X-ray diffraction (XRD), Scanning Electron Microscope (SEM) and Nitrogen Adsorption. The SEM images showed that there was no change in morphology of modified zeolite structure after lithium modification. XRD patterns showed that the structure ofmore » zeolite was sustained after lithium modification. The surface properties of parent and modified zeolite was also observed N{sub 2} adsortion-desorption technique and found some changes in surface area and pore size. In addition, the basic strength of prepared materials was measured by Hammet indicators and found that basic strength of Li-ZeY was highly improved. This modified zeolite was found highly thermal stable and active heterogamous basic catalyst for conversion of solvent free glycerol to polyglycerol. This reaction was conducted at different temperatures and 260 °C was found most active temperature for this process for reaction time from 6 to 12 h over this basic catalyst in the absence of solvent.« less

Infrared absorption spectroscopy characterization of liquid-solid interfaces: The case of chiral modification of catalysts

NASA Astrophysics Data System (ADS)

Zaera, Francisco

2018-03-01

An overview is provided here of our work on the characterization of chiral modifiers for the bestowing of enantioselectivity to metal-based hydrogenation catalysts, with specific reference to the so-called Orito reaction. We start with a brief discussion of the use of infrared absorption spectroscopy (IR) for the characterization of chemical species at liquid-solid interfaces, describing the options available as well as the information that can be extracted from such experiments and the advantages and disadvantages associated with the technique. We then summarize the main results that we have reported to date from our IR study of the adsorption of cinchona alkaloids and related compounds from solutions onto platinum surfaces. Several observations are highlighted and placed in context in terms of the existing knowledge and their relevance to catalysis. Key conclusions include the uniqueness of the nature of the adsorbed species when in the presence of the solvent (versus when the uptake is done under vacuum, or versus the pure or dissolved molecules), the fact that each modifier adopts unique and distinct adsorption geometries on the surface and that those change with the concentration of the solution in ways that correlate well with the performance of the catalyst, the potential tendency of at least some of these chiral modifiers to bind to the surface primarily via the nitrogen atom of the amine group, not the aromatic ring as it is often assumed, and the observation that the ability of one modifier to dominate the catalytic chemistry in solutions containing mixtures of two or more of those is linked to their capacity for displacing each other from the surface, which in turn is determined by a balance between the strength of their binding to the surface and their solubility in the liquid solvent.

Multinuclear group 4 catalysis: olefin polymerization pathways modified by strong metal-metal cooperative effects.

PubMed

McInnis, Jennifer P; Delferro, Massimiliano; Marks, Tobin J

2014-08-19

Polyolefins are produced today catalytically on a vast scale, and the manufactured polymers find use in everything from artificial limbs and food/medical packaging to automotive and electrical components and lubricants. Although polyolefin monomers are typically cheap (e.g., ethylene, propylene, α-olefins), the resulting polymer properties can be dramatically tuned by the particular polymerization catalyst employed, and reflect a rich interplay of macromolecular chemistry, materials science, and physics. For example, linear low-density polyethylene (LLDPE), produced by copolymerization of ethylene with linear α-olefin comonomers such as 1-butene, 1-hexene, or 1-octene, has small but significant levels of short alkyl branches (C2, C4, C6) along the polyethylene backbone, and is an important technology material due to outstanding rheological and mechanical properties. In 2013, the total world polyolefin production was approximately 211 million metric tons, of which about 11% was LLDPE. Historically, polyolefins were produced using ill-defined but highly active heterogeneous catalysts composed of supported groups 4 or 6 species (usually halides) activated by aluminum alkyls. In 1963, Karl Ziegler and Giulio Natta received the Nobel Prize for these discoveries. Beginning in the late 1980s, a new generation of group 4 molecule-based homogeneous olefin polymerization catalysts emerged from discoveries by Walter Kaminsky, a team led by James Stevens at The Dow Chemical Company, this Laboratory at Northwestern University, and a host of talented groups in Germany, Italy, Japan, the United Kingdom, and the United States. These new "single-site" catalysts and their activating cocatalysts were far better defined and more rationally tunable in terms of structure, mechanism, thermodynamics, and catalyst activity and selectivity than ever before possible. An explosion of research advances led to new catalysts, cocatalysts, deeper mechanistic understanding of both the homogeneous and heterogeneous systems, macromolecules with dramatically altered properties, and large-scale industrial processes. It is noteworthy that many metalloenzymes employ multiple active centers operating in close synergistic proximity to achieve high activity and selectivity. Such enzymes were the inspiration for the research discussed in this Account, focused on the properties of multimetallic olefin polymerization catalysts. Here we discuss how modifications in organic ligand architecture, metal···metal proximity, and cocatalyst can dramatically modify polyolefin molecular weight, branch structure, and selectively for olefinic comonomer enchainment. We first discuss bimetallic catalysts with identical group 4 metal centers and then heterobimetallic systems with either group 4 or groups 4 + 6 catalytic centers. We compare and contrast the polymerization properties of the bimetallic catalysts with their monometallic analogues, highlighting marked cooperative enchainment effects and unusual polymeric products possible via the proximate catalytic centers. Such multinuclear olefin polymerization catalysts exhibit the following distinctive features: (1) unprecedented levels of polyolefin branching; (2) enhanced enchainment selectivity for linear and encumbered α-olefin comonomers; (3) enhanced polyolefin tacticity and molecular weight; (4) unusual 1,2-insertion regiochemistry for styrenic monomers; (5) modified chain transfer kinetics, such as M-polymer β-hydride transfer to the metal or incoming monomer; (6) LLDPE synthesis with a single binuclear catalyst and ethylene.

Tuning Ni-catalyzed CO 2 hydrogenation selectivity via Ni-ceria support interactions and Ni-Fe bimetallic formation

DOE PAGES

Winter, Lea R.; Gomez, Elaine; Yan, Binhang; ...

2017-10-16

CO 2 hydrogenation over Fe-modified Ni/CeO 2 catalysts was investigated in a batch reactor using time-resolved in situ FTIR spectroscopy. Low loading of Ni/CeO 2 was associated with high selectivity to CO over CH 4, while higher Ni loading improved CO 2 hydrogenation activity with a reduced CO selectivity. X-ray absorption near-edge structure (XANES) analysis revealed Ni to be metallic for all catalysts including the CO-selective low loading 0.5% Ni catalyst, suggesting that the selectivity trend is due to structural rather than oxidation state effects. The loading amount of 1.5% Ni was selected for co-impregnation with Fe, based on themore » significant shift in product selectivity towards CH 4 for that loading amount, in order to shift the selectivity towards CO while maintaining high activity. Temperature programmed reduction (TPR) results indicated bimetallic interactions between Ni and Fe, and XANES analysis showed that about 70% of Fe in the bimetallic catalysts was oxidized. The Ni-Fe catalysts demonstrated improved selectivity towards CO without significantly compromising activity, coupling the high activity of Ni catalysts and the high CO selectivity of Fe. The general trends in Ni loading and bimetallic modification should guide efforts to develop non-precious metal catalysts for the selective production of CO by CO 2 hydrogenation.« less

Preparation and Characterization of TiO2-Based Photocatalysts by Chemical Vapour Deposition

NASA Astrophysics Data System (ADS)

Nacevski, Goran; Marinkovski, Mirko; Tomovska, Radmila; Fajgar, Radek

In the present work, a novel technique for the preparation of TiO2-based photocatalysts modified with SiO2 is presented, using a pulsed ArF laser to induce a chemical vapor deposition process. The irradiated gas mixture was composed of TiCl4/SiCl4 precursors in excess of oxygen. Laser irradiation at 193 nm with a repetition frequency of 10 Hz induced the deposition of thin nano-sized mixed oxide films. In order to improve the photocatalytic activity of the catalysts and to expand the activity from the UV to the visible part of the spectrum, doping of the catalysts with chromium oxides was performed. For that aim, the same technique of catalyst preparation was used, irradiating the same gas mixture with the addition of chromyl chloride as Cr precursor. The thin films prepared were annealed up to 500°C in order to remove crystal defects, which could be responsible for poor photocatalytic activity. The dependence of structure and properties on reaction process and irradiation conditions (laser energy and fluence, precursors pressure) were examined. The main aim was to find the best conditions for the production of highly photoactive catalysts and to decrease deactivation processes during the photo-oxidation. The composition, structure and morphology of the oxide catalysts prepared were studied by various spectroscopies, electron microscopy and diffraction techniques.

Water reduction by a p-GaInP2 photoelectrode stabilized by an amorphous TiO2 coating and a molecular cobalt catalyst.

PubMed

Gu, Jing; Yan, Yong; Young, James L; Steirer, K Xerxes; Neale, Nathan R; Turner, John A

2016-04-01

Producing hydrogen through solar water splitting requires the coverage of large land areas. Abundant metal-based molecular catalysts offer scalability, but only if they match noble metal activities. We report on a highly active p-GaInP2 photocathode protected through a 35-nm TiO2 layer functionalized by a cobaloxime molecular catalyst (GaInP2-TiO2-cobaloxime). This photoelectrode mediates H2 production with a current density of ∼9 mA cm(-2) at a potential of 0 V versus RHE under 1-sun illumination at pH 13. The calculated turnover number for the catalyst during a 20-h period is 139,000, with an average turnover frequency of 1.9 s(-1). Bare GaInP2 shows a rapid current decay, whereas the GaInP2-TiO2-cobaloxime electrode shows ≤5% loss over 20 min, comparable to a GaInP2-TiO2-Pt catalyst particle-modified interface. The activity and corrosion resistance of the GaInP2-TiO2-cobaloxime photocathode in basic solution is made possible by an atomic layer-deposited TiO2 and an attached cobaloxime catalyst.

Catalytic evaluation on liquid phase oxidation of vanillyl alcohol using air and H2O2 over mesoporous Cu-Ti composite oxide

NASA Astrophysics Data System (ADS)

Saha, Subrata; Hamid, Sharifah Bee Abd; Ali, Tammar Hussein

2017-02-01

A mesoporous, highly crystalline Cu-Ti composite oxide catalyst was prepared via facile, simple and modified solution method varying Cu and Ti ratio for selective liquid phase oxidation of vanillyl alcohol. Various spectroscopic procedures were employed to systematically characterize the catalyst structural and physicochemical properties. The defect chemistry of the catalyst was confirmed from the presence of surface defects revealed through HRTEM imagery between the TiO2 (101) and Cu3TiO4 (012) planes, complemented by the XRD profiling. Further, presence of oxygen vacancy evidenced by O 1s XPS spectra were observed on the catalyst surface. Moreover, the stoichiometry of Cu and Ti in the catalyst synthesis protocol was notably found to be the vital determinant to alter the redox properties of Cu-Ti composite oxide catalyst supported by H2-TPR. O2-TPD analysis. Moreover, a rational investigation was done using different oxidants such as air and H2O2 with variables reaction conditions. The catalyst was active for liquid phase oxidation of vanillyl alcohol to vanillin with performance of 66% conversion and 71% selectivity using H2O2 in base free condition. And also, catalytic activity was significantly improved by 94% conversion with 86% selectivity to vanillin in liquid phase aerobic oxidation at the optimum reaction conditions. To expand the superiority of the catalyst, three times reusability study was also examined with appreciable catalytic activity.

Degradation of Acid Orange 7 by peroxymonosulfate activated with the recyclable nanocomposites of g-C3N4 modified magnetic carbon.

PubMed

Guo, Furong; Lu, Jiahua; Liu, Qing; Zhang, Ping; Zhang, Aiqing; Cai, Yingjie; Wang, Qiang

2018-08-01

Carbon-based catalysts have attracted high attention since they are greener and cheaper, while magnetic nanomaterials are very useful in environmental application because of the easy recovery and operation given by the magnetic separability. Therefore, graphitic carbon nitride modified magnetic carbon nanocomposites Fe 3 O 4 @C/g-C 3 N 4 was prepared herein for the first time as a new carbon-based catalyst for the activation of peroxymonosulfate (PMS). The catalytic properties of Fe 3 O 4 @C/g-C 3 N 4 in activating PMS for the degradation of Acid Orange 7 (AO 7), a model organic pollutant, were investigated. AO 7 degradation efficiency was significantly enhanced after modification of Fe 3 O 4 @C with g-C 3 N 4 , and the composite Fe 3 O 4 @C/g-C 3 N 4 from loading of 5 wt% g-C 3 N 4 and calcined at 300 °C for 30 min exhibited the best performance. AO 7 could be efficiently decolorized using the "Fe 3 O 4 @C/C 3 N 4 (5%) + PSM" system within the pH range of 2-6, and 97% of AO 7 could be removed in 20 min without pH adjustment (pH = 4). Radical quenching and EPR studies confirmed that both sulfate and hydroxyl radicals produced from PMS activation were the active species responsible for the oxidation of AO 7. The degradation mechanism was suggested based on the experimental results and XPS analyses. It was proposed that the CO groups on the carbon surface of Fe 3 O 4 @C rather than the CO in g-C 3 N 4 played a key role as the active sites for PMS activation. The catalyst was magnetically separable and displayed good stability and reusability, thus providing a potentially green catalyst for sustainable remediation of organic pollutants. Copyright © 2018 Elsevier Ltd. All rights reserved.

An efficient and heterogeneous recyclable silicotungstic acid with modified acid sites as a catalyst for conversion of fructose and sucrose into 5-hydroxymethylfurfural in superheated water.

PubMed

Jadhav, Arvind H; Kim, Hern; Hwang, In Taek

2013-03-01

Acidity modified silver exchanged silicotungstic acid (AgSTA) catalyst was prepared and characterized by X-ray diffraction, FT-IR spectroscopy, Raman spectroscopy, FT-IR pyridine adsorption, SEM imaging, EDX mapping, and antimicrobial activity was also tested. The catalytic activity was evaluated for the dehydration of fructose and sucrose in superheated water. As a result, 98% conversion of fructose with 85.7% HMF yield and 87.4% HMF selectivity in 120 min reaction time at 120 °C reaction temperature using 10 wt.% of AgSTA catalyst was achieved. While, 92% sucrose conversion with 62.5% of HMF yield was obtained from sucrose at uniform condition in 160 min. The effect of reaction parameters, such as reaction temperature, time, catalyst dosage, and effect acidity on HMF yield was also investigated. The AgSTA catalyst was separated from the reaction mixture by filtration process at end of the reaction and reused eight times without loss of catalytic activity. Copyright © 2013 Elsevier Ltd. All rights reserved.

Rate and Selectivity Control in Thioether and Alkene Oxidation with H 2 O 2 over Phosphonate-Modified Niobium(V)-Silica Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thornburg, Nicholas E.; Notestein, Justin M.

Supported metal oxide catalysts are versatile materials for liquid-phase oxidations, including alkene epoxidation and thioether sulfoxidation with H2O2. Periodic trends in H2O2 activation was recently demonstrated for alkene epoxidation, highlighting Nb-SiO2 as a more active and selective catalyst than Ti-SiO2. Three representative catalysts are studied consisting of NbV, TiIV, and ZrIV on silica, each made through a molecular precursor approach that yields highly dispersed oxide sites, for thioanisole oxidation by H2O2. Initial rates trend Nb>Ti>>Zr, as for epoxidation, and Nb outperforms Ti for a number of other thioethers. In contrast, selectivity to sulfoxide vs. sulfone trends Ti>Nb>>Zr at all conversions.more » Modifying the Nb-SiO2 catalyst with phenylphosphonic acid does not completely remove sulfoxidation reactivity, as it did for photooxidation and epoxidation, and results in an unusual material active for sulfoxidation but neither epoxidation nor overoxidation to the sulfone.« less

The conversion of biomass to light olefins on Fe-modified ZSM-5 catalyst: Effect of pyrolysis parameters.

PubMed

Zhang, Shihong; Yang, Mingfa; Shao, Jingai; Yang, Haiping; Zeng, Kuo; Chen, Yingquan; Luo, Jun; Agblevor, Foster A; Chen, Hanping

2018-07-01

Light olefins are the key building blocks for the petrochemical industry. In this study, the effects of in-situ and ex-situ process, temperature, Fe loading, catalyst to feed ratio and gas flow rate on the olefins carbon yield and selectivity were explored. The results showed that Fe-modified ZSM-5 catalyst increased the olefins yield significantly, and the ex-situ process was much better than in-situ. With the increasing of temperature, Fe-loading amount, catalyst to feed ratio, and gas flow rate, the carbon yields of light olefins were firstly increased and further decreased. The maximum carbon yield of light olefins (6.98% C-mol) was obtained at the pyrolysis temperature of 600°C, catalyst to feed ratio of 2, gas flow rate of 100ml/min, and 3wt% Fe/ZSM-5 for cellulose. The selectivity of C 2 H 4 was more than 60% for all feedstock, and the total light olefins followed the decreasing order of cellulose, corn stalk, hemicelluloses and lignin. Copyright © 2018 Elsevier B.V. All rights reserved.

Defect-rich Ni-Ti layered double hydroxide as a highly efficient support for Au nanoparticles in base-free and solvent-free selective oxidation of benzyl alcohol.

PubMed

Liu, Mengran; Fan, Guoli; Yu, Jiaying; Yang, Lan; Li, Feng

2018-04-17

Tuning the surface properties of supported metal catalysts is of vital importance for governing their catalytic performances in nanocatalysis. Here, we report highly dispersed nanometric gold nanoparticles (NPs) supported on Ni-Ti layered double hydroxides (NiTi-LDHs), which were employed in solvent-free and base-free selective oxidation of benzyl alcohol. A series of characterization techniques demonstrated that defect-rich NiTi-LDHs could efficiently stabilize Au NPs and decrease surface electron density of Au NPs. The as-formed Au/NiTi-LDH catalyst with a Ni/Ti molar ratio of 3 : 1 and an Au loading of 0.71 wt% yielded the highest turnover frequency value of ∼4981 h-1 at 120 °C among tested Au/NiTi-LDH catalysts with different Ni/Ti molar ratios, along with a high benzaldehyde selectivity of 98%. High catalytic efficiency of the catalyst was mainly correlated with surface cooperation between unique defects (i.e. defective Ti3+ species and oxygen vacancies) and abundant hydroxyl groups on the brucite-like layers of the NiTi-LDH support, which could lead to the preferential adsorption and activation of an alcohol hydroxyl moiety in benzyl alcohol and oxygen molecule, as well as the formation of more electron-deficient Ni3+ and Au0 species on the catalyst surface. Furthermore, the present Au/NiTi-LDH catalyst tolerated the oxidation of a wide variety of substrate structures into the corresponding aldehydes, acids or ketones. Our primary results illustrate that defect-rich NiTi-LDHs are promising supports which can efficiently modify surface structure and electronic properties of supported metal catalysts and consequently improve their catalytic performances.

ATOMIC-SCALE DESIGN OF IRON FISCHER-TROPSCH CATALYSTS: A COMBINED COMPUTATIONAL CHEMISTRY, EXPERIMENTAL, AND MICROKINETIC MODELING APPROACH

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manos Mavrikakis; James A. Dumesic; Amit A. Gokhale

2005-03-22

Efforts during this first year focused on four areas: (1) searching/summarizing published FTS mechanistic and kinetic studies of FTS reactions on iron catalysts; (2) construction of mass spectrometer-TPD and Berty CSTR reactor systems; (3) preparation and characterization of unsupported iron and alumina-supported iron catalysts at various iron loadings (4) Determination of thermochemical parameters such as binding energies of reactive intermediates, heat of FTS elementary reaction steps, and kinetic parameters such as activation energies, and frequency factors of FTS elementary reaction steps on a number of model surfaces. Literature describing mechanistic and kinetic studies of Fischer-Tropsch synthesis on iron catalysts wasmore » compiled in a draft review. Construction of the mass spectrometer-TPD system is 90% complete and of a Berty CSTR reactor system 98% complete. Three unsupported iron catalysts and three alumina-supported iron catalysts were prepared by nonaqueous-evaporative deposition (NED) or aqueous impregnation (AI) and characterized by chemisorption, BET, extent-of-reduction, XRD, and TEM methods. These catalysts, covering a wide range of dispersions and metal loadings, are well-reduced and relatively thermally stable up to 500-600 C in H{sub 2}, thus ideal for kinetic and mechanistic studies. The alumina-supported iron catalysts will be used for kinetic and mechanistic studies. In the coming year, adsorption/desorption properties, rates of elementary steps, and global reaction rates will be measured for these catalysts, with and without promoters, providing a database for understanding effects of dispersion, metal loading, and support on elementary kinetic parameters and for validation of computational models that incorporate effects of surface structure and promoters. Furthermore, using state-of-the-art self-consistent Density Functional Theory (DFT) methods, we have extensively studied the thermochemistry and kinetics of various elementary steps on three different model surfaces: (1) Fe(110), (2) Fe(110) modified by subsurface C, and (3) Fe surface modified with Pt adatoms. These studies have yielded valuable insights into the reactivity of Fe surfaces for FTS, and provided accurate estimates for the effect of Fe modifiers such as subsurface C and surface Pt.« less

Morphological investigation of nanostructured CoMo catalysts

NASA Astrophysics Data System (ADS)

Pawelec, B.; Castaño, P.; Zepeda, T. A.

2008-04-01

This work reports the morphological investigation of nanostructured sulfided CoMo catalysts by means of high-resolution transmission electron microscopy (HRTEM). The catalysts were supported on Ti-modified hexagonal mesoporous silica (HMS-Ti) and P-modified HMS-Ti (P/HMS-Ti) materials. The oxide precursors were characterized by specific surface area (S BET), temperature-programmed reduction (TPR), diffuse reflectance infrared Fourier transform spectroscopy in the OH region (DRIFTS-OH) and X-ray photoelectron spectroscopy (XPS) in order to elucidate the influence of the impregnation sequence (successive vs. simultaneous) and the effect of P-incorporation into HMS-Ti material on the morphology of calcined CoMo catalysts. Both TPR and XPS measurements indicate that the catalysts prepared by successive impregnation possess well-dispersed MoO 3 and CoO phases, whereas their counterparts prepared by simultaneous impregnation additionally possess the CoMoO 4 phase. For all sulfided catalysts, the presence of MoS 2 phase with particle size in the range 3.3-4.4 nm was confirmed by HRTEM. Catalytic activity was evaluated in the reaction of hydrodesulfurization (HDS) of dibenzothiophene (DBT) carried out in a flow reactor at 593 K and hydrogen pressure of 5.5 MPa. P-incorporation into the HMS-Ti material led to an overall increase in HDS activity and the hydrogenation ability of the sulfided catalysts. All catalysts proved to be stable during 10 h time-on-stream (TOS) operation. The activity of sulfide catalysts in the target reaction depends linearly on the surface exposure of Co species in the oxide precursors, as determined by XPS, and on the morphology of the sulfide form of catalysts (surface density of MoS 2 particles and their sizes) as determined by HRTEM.

Rhodium(II) metallopeptide catalyst design enables fine control in selective functionalization of natural SH3 domains.

PubMed

Vohidov, Farrukh; Coughlin, Jane M; Ball, Zachary T

2015-04-07

Chemically modified proteins are increasingly important for use in fundamental biophysical studies, chemical biology, therapeutic protein development, and biomaterials. However, chemical methods typically produce heterogeneous labeling and cannot approach the exquisite selectivity of enzymatic reactions. While bioengineered methods are sometimes an option, selective reactions of natural proteins remain an unsolved problem. Here we show that rhodium(II) metallopeptides combine molecular recognition with promiscuous catalytic activity to allow covalent decoration of natural SH3 domains, depending on choice of catalyst but independent of the specific residue present. A metallopeptide catalyst succeeds in modifying a single SH3-containing kinase at endogenous concentrations in prostate cancer (PC-3) cell lysate. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ/operando studies for the production of hydrogen through the water-gas shift on metal oxide catalysts.

PubMed

Rodriguez, José A; Hanson, Jonathan C; Stacchiola, Dario; Senanayake, Sanjaya D

2013-08-07

In this perspective article, we show how a series of in situ techniques {X-ray diffraction (XRD), pair-distribution-function analysis (PDF), X-ray absorption fine structure (XAFS), environmental transmission electron microscopy (ETEM), infrared spectroscopy (IR), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS)} can be combined to perform detailed studies of the structural, electronic and chemical properties of metal oxide catalysts used for the production of hydrogen through the water-gas shift reaction (WGS, CO + H2O → H2 + CO2). Under reaction conditions most WGS catalysts undergo chemical transformations that drastically modify their composition with respect to that obtained during the synthesis process. Experiments of time-resolved in situ XRD, XAFS, and PDF indicate that the active phase of catalysts which combine Cu, Au or Pt with oxides such as ZnO, CeO2, TiO2, CeOx/TiO2 and Fe2O3 essentially involves nanoparticles of the reduced noble metals. The oxide support undergoes partial reduction and is not a simple spectator, facilitating the dissociation of water and in some cases modifying the chemical properties of the supported metal. Therefore, to optimize the performance of these catalysts one must take into consideration the properties of the metal and oxide phases. IR and AP-XPS have been used to study the reaction mechanism for the WGS on metal oxide catalysts. Data of IR spectroscopy indicate that formate species are not necessarily involved in the main reaction path for the water-gas shift on Cu-, Au- and Pt-based catalysts. Thus, a pure redox mechanism or associative mechanisms that involve either carbonate-like (CO3, HCO3) or carboxyl (HOCO) species should be considered. In the last two decades, there have been tremendous advances in our ability to study catalytic materials under reaction conditions and we are moving towards the major goal of fully understanding how the active sites for the production of hydrogen through the WGS actually work.

Chemically-modified cellulose paper as a microstructured catalytic reactor.

PubMed

Koga, Hirotaka; Kitaoka, Takuya; Isogai, Akira

2015-01-15

We discuss the successful use of chemically-modified cellulose paper as a microstructured catalytic reactor for the production of useful chemicals. The chemical modification of cellulose paper was achieved using a silane-coupling technique. Amine-modified paper was directly used as a base catalyst for the Knoevenagel condensation reaction. Methacrylate-modified paper was used for the immobilization of lipase and then in nonaqueous transesterification processes. These catalytic paper materials offer high reaction efficiencies and have excellent practical properties. We suggest that the paper-specific interconnected microstructure with pulp fiber networks provides fast mixing of the reactants and efficient transport of the reactants to the catalytically-active sites. This concept is expected to be a promising route to green and sustainable chemistry.

Biodegradable polyester-based eco-composites containing hemp fibers modified with macrocyclic oligomers

NASA Astrophysics Data System (ADS)

Conzatti, Lucia; Utzeri, Roberto; Hodge, Philip; Stagnaro, Paola

2016-05-01

An original compatibilizing pathway for hemp fibers/poly(1,4-butylene adipate-co-terephtalate) (PBAT) eco-composites was explored exploiting the capability of macrocyclic oligomers (MCOs), obtained by cyclodepolymerization (CDP) of PBAT at high dilution, of being re-converted into linear chains by entropically-driven ring-opening polymerization (ED-ROP) that occurs simply heating the MCOS in the bulk. CDP reaction of PBAT was carried out varying solvent, catalyst and reaction time. Selected MCOs were used to adjust the conditions of the ED-ROP reaction. The best experimental conditions were then adopted to modify hemp fibers. Eco-composites based on PBAT and hemp fibers as obtained or modified with PBAT macrocyclics or oligomers were prepared by different process strategies. The best fiber-PBAT compatibility was observed when the fibers were modified with PBAT oligomers before incorporation in the polyester matrix.

Effect of one step KOH activation and CaO modified carbon in transesterification reaction

NASA Astrophysics Data System (ADS)

Yacob, Abd Rahim; Zaki, Muhammad Azam Muhammad

2017-11-01

In this work, one step activation was introduced using potassium hydroxide (KOH) and calcium oxide (CaO) modified palm kernel shells. Various concentration of calcium oxide was used as catalyst while maintaining the same concentration of potassium hydroxide to activate and impregnate the palm kernel shell before calcined at 500°C for 5 hours. All the prepared samples were characterized using Fourier Transform Infrared (FTIR) and Field Emission Scanning Electron Microscope (FESEM). FTIR analysis of raw palm kernel shell showed the presence of various functional groups. However, after activation, most of the functional groups were eliminated. The basic strength of the prepared samples were determined using back titration method. The samples were then used as base heterogeneous catalyst for the transesterification reaction of rice bran oil with methanol. Analysis of the products were performed using Gas Chromatography Flame Ionization Detector (GC-FID) to calculate the percentage conversion of the biodiesel products. This study shows, as the percentage of one step activation potassium and calcium oxide doped carbon increases thus, the basic strength also increases followed by the increase in biodiesel production. Optimization study shows that the optimum biodiesel production was at 8 wt% catalyst loading, 9:1 methanol: oil molar ratio at 65°C and 6 hours which gives a conversion up to 95%.

Ordered macroporous platinum electrode and enhanced mass transfer in fuel cells using inverse opal structure.

PubMed

Kim, Ok-Hee; Cho, Yong-Hun; Kang, Soon Hyung; Park, Hee-Young; Kim, Minhyoung; Lim, Ju Wan; Chung, Dong Young; Lee, Myeong Jae; Choe, Heeman; Sung, Yung-Eun

2013-01-01

Three-dimensional, ordered macroporous materials such as inverse opal structures are attractive materials for various applications in electrochemical devices because of the benefits derived from their periodic structures: relatively large surface areas, large voidage, low tortuosity and interconnected macropores. However, a direct application of an inverse opal structure in membrane electrode assemblies has been considered impractical because of the limitations in fabrication routes including an unsuitable substrate. Here we report the demonstration of a single cell that maintains an inverse opal structure entirely within a membrane electrode assembly. Compared with the conventional catalyst slurry, an ink-based assembly, this modified assembly has a robust and integrated configuration of catalyst layers; therefore, the loss of catalyst particles can be minimized. Furthermore, the inverse-opal-structure electrode maintains an effective porosity, an enhanced performance, as well as an improved mass transfer and more effective water management, owing to its morphological advantages.

TiO2@TDI@DMAPA: an amine-modified nanoparticle, tailored to act as an economic basic heterogeneous nanocatalyst

NASA Astrophysics Data System (ADS)

Esfahanian, Farzane; Amoozadeh, Ali; Bitaraf, Mehrnoosh

2018-06-01

This study has represented an easy and inexpensive method for the synthesis of a new basic nanocatalyst. In this regard, 3-dimethylaminopropylamine (DMAPA), an economic, industrial, and readily obtainable basic compound, has been grafted onto nano-titania particles by the use of 2,4-toluene diisocyanate (TDI) as a bi-functional, inexpensive, and highly reactive linker. The prepared catalyst has been characterized using the spectroscopic FT-IR method, XRD, FE-SEM, EDX, and back titration. Furthermore, it was identified as an effective catalyst in the preparation of DHPM derivatives and pyranopyrazoles which results in high purity and high yields of products. Response surface methodology (RSM) based on a central composite design (CCD) was employed to reach the optimal conditions. The catalyst can be readily separated and recycled up to six times. [Figure not available: see fulltext.

Experimental evidence of {alpha}-olefin readsorption in Fischer-Tropsch synthesis on ruthenium-supported ETS-10 titanium silicate catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bianchi, C.L.; Ragaini, V.

1997-05-01

Fischer-Tropsch synthesis seems to develop the following two consecutive paths: a primary process that involves the formation of {alpha}-olefin products and a secondary process leading to the production of branched isomers and paraffins and requiring the readsorption of primary {alpha}-olefin products. It was already shown by Iglesia et al. that such readsorption steps are of fundamental importance for Ru catalysts and that they occur due to the slow diffusive removal of {alpha}-olefins when the molecular size increases, this resulting in a long intraparticle residence time. In the present paper {alpha}-olefins readsorption was enhanced by changing the metal distribution inside themore » pores of a titanium silicate (ETS-10), modified by ion exchange with alkali metal ions, used as a support for Ru-based catalysts. 24 refs., 5 figs., 3 tabs.« less

Self-healing polymers---The importance of choosing an adequate healing monomer, and the olefin metathesis polymerization of agricultural oils

NASA Astrophysics Data System (ADS)

Mauldin, Timothy C.

Modern society's immense and ill-fated reliance on petrochemical-based polymeric materials will likely necessitate a shift in polymer production paradigms in the near future. The work presented herein attempts to address this issue via a two-pronged approach. First, efforts to improve the duration of composite materials by incorporation of a self-healing function are discussed, the fruitful application of which can potentially reduce or eliminate the massive carbon footprints associated with the repair/replacement of damaged materials. And second, polymeric materials derived predominately from natural and renewable feedstock---namely vegetable oils---are developed. Early microcapsule-based self-healing materials utilized dicyclopentadiene-filled microcapsules and Grubbs' olefin metathesis catalyst to initiate the healing mechanism. However, the patent-protected catalyst, made from the precious metal ruthenium and sometimes costly ligands, will likely never be inexpensive and therefore limit large-scale applications. Hence, clever approaches to reduce the healing catalyst loading in self-healing polymers are of great interest. To this end, our efforts have revolved around solving the problem of the relatively inefficient use of Grubbs' catalyst during the healing mechanism. Given that the mismatch of the olefin metathesis polymerization and Grubbs' catalyst dissolution (in monomer) kinetics is a known cause of this inefficient use of the catalyst, we attempted to tune the "latency" (i.e. pot life) of the olefin metathesis polymerization to ensure more complete dissolution of catalyst in monomer. In an alternative approach to improving efficient catalyst dissolution, we developed a simple model to predict relative dissolution rates of Grubbs' catalyst in a small library of healing monomers. This model was shown experimentally to be able to aid in the selection of, for example, reactive monomer additives that can yield impressive improvements in catalyst dissolution at small loadings. Furthermore, we have recently developed a novel rheokinetic technique designed to mimic the self-healing mechanism. This new analytical technique allows for collection of copious amounts of information related to the self-healing mechanism (e.g. healing kinetics, rheological and mechanical changes of polymerizing healing agents, adhesive interactions between healing agent and polymer matrix, etc.) to be extracted from a single experiment. New polymers derived from renewable feeds were synthesized via olefin metathesis polymerization techniques, which are ideally suited to react with the unactivated olefins (i.e. non-styrenic, non-acrylated, non-conjugated, etc.) prominent in most vegetable oils. Various vegetable oils were modified to contain norbornenyl functional groups via the high-pressure Diels-Alder addition of cyclopentadiene to their olefins to yield ROMP-reactive monomers. These monomers, polymerized in the presence of Grubbs' catalyst and the occasional comonomer, were able to yield highly crosslinked thermosets with ambient temperature storage moduli, glass transition temperatures and decomposition temperatures comparable to their currently-used, petrochemical-based counterparts. Other research thrusts in this area have focused on the development of renewable thermoplastic polymers. Vegetable oils were chemically modified to yield a series of alpha,o-dienes, from which polymers were formed via acyclic diene metathesis (ADMET). The resulting polymers were shown to have unique material properties, comparable to that of other biopolyesters (poly(lactic acid), poly(glycolides), poly(caprolactones), etc.) and common, petrochemical-derived polyesters.

NO removal by nonthermal plasma with modified sepiolite catalyst

NASA Astrophysics Data System (ADS)

Chen, M. G.; Yu, D. X.; Rong, J. F.; Wan, Y. L.; Li, G. C.; Ni, Y. M.; Fan, X.; Hou, G. H.; Xu, N.

2013-03-01

Non-Thermal Plasma (NTP) combined with a catalyst is one of the effective ways to remove NO from auto exhaust gas. Sepiolite Ore Powder (SOP), which was modified by acid washing, copper nitrate soaking, drying and calcinations, served as the Modified Sepiolite Catalyst (MSC) for NO removal in a rod-cylinder Dielectric Barrier Discharge (DBD) reactor. The characteristic of the MSC was characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The experiment showed that the acid concentration, washing time, the packed site of MSC and input voltage of the NTP impacted the NO removal rate effectively. The NO removal rate increased and then decreased with an increase in the acid concentration and the washing time, and the NO removal rate increased monotonously with the increased input voltage. The NO removal rate was higher at the beginning, decreased gradually then maintained stability after 10 min. Thus, the result indicated that MSC has a good ability for adsorption and storage of NO.

Citrate-capped superparamagnetic iron oxide (Fe3O4-CA) nanocatalyst for synthesis of pyrimidine derivative compound as antioxidative agent

NASA Astrophysics Data System (ADS)

Cahyana, A. H.; Pratiwi, D.; Ardiansah, B.

2017-04-01

The development of a recyclable catalyst based on magnetic nanoparticles has attracted an increasing interest as the emerging application in the heterogeneous catalyst field. Superparamagnetic iron oxide nanoparticle with citric acid as capping agent was successfully obtained from iron (III) chloride solution via two steps synthesis. The first step involving the formation of magnetite nanoparticle by bioreduction using Sargassum Sp, then its surface was modified by adding citric acid solution in the second step. The structural, surface morphology and magnetic properties of the nanocatalyst were investigated by various instrumentations such as scanning electron microscope with energy dispersive (SEM-EDS), and particle size analyser (PSA). Fe3O4-CA was then applied as reusable catalyst for Knoevenagel condensation of barbituric acid and cinnamaldehyde to produce (E)-5-(3-phenylallylidene)pyrimidine-2,4,6(1H,3H,5H)-trione. The optimum condition of this reaction was achieved by using 7.5% mole of catalyst at 50°C for 6 h to give 83% yield. Some spectroscopy techniques such as UV-Vis, FTIR, LC-MS and 1H-NMR were used to confirm the product’s structure. Furthermore, the synthesized compound has an attractive antioxidant activity based on the in-vitro analysis using DPPH method.

Adsorption properties of regenerative materials for removal of low concentration of toluene.

PubMed

Xie, Zhen-Zhen; Wang, Lin; Cheng, Ge; Shi, Lei; Zhang, Yi-Bo

2016-12-01

A specific type of material, activated carbon fiber (ACF), was modified by SiO 2 , and the final products ACF-x were obtained as ACF-12.5, ACF-20, ACF-40, and ACF-80 according to different dosages of tetraethoxysilane (TEOS). The modified material on the ACF surface had a significant and smooth cover layer with low content of silica from scanning electron microscope (SEM) image. The modified ACF-x showed the stronger hydrophobicity, thermal stability, and adsorption capacity, which had almost no effect in the presence of water vapor and no destruction in multiple cycles. ACF-20 was proven as the most efficient adsorbent in humid conditions. The dual-function system composed of the regenerative adsorbents and the combustion catalyst would be efficient in consecutive toluene adsorption/oxidation cycles, in which the combustion catalyst was prepared by the displacement reaction of H 2 PtCl 6 with foam Ni. Therefore, the adsorption/catalytic oxidation could be a promising technique in the indoor air purification, especially in the case of very low volatile organic compound (VOC; toluene) concentration levels. Exploring highly effective adsorptive materials with less expensive costs becomes an urgent issue in the indoor air protection. ACF-20 modified by SiO 2 with Pt/Ni catalysts shows stronger hydrophobicity, thermal stability, and adsorption capacity. This dual-function system composed of the regenerative materials and the combustion catalyst would be a promising technique in the indoor air purification, especially in the case of removal of very low concentration of toluene.

Functionalization of multi-walled carbon nanotubes with iron phthalocyanine via a liquid chemical reaction for oxygen reduction in alkaline media

NASA Astrophysics Data System (ADS)

Yan, Xiaomei; Xu, Xiao; Liu, Qin; Guo, Jia; Kang, Longtian; Yao, Jiannian

2018-06-01

Iron single-atom catalyst in form of iron-nitrogen-carbon structure possesses the excellent catalytic activity in various chemical reactions. However, exploring a sustainable and stable single-atom metal catalyst still faces a great challenge due to low yield and complicated synthesis. Here, we report a functional multi-wall carbon nanotubes modified with iron phthalocyanine molecules via a liquid chemical reaction and realize the performance of similar single-atom catalysis for oxygen reduction reaction. A serial of characterizations strongly imply the structure change of iron phthalocyanine molecule and its close recombination with multi-wall carbon nanotubes, which are in favor of ORR catalysis. Compared to commercial platinum-carbon catalyst, composites exhibit superior activity for oxygen reduction reaction with higher half-wave potential (0.86 V), lower Tafel slope (38 mV dec-1), higher limiting current density and excellent electrochemical stability. The corresponding Zinc-air battery also presents higher maximum power density and discharge stability. Therefore, these findings provide a facile route to synthesize a highly efficient non-precious metal carbon-based catalyst.

Catalytic wet peroxide oxidation of aniline in wastewater using copper modified SBA-15 as catalyst.

PubMed

Kong, Liming; Zhou, Xiang; Yao, Yuan; Jian, Panming; Diao, Guowang

2016-01-01

SBA-15 mesoporous molecular sieves modified with copper (Cu-SBA-15) were prepared by pH-adjusting hydrothermal method and characterized by X-ray diffraction, BET, transmission electron microscopy, UV-Vis and (29)Si MAS NMR. The pH of the synthesis gel has a significant effect on the amount and the dispersion of copper on SBA-15. The Cu-SBA-15(4.5) (where 4.5 denotes the pH value of the synthesis gel) modified with highly dispersed copper was used as catalyst for the oxidation of aniline by H2O2. The Cu-SBA-15(4.5) shows a higher catalytic activity compared to CuO on the surface of SBA-15. The influences of reaction conditions, such as initial pH of the aqueous solutions, temperature, as well as the dosages of H2O2 and catalyst were investigated. Under weakly alkaline aqueous solution conditions, the aniline conversion, the H2O2 decomposition and the total organic carbon (TOC) removal could be increased significantly compared to the acid conditions. The percentage of leaching Cu(2+) could be decreased from 45.0% to 3.66% when the initial pH of solution was increased from 5 to 10. The TOC removal could be enhanced with the increases of temperature, H2O2 and catalyst dosage, but the aniline conversion and H2O2 decomposition change slightly with further increasing dosage of catalyst and H2O2. At 343 K and pH 8.0, 100% aniline conversion and 66.9% TOC removal can be achieved under the conditions of 1.0 g/L catalyst and 0.05 mol/L H2O2 after 180 min. Although copper might be slightly leached from catalyst, the homogeneous Cu(2+) contribution to the whole catalytic activity is unimportant, and the highly dispersed copper on SBA-15 plays a dominant role.

Application of surface modified nano ferrite nickel in catalytic reaction (epoxidation of alkenes) and investigation on its antibacterial and antifungal activities.

PubMed

Golkhatmi, Faezeh Mahdinejad; Bahramian, Bahram; Mamarabadi, Mojtaba

2017-09-01

Newly, magnetic nanoparticles have extensively been used as alternative catalyst supports, in the view of their high surface area which results in high catalyst loading capacity, high dispersion, low toxicity, environmental preservation, distinguished stability, and suitable catalyst reusing. In the present study, the magnetite nanoparticles, NiFe 2 O 4 @Ag and NiFe 2 O 4 @Mo, were synthesized and characterized. The antimicrobial activities and catalytic properties of synthesized nanoparticles were tested afterwards. For synthetizing the nanoparticle NiFe 2 O 4 @Ag, silver ions were loaded onto the surface of the modified NiFe 2 O 4 and reduced to silver crystal by adding NaBH 4 . The antibacterial effects of NiFe 2 O 4 @Ag were examined against two species of soil and plant related bacteria named Bacillus subtilis (gram positive) and Pseudomonas syringae (gram negative), respectively. The antifungal activity of this nanoparticle was evaluated against two species of plant pathogenic fungi called Alternaria solani and Fusarium oxysporum. Biological results indicated that the synthesized material has shown an excellent antibacterial and antifungal activity against all examined bacteria and fungi so that, their growth were completely inhibited 24h after treatment with NiFe 2 O 4 @Ag. For the synthesis of a heterogeneous catalyst NiFe 2 O 4 @Mo, complex Mo(CO) 6 was loaded onto the surface of the modified NiFe 2 O 4 nanoparticle. This catalyst was found as an efficient catalyst for epoxidation of cis-cyclooctene and a wide variety of alkenes, including aromatic and aliphatic terminal ones using tert-butyl hydroperoxide as oxidant. This new heterogenized catalyst could easily be recovered by using a magnetic separator and reused four consecutive and loss only 13% of its catalytic activity. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis of fatty acid methyl ester from crude jatropha (Jatropha curcas Linnaeus) oil using aluminium oxide modified Mg-Zn heterogeneous catalyst.

PubMed

Olutoye, M A; Hameed, B H

2011-06-01

The synthesis of fatty acid methyl esters (FAME) as a substitute to petroleum diesel was investigated in this study from crude jatropha oil (CJO), a non-edible, low-cost alternative feedstock, using aluminium modified heterogeneous basic oxide (Mg-Zn) catalyst. The transesterification reaction with methanol to methyl esters yielded 94% in 6h with methanol-oil ratio of 11:1, catalyst loading of 8.68 wt.% at 182°C and the properties of CJO fuel produced were determine and found to be comparable to the standards according to ASTM. In the range of experimental parameters investigated, it showed that the catalyst is selective to production of methyl esters from oil with high free fatty acid (FFA) and water content of 7.23% and 3.28%, respectively in a single stage process. Thus, jatropha oil is a promising feedstock for methyl ester production and large scale cultivation will help to reduce the product cost. Copyright © 2011 Elsevier Ltd. All rights reserved.

Direct observation of morphological evolution of a catalyst during carbon nanotube forest growth: new insights into growth and growth termination

NASA Astrophysics Data System (ADS)

Jeong, Seojeong; Lee, Jaegeun; Kim, Hwan-Chul; Hwang, Jun Yeon; Ku, Bon-Cheol; Zakharov, Dmitri N.; Maruyama, Benji; Stach, Eric A.; Kim, Seung Min

2016-01-01

In this study, we develop a new methodology for transmission electron microscopy (TEM) analysis that enables us to directly investigate the interface between carbon nanotube (CNT) arrays and the catalyst and support layers for CNT forest growth without any damage induced by a post-growth TEM sample preparation. Using this methodology, we perform in situ and ex situ TEM investigations on the evolution of the morphology of the catalyst particles and observe the catalyst particles to climb up through CNT arrays during CNT forest growth. We speculate that the lifted catalysts significantly affect the growth and growth termination of CNT forests along with Ostwald ripening and sub-surface diffusion. Thus, we propose a modified growth termination model which better explains various phenomena related to the growth and growth termination of CNT forests.In this study, we develop a new methodology for transmission electron microscopy (TEM) analysis that enables us to directly investigate the interface between carbon nanotube (CNT) arrays and the catalyst and support layers for CNT forest growth without any damage induced by a post-growth TEM sample preparation. Using this methodology, we perform in situ and ex situ TEM investigations on the evolution of the morphology of the catalyst particles and observe the catalyst particles to climb up through CNT arrays during CNT forest growth. We speculate that the lifted catalysts significantly affect the growth and growth termination of CNT forests along with Ostwald ripening and sub-surface diffusion. Thus, we propose a modified growth termination model which better explains various phenomena related to the growth and growth termination of CNT forests. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05547d

Clean Transformation of Ethanol to Useful Chemicals. The Behavior of a Gold-Modified Silicalite Catalyst.

PubMed

Falletta, Ermelinda; Rossi, Michele; Teles, Joaquim Henrique; Della Pina, Cristina

2016-03-19

Upon addition of gold to silicalite-1 pellets (a MFI-type zeolite), the vapor phase oxidation of ethanol could be addressed to acetaldehyde or acetic acid formation. By optimizing the catalyst composition and reaction conditions, the conversion of ethanol could be tuned to acetaldehyde with 97% selectivity at 71% conversion or to acetic acid with 78% selectivity at total conversion. Considering that unloaded silicalite-1 was found to catalyze the dehydration of ethanol to diethylether or ethene, a green approach for the integrated production of four important chemicals is herein presented. This is based on renewable ethanol as a reagent and a modular catalytic process.

Hierarchical SAPO‐34 Architectures with Tailored Acid Sites using Sustainable Sugar Templates

PubMed Central

Miletto, Ivana; Ivaldi, Chiara; Paul, Geo; Chapman, Stephanie; Marchese, Leonardo; Raja, Robert

2018-01-01

Abstract In a distinct, bottom‐up synthetic methodology, monosaccharides (fructose and glucose) and disaccharides (sucrose) have been used as mesoporogens to template hierarchical SAPO‐34 catalysts. Detailed materials characterization, which includes solid‐state magic angle spinning NMR and probe‐based FTIR, reveals that, although the mesopore dimensions are modified by the identity of the sugar template, the desirable acid characteristics of the microporous framework are retained. When the activity of the hierarchical SAPO‐34 catalysts was evaluated in the industrially relevant Beckmann rearrangement, under liquid‐phase conditions, the enhanced mass‐transport properties of sucrose‐templated hierarchical SAPO‐34 were found to deliver a superior yield of ϵ‐caprolactam. PMID:29686961

Ultrafine cobalt nanoparticles supported on reduced graphene oxide: Efficient catalyst for fast reduction of hexavalent chromium at room temperature

NASA Astrophysics Data System (ADS)

Xu, Tingting; Xue, Jinjuan; Zhang, Xiaolei; He, Guangyu; Chen, Haiqun

2017-04-01

A novel composite ultrafine cobalt nanoparticles-reduced graphene oxide (Co-RGO) was firstly synthesized through a modified one-step solvothermal method with Co(OH)2 as the precursor. The prepared low-cost Co-RGO composite exhibited excellent catalytic activity for the reduction of highly toxic Cr(VI) to nontoxic Cr(III) at room temperature when formic acid (HCOOH) was employed as the reductant, and its catalytic performance was even comparable with that of noble metal-based catalysts in the same reduction reaction. Moreover, Co-RGO composite could be readily recovered under an external magnetic field and efficiently participated in recycled reaction for Cr(VI) reduction.

Propitious Dendritic Cu2O-Pt Nanostructured Anodes for Direct Formic Acid Fuel Cells.

PubMed

El-Nagar, Gumaa A; Mohammad, Ahmad M; El-Deab, Mohamed S; El-Anadouli, Bahgat E

2017-06-14

This study introduces a novel competent dendritic copper oxide-platinum nanocatalyst (nano-Cu 2 O-Pt) immobilized onto a glassy carbon (GC) substrate for formic acid (FA) electro-oxidation (FAO); the prime reaction in the anodic compartment of direct formic acid fuel cells (DFAFCs). Interestingly, the proposed catalyst exhibited an outstanding improvement for FAO compared to the traditional platinum nanoparticles (nano-Pt) modified GC (nano-Pt/GC) catalyst. This was evaluated from steering the reaction mechanism toward the desired direct route producing carbon dioxide (CO 2 ); consistently with mitigating the other undesired indirect pathway producing carbon monoxide (CO); the potential poison deteriorating the catalytic activity of typical Pt-based catalysts. Moreover, the developed catalyst showed a reasonable long-term catalytic stability along with a significant lowering in onset potential of direct FAO that ultimately reduces the polarization and amplifies the fuel cell's voltage. The observed catalytic enhancement was believed to originate bifunctionally; while nano-Pt represented the base for the FA adsorption, nanostructured copper oxide (nano-Cu 2 O) behaved as a catalytic mediator facilitating the charge transfer during FAO and providing the oxygen atmosphere inspiring the poison's (CO) oxidation at relatively lower potential. Surprisingly, moreover, nano-Cu 2 O induced a surface retrieval of nano-Pt active sites by capturing the poisoning CO via "a spillover mechanism" to renovate the Pt surface for the direct FAO. Finally, the catalytic tolerance of the developed catalyst toward halides' poisoning was discussed.

Studies on photocatalytic activity of the synthesised TiO2 and Ag/TiO2 photocatalysts under UV and sunlight irradiations.

PubMed

Vaithiyanathan, R; Sivakumar, T

2011-01-01

Photocatalytic decolorisation and degradation of Reactive Red 120 (RR 120) has been investigated under UV (365 nm) and solar light as radiation sources using synthesised nano titania catalyst prepared via sol-gel method. The study encompassed calcination of synthesised titania catalyst at a range of temperature up to 1,000°C. The effects of calcination temperature on titania catalyst have been evaluated on the decolorisation of RR 120. The analysis revealed complete decolorisation of dye solution in 100 min under UV light with the TiO2 catalyst calcined at 200°C. Only a maximum of 47% dye decolorisation was achieved under sunlight in 4 h with no improvement even after prolonged irradiation. In an endeavour to improve the catalytic activity, bare titania was modified with silver metal and a comprehensive study on the characteristics of silver modified catalyst was made. The result was an enhancement of the rate of decolorisation of dye under both UV and solar light sources. All the catalysts were characterised by XRD and BET analyses. Optimisation of the degradation of RR 120 has been carried out using the unmodified catalyst by varying the amount of catalyst, substrate concentration, pH of dye solution. Effects of addition of small amounts of various oxidants such as H2O2, KBrO3 and (NH4)2S2O8 have also been studied. Pseudo first order kinetics was observed in the photocatalytic decolorisation of dye. The mineralisation of RR 120 was monitored by TOC analysis.

Highly recoverable pyridinium-tagged Hoveyda-Grubbs pre-catalyst for olefin metathesis. Design of the boomerang ligand toward the optimal compromise between activity and reusability.

PubMed

Rix, Diane; Caïjo, Fréderic; Laurent, Isabelle; Gulajski, Lukasz; Grela, Karol; Mauduit, Marc

2007-09-28

Whereas the boomerang ligand of Hoveyda-Grubbs pre-catalysts can be modified by attachment of a pyridinium tag to its benzylidene moiety, a precise adjustment of the length of the spacer allows the optimum balance to be reached between the activity of the catalyst and its recoverability, exceeding 98% after 6 catalytic runs in the best case.

Paper-Based Analytical Devices Relying on Visible-Light-Enhanced Glucose/Air Biofuel Cells.

PubMed

Wu, Kaiqing; Zhang, Yan; Wang, Yanhu; Ge, Shenguang; Yan, Mei; Yu, Jinghua; Song, Xianrang

2015-11-04

A strategy that combines visible-light-enhanced biofuel cells (BFCs) and electrochemical immunosensor into paper-based analytical devices was proposed for sensitive detection of the carbohydrate antigen 15-3 (CA15-3). The gold nanoparticle modified paper electrode with large surface area and good conductibility was applied as an effective matrix for primary antibodies. The glucose dehydrogenase (GDH) modified gold-silver bimetallic nanoparticles were used as bioanodic biocatalyst and signal magnification label. Poly(terthiophene) (pTTh), a photoresponsive conducting polymer, served as catalyst in cathode for the reduction of oxygen upon illumination by visible light. In the bioanode, electrons were generated through the oxidation of glucose catalyzed by GDH. The amount of electrons is determined by the amount of GDH, which finally depended on the amount of CA15-3. In the cathode, electrons from the bioanode could combine with the generated holes in the HOMO energy level of cathode catalysts pTTh. Meanwhile, the high energy level photoexcited electrons were generated in the LUMO energy level and involved in the oxygen reduction reaction, finally resulting in an increasing current and a decreasing overpotential. According to the current signal, simple and efficient detection of CA15-3 was achieved.

Co-Pt core-shell nanostructured catalyst prepared by selective chemical vapor pulse deposition of Pt on Co as a cathode in polymer electrolyte fuel cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seo, Sang-Joon; Chung, Ho-Kyoon; Yoo, Ji-Beom

2014-01-15

A new type of PtCo/C catalyst for use as a cathode in polymer electrolyte fuel cells was prepared by selective chemical vapor pulse deposition (CVPD) of Pt on the surface of Co. The activity of the prepared catalyst for oxygen reduction was higher than that of a catalyst prepared by sequential impregnation (IMP) with the two metallic components. This catalytic activity difference occurs because the former catalyst has smaller Pt crystallites that produce stronger Pt-Co interactions and have a larger Pt surface area. Consequently, the CVPD catalyst has a great number of Co particles that are in close contact withmore » the added Pt. The Pt surface was also electronically modified by interactions with Co, which were stronger in the CVPD catalyst than in the IMP catalyst, as indicated by X-ray diffraction, X-ray photoemission spectroscopy, and cyclic voltammetry measurements of the catalysts.« less

Apparatus and Process for Controlled Nanomanufacturing Using Catalyst Retaining Structures

NASA Technical Reports Server (NTRS)

Nguyen, Cattien (Inventor)

2013-01-01

An apparatus and method for the controlled fabrication of nanostructures using catalyst retaining structures is disclosed. The apparatus includes one or more modified force microscopes having a nanotube attached to the tip portion of the microscopes. An electric current is passed from the nanotube to a catalyst layer of a substrate, thereby causing a localized chemical reaction to occur in a resist layer adjacent the catalyst layer. The region of the resist layer where the chemical reaction occurred is etched, thereby exposing a catalyst particle or particles in the catalyst layer surrounded by a wall of unetched resist material. Subsequent chemical vapor deposition causes growth of a nanostructure to occur upward through the wall of unetched resist material having controlled characteristics of height and diameter and, for parallel systems, number density.

Effect of different catalysts on urea-formaldehyde resin synthesis

Treesearch

Qi-Ning Sun; Chung-Yun Hse; Todd F. Shupe

2014-01-01

Four catalysts (H2SO4, HCl, H3PO4, and NaOH/NH4OH) were studied in the preparation of melamine modified urea– formaldehyde (UFM) resins. 13C-nuclear magnetic resonance spectroscopic analysis of the UFM resins at different synthesis stages revealed the...

Catalytic conversion of biomass pyrolysis-derived compounds with chemical liquid deposition (CLD) modified ZSM-5.

PubMed

Zhang, Huiyan; Luo, Mengmeng; Xiao, Rui; Shao, Shanshan; Jin, Baosheng; Xiao, Guomin; Zhao, Ming; Liang, Junyu

2014-03-01

Chemical liquid deposition (CLD) with KH550, TEOS and methyl silicone oil as the modifiers was used to modify ZSM-5 and deposit its external acid sites. The characteristics of modified catalysts were tested by catalytic conversion of biomass pyrolysis-derived compounds. The effects of different modifying conditions (deposited amount, temperature, and time) on the product yields and selectivities were investigated. The results show KH550 modified ZSM-5 (deposited amount of 4%, temperature of 20°C and time of 6h) produced the maximum yields of aromatics (24.5%) and olefins (16.5%), which are much higher than that obtained with original ZSM-5 catalyst (18.8% aromatics and 9.8% olefins). The coke yield decreased from 44.1% with original ZSM-5 to 26.7% with KH550 modified ZSM-5. The selectivities of low-molecule-weight hydrocarbons (ethylene and benzene) decreased, while that of higher molecule-weight hydrocarbons (propylene, butylene, toluene, and naphthalene) increased comparing with original ZSM-5. Copyright © 2013 Elsevier Ltd. All rights reserved.

Ten-gram-scale preparation of PTMS-based monodisperse ORMOSIL nano- and microparticles and conversion to silica particles

NASA Astrophysics Data System (ADS)

Kim, Jung Soo; Jung, Gyu Il; Kim, Soo Jung; Koo, Sang Man

2018-03-01

Monodisperse organically modified silica (ORMOSIL) particles, with an average diameter ranging from 550 nm to 4.2 μm, were prepared at low temperature at a scale of about 10 g/batch by a simple one-step self-emulsion process. The reaction mixture was composed only of water, phenyltrimethoxysilane (PTMS), and a base catalyst, without any surfactants. The size control of the particles and the monodispersity of resultant particles were achieved through the controlled supply of hydrolyzed PTMS monomer molecules, which was enabled by manipulating the reaction parameters, such as monomer concentration, type and amount of base catalyst, stirring rate, and reaction temperature. PTMS-based ORMOSIL particles were converted into silica particles by employing either a wet chemical reaction with an oleum-sulfuric acid mixture or thermal treatment above 650 °C. Complete removal of organic groups from the ORMOSIL particles was achieved by the thermal treatment while 74% removal was done by the chemical process used. [Figure not available: see fulltext.

Methanol Steam Reforming Promoted by Molten Salt-Modified Platinum on Alumina Catalysts

PubMed Central

Kusche, Matthias; Agel, Friederike; Ní Bhriain, Nollaig; Kaftan, Andre; Laurin, Mathias; Libuda, Jörg; Wasserscheid, Peter

2014-01-01

We herein describe a straight forward procedure to increase the performance of platinum-on-alumina catalysts in methanol steam reforming by applying an alkali hydroxide coating according to the “solid catalyst with ionic liquid layer” (SCILL) approach. We demonstrate by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed desorption (TPD) studies that potassium doping plays an important role in the catalyst activation. Moreover, the hygroscopic nature and the basicity of the salt modification contribute to the considerable enhancement in catalytic performance. During reaction, a partly liquid film of alkali hydroxides/carbonates forms on the catalyst/alumina surface, thus significantly enhancing the availability of water at the catalytically active sites. Too high catalyst pore fillings with salt introduce a considerable mass transfer barrier into the system as indicated by kinetic studies. Thus, the optimum interplay between beneficial catalyst modification and detrimental mass transfer effects had to be identified and was found on the applied platinum-on-alumina catalyst at KOH loadings around 7.5 mass %. PMID:25124120

Visible-Light-Responsive Catalysts Using Quantum Dot-Modified TiO2 for Air and Water Purification

NASA Technical Reports Server (NTRS)

Coutts, Janelle L.; Hintze, Paul E.; Clausen, Christian; Richards, Jeffrey Todd

2014-01-01

Photocatalysis, the oxidation or reduction of contaminants by light-activated catalysts, utilizing titanium dioxide (TiO2) as the catalytic substrate has been widely studied for trace contaminant control in both air and water applications. The interest in this process is due primarily to its low energy consumption and capacity for catalyst regeneration. Titanium dioxide requires ultraviolet light for activation due to its relatively large band gap energy of 3.2 eV. Traditionally, Hg-vapor fluorescent light sources are used in PCO reactors; however, the use of mercury precludes the use of this PCO technology in a spaceflight environment due to concerns over crew Hg exposure. The development of a visible-light responsive (VLR) TiO2-based catalyst would eliminate the concerns over mercury contamination. Further, VLR development would allow for the use of ambient visible solar radiation or highly efficient LEDs, both of which would make PCO approaches more efficient, flexible, economical, and safe. Though VLR catalyst development has been an active area of research for the past two decades, there are few commercially available VLR catalysts. Those VLR catalysts that are commercially available do not have adequate catalytic activity, in the visible region, to make them competitive with those operating under UV irradiation. This study was initiated to develop more effective VLR catalysts through a novel method in which quantum dots (QD) consisting of narrow band gap semiconductors (e.g., CdS, CdSe, PbS, ZnSe, etc.) are coupled to TiO2 via two preparation methods: 1) photodeposition and 2) mechanical alloying using a high-speed ball mill. A library of catalysts was developed and screened for gas and aqueous phase applications using ethanol and 4-chlorophenol as the target contaminants, respectively. Both target compounds are well studied in photocatalytic systems and served as model contaminants for this research. Synthesized catalysts were compared in terms of preparation method, nature of the quantum dots, and dosage of quantum dots.

Synthesis of Copper-Based Nanostructured Catalysts on SiO2-Al2O3, SiO2-TiO2, and SiO2-ZrO2 Supports for NO Reduction.

PubMed

Namkhang, Pornpan; Kongkachuichay, Paisan

2015-07-01

The selective catalytic reduction of NO over a series of Cu-based catalysts supported on modified silica including SiO2-Al2O3, SiO2-TiO2, and SiO2-ZrO2 prepared via a sol-gel process and a flame spray pyrolysis (FSP) was studied. The prepared catalysts were characterized by means of TEM, XRD, XRF, TPR, and nitrogen physisorption measurement techniques, to determine particle diameter, morphology, crystallinity, phase composition, copper reducibility, surface area, and pore size of catalysts. The particles obtained from sol-gel method were almost spherical while the particles obtained from the FSP were clearly spherical and non-porous nanosized particles. The effects of Si:Al, Si:Ti, and Si:Zr molar ratio of precursor were identified as the domain for different crystalline phase of materials. It was clearly seen that a high SiO2 content inhibited the crystallization of materials. The BET surface area of catalysts obtained from sol-gel method was higher than that from the FSP and it shows that surface area increased with increasing SiO2 molar ratio due to high surface area from SiO2. The catalyst performances were tested for the selective catalytic reduction of NO with H2. It was found that the catalyst prepared over 7 wt% Cu on Si02-Al2O3 support was the most active compared with the others which converted NO as more than 70%. Moreover, the excess copper decreased the performance of NO reduction, due to the formation of CuO agglomeration covered on the porous silica as well as the alumina surface, preventing the direct contact of CO2 and AL2O3.

From atactic to isotactic CO/p-methylstyrene copolymer by proper modification of Pd(II) catalysts bearing achiral alpha-diimines.

PubMed

Binotti, Barbara; Carfagna, Carla; Zuccaccia, Cristiano; Macchioni, Alceo

2005-01-07

Cationic Pd(II) complexes modified with achiral C(2v)-symmetric alpha-diimine ligands allow preparation of atactic or isotactic stereoblock CO/p-methylstyrene copolymers; both catalyst activity and polyketone microstructure depend on the choice of alpha-diimine substituents and counterion.

Edge-terminated molybdenum disulfide with a 9.4-Å interlayer spacing for electrochemical hydrogen production

DOE PAGES

Gao, Min -Rui; Chan, Maria K. Y.; Sun, Yugang

2015-07-03

In this study, layered molybdenum disulfide has demonstrated great promise as a low-cost alternative to platinum-based catalysts for electrochemical hydrogen production from water. Research effort on this material has focused mainly on synthesizing highly nanostructured molybdenum disulfide that allows the exposure of a large fraction of active edge sites. Here we report a promising microwave-assisted strategy for the synthesis of narrow molybdenum disulfide nanosheets with edge-terminated structure and a significantly expanded interlayer spacing, which exhibit striking kinetic metrics with onset potential of -103 mV, Tafel slope of 49 mV per decade and exchange current density of 9.62 × 10 -3more » mA cm -2, performing among the best of current molybdenum disulfide catalysts. Besides benefits from the edge-terminated structure, the expanded interlayer distance with modified electronic structure is also responsible for the observed catalytic improvement, which suggests a potential way to design newly advanced molybdenum disulfide catalysts through modulating the interlayer distance.« less

Edge-terminated molybdenum disulfide with a 9.4-Å interlayer spacing for electrochemical hydrogen production

PubMed Central

Gao, Min-Rui; Chan, Maria K.Y.; Sun, Yugang

2015-01-01

Layered molybdenum disulfide has demonstrated great promise as a low-cost alternative to platinum-based catalysts for electrochemical hydrogen production from water. Research effort on this material has focused mainly on synthesizing highly nanostructured molybdenum disulfide that allows the exposure of a large fraction of active edge sites. Here we report a promising microwave-assisted strategy for the synthesis of narrow molybdenum disulfide nanosheets with edge-terminated structure and a significantly expanded interlayer spacing, which exhibit striking kinetic metrics with onset potential of −103 mV, Tafel slope of 49 mV per decade and exchange current density of 9.62 × 10−3 mA cm−2, performing among the best of current molybdenum disulfide catalysts. Besides benefits from the edge-terminated structure, the expanded interlayer distance with modified electronic structure is also responsible for the observed catalytic improvement, which suggests a potential way to design newly advanced molybdenum disulfide catalysts through modulating the interlayer distance. PMID:26138031

A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution

DOE PAGES

Hod, Idan; Deria, Pravas; Bury, Wojciech; ...

2015-09-14

The availability of efficient hydrogen evolution reaction (HER) catalysts is of high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization of large-scale hydrogen production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, high porosity, metal-organic framework (MOF) films have been used as scaffolds for the deposition of a Ni-S electrocatalyst. Compared with an MOF-free Ni-S, the resulting hybrid materials exhibit significantly enhanced performance for HER from aqueous acid, decreasing the kinetic overpotential by more than 200 mV at a benchmark current density of 10 mA cm −2. In conclusion,more » although the initial aim was to improve electrocatalytic activity by greatly boosting the active area of the Ni-S catalyst, the performance enhancements instead were found to arise primarily from the ability of the proton-conductive MOF to favourably modify the immediate chemical environment of the sulfide-based catalyst.« less

Organocatalytic removal of formaldehyde adducts from RNA and DNA bases.

PubMed

Karmakar, Saswata; Harcourt, Emily M; Hewings, David S; Scherer, Florian; Lovejoy, Alexander F; Kurtz, David M; Ehrenschwender, Thomas; Barandun, Luzi J; Roost, Caroline; Alizadeh, Ash A; Kool, Eric T

2015-09-01

Formaldehyde is universally used to fix tissue specimens, where it forms hemiaminal and aminal adducts with biomolecules, hindering the ability to retrieve molecular information. Common methods for removing these adducts involve extended heating, which can cause extensive degradation of nucleic acids, particularly RNA. Here, we show that water-soluble bifunctional catalysts (anthranilates and phosphanilates) speed the reversal of formaldehyde adducts of mononucleotides over standard buffers. Studies with formaldehyde-treated RNA oligonucleotides show that the catalysts enhance adduct removal, restoring unmodified RNA at 37 °C even when extensively modified, while avoiding the high temperatures that promote RNA degradation. Experiments with formalin-fixed, paraffin-embedded cell samples show that the catalysis is compatible with common RNA extraction protocols, with detectable RNA yields increased by 1.5-2.4-fold using a catalyst under optimized conditions and by 7-25-fold compared with a commercial kit. Such catalytic strategies show promise for general use in reversing formaldehyde adducts in clinical specimens.

Organocatalytic Removal of Formaldehyde Adducts from RNA and DNA Bases

PubMed Central

Karmakar, Saswata; Harcourt, Emily M.; Hewings, David S.; Lovejoy, Alexander F.; Kurtz, David M.; Ehrenschwender, Thomas; Barandun, Luzi J.; Roost, Caroline; Alizadeh, Ash A.; Kool, Eric T.

2015-01-01

Formaldehyde is universally employed to fix tissue specimens, where it forms hemiaminal and aminal adducts with biomolecules, hindering the ability to retrieve molecular information. Common methods for removing these adducts involve extended heating, which can cause extensive degradation of nucleic acids, particularly RNA. Here we show that water-soluble bifunctional catalysts (anthranilates and phosphanilates) speed the reversal of formaldehyde adducts of mononucleotides over standard buffers. Studies with formaldehyde-treated RNA oligonucleotides show that the catalysts enhance adduct removal, restoring unmodified RNA at 37 °C even when extensively modified, and avoiding high temperatures that promote RNA degradation. Experiments with formalin-fixed, paraffin-embedded cell samples show that the catalysis is compatible with common RNA extraction protocols, with detectable RNA yields increased by 1.5–2.4 fold using a catalyst under optimized conditions, and by 7–25 fold compared to a commercial kit. Such catalytic strategies show promise for general use in reversing formaldehyde adducts in clinical specimens. PMID:26291948

To alloy or not to alloy? Cr modified Pt/C cathode catalysts for PEM fuel cells.

PubMed

Wells, Peter P; Qian, Yangdong; King, Colin R; Wiltshire, Richard J K; Crabb, Eleanor M; Smart, Lesley E; Thompsett, David; Russell, Andrea E

2008-01-01

The cathode electrocatalysts for proton exchange membrane (PEM) fuel cells are commonly platinum and platinum based alloy nanoparticles dispersed on a carbon support. Control over the particle size and composition has, historically, been attained empirically, making systematic studies of the effects of various structural parameters difficult. The controlled surface modification methodology used in this work has enabled the controlled modification of carbon supported Pt nanoparticles by Cr so as to yield nanoalloy particles with defined compositions. Subsequent heat treatment in 5% H2 in N2 resulted in the formation of a distinct Pt3Cr alloy phase which was either restricted to the surface of the particles or present throughout the bulk of the particle structure. Measurement of the oxygen reduction activity of the catalysts was accomplished using the rotating thin film electrode method and the activities obtained were related to the structure of the nanoalloy catalyst particles, largely determined using Cr K edge and Pt L3 edge XAS.

A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution

PubMed Central

Hod, Idan; Deria, Pravas; Bury, Wojciech; Mondloch, Joseph E.; Kung, Chung-Wei; So, Monica; Sampson, Matthew D.; Peters, Aaron W.; Kubiak, Cliff P.; Farha, Omar K.; Hupp, Joseph T.

2015-01-01

The availability of efficient hydrogen evolution reaction (HER) catalysts is of high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization of large-scale hydrogen production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, high porosity, metal-organic framework (MOF) films have been used as scaffolds for the deposition of a Ni-S electrocatalyst. Compared with an MOF-free Ni-S, the resulting hybrid materials exhibit significantly enhanced performance for HER from aqueous acid, decreasing the kinetic overpotential by more than 200 mV at a benchmark current density of 10 mA cm−2. Although the initial aim was to improve electrocatalytic activity by greatly boosting the active area of the Ni-S catalyst, the performance enhancements instead were found to arise primarily from the ability of the proton-conductive MOF to favourably modify the immediate chemical environment of the sulfide-based catalyst. PMID:26365764

Evaluation of Mn and Sn-Modified Pd-Ce-Based Catalysts for Low-Temperature Diesel Exhaust Oxidation

DOE PAGES

Wang, Chao; Binder, Andrew J.; Toops, Todd J.; ...

2016-12-07

Pd-impregnated Ce-based catalysts were tested for carbon monoxide (CO) and hydrocarbon (HC) oxidation under challenging low-temperature diesel combustion conditions. The results indicate that the light-off temperatures for CO over Pd/CeO 2, Pd/MnO x-CeO 2 (Pd/MC), and Pd/SnO 2-MnO x-CeO 2 (Pd/SMC) catalysts shift to higher temperatures in the presence of simulated diesel exhaust gas. The lowest T 50 for CO is observed over Pd/MC at 173 °C, whereas Pd/CeO 2 is shown to oxidize most of the HCs at temperatures below 400 °C. In all catalysts, the oxidation of HCs starts right after the onset of CO oxidation, revealing thatmore » the competitive adsorption of CO, NO, and alkenes controls the catalytic activity. Further evaluation of the catalytic activity in the presence of only CO and C 3H 6 reveals the immediate inhibiting effect of C 3H 6 at catalyst temperatures below 150 °C. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments performed over Pd/CeO 2, Pd/MC, and Pd/SMC show that C 3H 6 inhibits the formation of carbonyl species on Pd n+ sites, which limits the catalytic activity for CO. Lastly, such inhibition is observed on all supports, implying that the activity is independent of oxygen storage capacity (OSC) or lattice oxygen reducibility of the supports in the presence of C 3H 6.« less

Evaluation of Mn and Sn-Modified Pd-Ce-Based Catalysts for Low-Temperature Diesel Exhaust Oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Chao; Binder, Andrew J.; Toops, Todd J.

Pd-impregnated Ce-based catalysts were tested for carbon monoxide (CO) and hydrocarbon (HC) oxidation under challenging low-temperature diesel combustion conditions. The results indicate that the light-off temperatures for CO over Pd/CeO 2, Pd/MnO x-CeO 2 (Pd/MC), and Pd/SnO 2-MnO x-CeO 2 (Pd/SMC) catalysts shift to higher temperatures in the presence of simulated diesel exhaust gas. The lowest T 50 for CO is observed over Pd/MC at 173 °C, whereas Pd/CeO 2 is shown to oxidize most of the HCs at temperatures below 400 °C. In all catalysts, the oxidation of HCs starts right after the onset of CO oxidation, revealing thatmore » the competitive adsorption of CO, NO, and alkenes controls the catalytic activity. Further evaluation of the catalytic activity in the presence of only CO and C 3H 6 reveals the immediate inhibiting effect of C 3H 6 at catalyst temperatures below 150 °C. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments performed over Pd/CeO 2, Pd/MC, and Pd/SMC show that C 3H 6 inhibits the formation of carbonyl species on Pd n+ sites, which limits the catalytic activity for CO. Lastly, such inhibition is observed on all supports, implying that the activity is independent of oxygen storage capacity (OSC) or lattice oxygen reducibility of the supports in the presence of C 3H 6.« less

A methodology for investigating new nonprecious metal catalysts for PEM fuel cells.

PubMed

Susac, D; Sode, A; Zhu, L; Wong, P C; Teo, M; Bizzotto, D; Mitchell, K A R; Parsons, R R; Campbell, S A

2006-06-08

This paper reports an approach to investigate metal-chalcogen materials as catalysts for the oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells. The methodology is illustrated with reference to Co-Se thin films prepared by magnetron sputtering onto a glassy-carbon substrate. Scanning Auger microscopy (SAM), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDX), and X-ray diffraction (XRD) have been used, in parallel with electrochemical activity and stability measurements, to assess how the electrochemical performance relates to chemical composition. It is shown that Co-Se thin films with varying Se are active for oxygen reduction, although the open circuit potential (OCP) is lower than for Pt. A kinetically controlled process is observed in the potential range 0.5-0.7 V (vs reversible hydrogen electrode) for the thin-film catalysts studied. An initial exposure of the thin-film samples to an acid environment served as a pretreatment, which modified surface composition prior to activity measurements with the rotating disk electrode (RDE) method. Based on the SAM characterization before and after electrochemical tests, all surfaces demonstrating activity are dominated by chalcogen. XRD shows that the thin films have nanocrystalline character that is based on a Co(1-x)Se phase. Parallel studies on Co-Se powder supported on XC72R carbon show comparable OCP, Tafel region, and structural phase as for the thin-film model catalysts. A comparison for ORR activity has also been made between this Co-Se powder and a commercial Pt catalyst.

Electrocatalysts for Hydrogen Evolution in Alkaline Electrolytes: Mechanisms, Challenges, and Prospective Solutions.

PubMed

Mahmood, Nasir; Yao, Yunduo; Zhang, Jing-Wen; Pan, Lun; Zhang, Xiangwen; Zou, Ji-Jun

2018-02-01

Hydrogen evolution reaction (HER) in alkaline medium is currently a point of focus for sustainable development of hydrogen as an alternative clean fuel for various energy systems, but suffers from sluggish reaction kinetics due to additional water dissociation step. So, the state-of-the-art catalysts performing well in acidic media lose considerable catalytic performance in alkaline media. This review summarizes the recent developments to overcome the kinetics issues of alkaline HER, synthesis of materials with modified morphologies, and electronic structures to tune the active sites and their applications as efficient catalysts for HER. It first explains the fundamentals and electrochemistry of HER and then outlines the requirements for an efficient and stable catalyst in alkaline medium. The challenges with alkaline HER and limitation with the electrocatalysts along with prospective solutions are then highlighted. It further describes the synthesis methods of advanced nanostructures based on carbon, noble, and inexpensive metals and their heterogeneous structures. These heterogeneous structures provide some ideal systems for analyzing the role of structure and synergy on alkaline HER catalysis. At the end, it provides the concluding remarks and future perspectives that can be helpful for tuning the catalysts active-sites with improved electrochemical efficiencies in future.

Electrocatalysts for Hydrogen Evolution in Alkaline Electrolytes: Mechanisms, Challenges, and Prospective Solutions

PubMed Central

Mahmood, Nasir; Yao, Yunduo; Zhang, Jing‐Wen; Pan, Lun; Zhang, Xiangwen

2017-01-01

Abstract Hydrogen evolution reaction (HER) in alkaline medium is currently a point of focus for sustainable development of hydrogen as an alternative clean fuel for various energy systems, but suffers from sluggish reaction kinetics due to additional water dissociation step. So, the state‐of‐the‐art catalysts performing well in acidic media lose considerable catalytic performance in alkaline media. This review summarizes the recent developments to overcome the kinetics issues of alkaline HER, synthesis of materials with modified morphologies, and electronic structures to tune the active sites and their applications as efficient catalysts for HER. It first explains the fundamentals and electrochemistry of HER and then outlines the requirements for an efficient and stable catalyst in alkaline medium. The challenges with alkaline HER and limitation with the electrocatalysts along with prospective solutions are then highlighted. It further describes the synthesis methods of advanced nanostructures based on carbon, noble, and inexpensive metals and their heterogeneous structures. These heterogeneous structures provide some ideal systems for analyzing the role of structure and synergy on alkaline HER catalysis. At the end, it provides the concluding remarks and future perspectives that can be helpful for tuning the catalysts active‐sites with improved electrochemical efficiencies in future. PMID:29610722

Selective Fenton-like oxidation of methylene blue on modified Fe-zeolites prepared via molecular imprinting technique.

PubMed

Zhang, Yuanyuan; Shang, Jiaobo; Song, Yanqun; Rong, Chuan; Wang, Yinghui; Huang, Wenyu; Yu, Kefu

2017-02-01

A facile strategy to increase the selectivity of heterogeneous Fenton oxidation is investigated. The increase was reached by increasing selective adsorption of heterogeneous Fenton catalyst to a target pollutant. The heterogeneous Fenton catalyst was prepared by a two-step process. First, zeolite particles were imprinted by the target pollutant, methylene blue (MB), in their aggregations, and second, iron ions were loaded on the zeolite aggregations to form the molecule imprinted Fe-zeolites (MI-FZ) Fenton catalyst. Its adsorption amount for MB reached as high as 44.6 mg g -1 while the adsorption amount of un-imprinted Fe-zeolites (FZ) is only 15.6 mg g -1 . Fenton removal efficiency of MI-FZ for MB was 87.7%, being 33.9% higher than that of FZ. The selective Fenton oxidation of MI-FZ for MB was further confirmed by its removal performance for the mixed MB and bisphenol A (BPA) in solution. The removal efficiency of MB was 44.7% while that of BPA was only 14.9%. This fact shows that molecular imprinting is suitable to prepare the Fe-zeolites (FZ)-based Fenton catalyst with high selectivity for removal of target pollutants, at least MB.

Synthesis of Bio-aromatics from Black Liquors Using Catalytic Pyrolysis

PubMed Central

2018-01-01

Bio-aromatics (benzene, toluene, xylenes, BTX) were prepared by the catalytic pyrolysis of six different black liquors using both in situ and ex situ approaches. A wide range of catalysts was screened and conditions were optimized in microscale reactors. Up to 7 wt % of BTX, based on the organic fraction of the black liquors, was obtained for both the in situ and ex situ pyrolysis (T = 500–600 °C) using a Ga-modified H-ZSM-5 catalyst. The in situ catalytic pyrolysis of black liquors from hardwood paper mills afforded slightly higher yields of aromatics/BTX than softwood black liquors, a trend that could be confirmed by the results obtained in the ex situ catalytic pyrolysis. An almost full deoxygenation of the lignin and carbohydrate fraction was achieved and both organic fractions were converted to a broad range of (substituted) aromatics. The zeolite catalyst used was remarkably stable and even after 100 experiments in batch mode with intermittent oxidative catalyst regeneration, the yields and selectivity toward BTX remained similar. The ex situ pyrolysis of black liquor has potential for large-scale implementation in a paper mill without disturbing the paper production process. PMID:29607268

Ship-in-a-bottle catalysts

DOEpatents

Haw, James F.; Song, Weiguo

2006-07-18

In accordance with the present invention there is provided a novel catalyst system in which the catalytic structure is tailormade at the nanometer scale using the invention's novel ship-in-a-bottle synthesis techniques. The invention describes modified forms of solid catalysts for use in heterogeneous catalysis that have a microporous structure defined by nanocages. Examples include zeolites, SAPOs, and analogous materials that have the controlled pore dimensions and hydrothermal stability required for many industrial processes. The invention provides for modification of these catalysts using reagents that are small enough to pass through the windows used to access the cages. The small reagents are then reacted to form larger molecules in the cages.

Photo-oxidation catalysts

DOEpatents

Pitts, J Roland [Lakewood, CO; Liu, Ping [Irvine, CA; Smith, R Davis [Golden, CO

2009-07-14

Photo-oxidation catalysts and methods for cleaning a metal-based catalyst are disclosed. An exemplary catalyst system implementing a photo-oxidation catalyst may comprise a metal-based catalyst, and a photo-oxidation catalyst for cleaning the metal-based catalyst in the presence of light. The exposure to light enables the photo-oxidation catalyst to substantially oxidize absorbed contaminants and reduce accumulation of the contaminants on the metal-based catalyst. Applications are also disclosed.

Multiscale Evaluation of Catalytic Upgrading of Biomass Pyrolysis Vapors on Ni- and Ga-Modified ZSM-5

DOE PAGES

Yung, Matthew M.; Stanton, Alexander R.; Iisa, Kristiina; ...

2016-10-07

Metal-impregnated (Ni or Ga) ZSM-5 catalysts were studied for biomass pyrolysis vapor upgrading to produce hydrocarbons using three reactors constituting a 100 000x change in the amount of catalyst used in experiments. Catalysts were screened for pyrolysis vapor phase upgrading activity in two small-scale reactors: (i) a Pyroprobe with a 10 mg catalyst in a fixed bed and (ii) a fixed-bed reactor with 500 mg of catalyst. The best performing catalysts were then validated with a larger scale fluidized-bed reactor (using ~1 kg of catalyst) that produced measurable quantities of bio-oil for analysis and evaluation of mass balances. Despite somemore » inherent differences across the reactor systems (such as residence time, reactor type, analytical techniques, mode of catalyst and biomass feed) there was good agreement of reaction results for production of aromatic hydrocarbons, light gases, and coke deposition. Relative to ZSM-5, Ni or Ga addition to ZSM-5 increased production of fully deoxygenated aromatic hydrocarbons and light gases. In the fluidized bed reactor, Ga/ZSM-5 slightly enhanced carbon efficiency to condensed oil, which includes oxygenates in addition to aromatic hydrocarbons, and reduced oil oxygen content compared to ZSM-5. Ni/ZSM-5, while giving the highest yield of fully deoxygenated aromatic hydrocarbons, gave lower overall carbon efficiency to oil but with the lowest oxygen content. Reaction product analysis coupled with fresh and spent catalyst characterization indicated that the improved performance of Ni/ZSM-5 is related to decreasing deactivation by coking, which keeps the active acid sites accessible for the deoxygenation and aromatization reactions that produce fully deoxygenated aromatic hydrocarbons. The addition of Ga enhances the dehydrogenation activity of the catalyst, which leads to enhanced olefin formation and higher fully deoxygenated aromatic hydrocarbon yields compared to unmodified ZSM-5. Catalyst characterization by ammonia temperature programmed desorption, surface area measurements, and postreaction temperature-programmed oxidation (TPO) also showed that the metal-modified zeolites retained a greater percentage of their initial acidity and surface area, which was consistent between the reactor scales. These results demonstrate that the trends observed with smaller (milligram to gram) catalyst reactors are applicable to larger, more industrially relevant (kg) scales to help guide catalyst research toward application.« less

Silicoaluminates as “Support Activator” Systems in Olefin Polymerization Processes

PubMed Central

Tabernero, Vanessa; Camejo, Claudimar; Terreros, Pilar; Alba, María Dolores; Cuenca, Tomás

2010-01-01

In this work we report the polymerization behaviour of natural clays (montmorillonites, MMT) as activating supports. These materials have been modified by treatment with different aluminium compounds in order to obtain enriched aluminium clays and to modify the global Brönsted/Lewis acidity. As a consequence, the intrinsic structural properties of the starting materials have been changed. These changes were studied and these new materials used for ethylene polymerization using a zirconocene complex as catalyst. All the systems were shown to be active in ethylene polymerization. The catalyst activity and the dependence on acid strength and textural properties have been also studied. The behaviour of an artificial silica (SBA 15) modified with an aluminium compound to obtain a silicoaluminate has been studied, but no ethylene polymerization activity has been found yet.

Zinc Tantalum Oxynitride (ZnTaO2N) Photoanode Modified with Cobalt Phosphate Layers for the Photoelectrochemical Oxidation of Alkali Water

PubMed Central

T. Weller, Mark

2018-01-01

Photoanodes fabricated by the electrophoretic deposition of a thermally prepared zinc tantalum oxynitride (ZnTaO2N) catalyst onto indium tin oxide (ITO) substrates show photoactivation for the oxygen evolution reaction (OER) in alkaline solutions. The photoactivity of the OER is further boosted by the photodeposition of cobalt phosphate (CoPi) layers onto the surface of the ZnTaO2N photoanodes. Structural, morphological, and photoelectrochemical (PEC) properties of the modified ZnTaO2N photoanodes are studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet visible (UV−Vis) diffuse reflectance spectroscopy, and electrochemical techniques. The presence of the CoPi layer significantly improved the PEC performance of water oxidation in an alkaline sulphate solution. The photocurrent-voltage behavior of the CoPi-modified ZnTaO2N anodes was improved, with the influence being more prominent at lower oxidation potentials. A stable photocurrent density of about 2.3 mA·cm−2 at 1.23 V vs. RHE was attained upon visible light illumination. Relative to the ZnTaO2N photoanodes, an almost three-fold photocurrent increase was achieved at the CoPi/ZnTaO2N photoelectrode. Perovskite-based oxynitrides are modified using an oxygen-evolution co-catalyst of CoPi, and provide a new dimension for enhancing the photoactivity of oxygen evolution in solar-assisted water-splitting reactions. PMID:29346306

n-hydrocarbons conversions over metal-modified solid acid catalysts

NASA Astrophysics Data System (ADS)

Zarubica, A.; Ranđelović, M.; Momčilović, M.; Radulović, N.; Putanov, P.

2013-12-01

The quality of a straight-run fuel oil can be improved if saturated n-hydrocarbons of low octane number are converted to their branched counterparts. Poor reactivity of traditional catalysts in isomerization reactions imposed the need for the development of new catalysts among which noble metal promoted acid catalysts, liquid and/or solid acid catalysts take a prominent place. Sulfated zirconia and metal promoted sulfated zirconia exhibit high activity for the isomerization of light alkanes at low temperatures. The present paper highlights the original results which indicate that the modification of sulfated zirconia by incorporation of metals (platinum and rhenium) significantly affects catalytic performances in n-hydrocarbon conversion reactions. Favourable activity/selectivity of the promoted sulfated zirconia depends on the crystal phase composition, critical crystallites sizes, platinum dispersion, total acidity and type of acidity. Attention is also paid to the recently developed solid acid catalysts used in other conversion reactions of hydrocarbons.

Studies of long-life pulsed CO2 laser with Pt/SnO2 catalyst

NASA Technical Reports Server (NTRS)

Sidney, Barry D.

1987-01-01

Closed-cycle CO2 laser testing with and without a catalyst and with and without CO addition indicate that a catalyst is necessary for long-term operation. Initial results indicate that CO addition with a catalyst may prove optimal, but a precise gas mix has not yet been determined. A long-term run of 10 to the 6th power pulses using 1.3% added CO and a 2% Pt on SnO2 catalyst yields an efficiency of about 95% of open-cycle steady-state power. A simple mathematical analysis yields results which may be sufficient for determining optimum running conditions. Future plans call for testing various catalysts in the laser and longer tests, 10 to the 7th power pulses. A Gas Chromatograph will be installed to measure gas species concentration and the analysis will be slightly modified to include neglected but possibly important parameters.

Guided evolution of bulk metallic glass nanostructures: A platform for designing three-dimensional electrocatalytic surfaces

DOE PAGES

Doubek, Gustavo; Sekol, Ryan C.; Li, Jinyang; ...

2015-12-22

Precise control over catalyst surface composition and structure is necessary to improve the function of electrochemical systems. To that end, bulk metallic glass (BMG) alloys with atomically dispersed elements provide a highly processable, nanoscale platform for electrocatalysis and surface modification. Here we report on nanostructures of Pt-based BMGs that are modified with various subtractive and additive processes to improve their electrochemical performance.

One molecule of ionic liquid and tert-alcohol on a polystyrene-support as catalysts for efficient nucleophilic substitution including fluorination.

PubMed

Shinde, Sandip S; Patil, Sunil N

2014-12-07

The tert-alcohol and ionic liquid solvents in one molecule [mim-(t)OH][OMs] was immobilized on polystyrene and reported to be a highly efficient catalyst in aliphatic nucleophilic substitution using alkali metal salts. Herein, we investigated the catalytic activity of a new structurally modified polymer-supported tert-alcohol functionalized imidazolium salt catalyst in nucleophilic substitution of 2-(3-methanesulfonyloxypropyoxy)naphthalene as a model substrate with various metal nucleophiles. The tert-alcohol moiety of the ionic liquid with a hexyl chain distance from polystyrene had a better catalytic activity compared to the other resin which lacked an alkyl linker and tert-alcohol moiety. We found that the maximum [mim-(t)OH][OMs] loading had the best catalytic efficacy among the tested polystyrene-based ionic liquids (PSILs) in nucleophilic fluorination. The catalytic efficiency of the PS[him-(t)OH][OMs] as a phase transfer catalyst (PTC) was determined by carrying out various nucleophilic substitutions using the corresponding alkali metal salts from the third to sixth periodic in CH3CN or tert-BuOH media. The scope of this protocol with primary and secondary polar substrates containing many heteroatoms is also reported. This PS[him-(t)OH][OMs] catalyst not only enhances the reactivity of alkali metal salts and reduces the formation of by-products but also affords high yield with easy isolation.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Getsoian, Andrew "Bean"; Das, Ujjal; Camacho-Bunquin, Jeffrey

Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order tomore » better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. Furthermore, these findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Getsoian, Andrew “Bean”; Das, Ujjal; Camacho-Bunquin, Jeffrey

Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order tomore » better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. These findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.« less

Visible Light Responsive Catalysts Using Quantum Dot-Modified Ti02 for Air and Water Purification

NASA Technical Reports Server (NTRS)

Coutts, Janelle L.; Levine, Lanfang H.; Richards, Jeffrey T.; Hintze, paul; Clausen, Christian

2012-01-01

The method of photocatalysis utilizing titanium dioxide, TiO2, as the catalyst has been widely studied for trace contaminant control for both air and water applications because of its low energy consumption and use of a regenerable catalyst. Titanium dioxide requires ultraviolet light for activation due to its band gap energy of 3.2 eV. Traditionally, Hg-vapor fluorescent light sources are used in PCO reactors and are a setback for the technology for space application due to the possibility of Hg contamination. The development of a visible light responsive (VLR) TiO2-based catalyst could lead to the use of solar energy in the visible region (approx.45% of the solar spectrum lies in the visible region; > 400 nm) or highly efficient LEDs (with wavelengths > 400 nm) to make PCO approaches more efficient, economical, and safe. Though VLR catalyst development has been an active area of research for the past two decades, there are few commercially available VLR catalysts; those that are available still have poor activity in the visible region compared to that in the UV region. Thus, this study was aimed at the further development of VLR catalysts by a new method - coupling of quantum dots (QD) of a narrow band gap semiconductor (e.g., CdS, CdSe, PbS, ZnSe, etc.) to the TiO2 by two preparation methods: 1) photodeposition and 2) mechanical alloying using a high-speed ball mill. A library of catalysts was developed and screened for gas and aqueous phase applications, using ethanol and 4-chlorophenol as the target contaminants, respectively. Both target compounds are well studied in photocatalytic systems serve as model contaminants for this research. Synthesized catalysts were compared in terms of preparation method, type of quantum dots, and dosage of quantum dots.

Investigation of TiO2 based Mixed-metal Oxide Catalysts for the Production of Hydrogen

NASA Astrophysics Data System (ADS)

Luo, Si

Abstract of the Dissertation. Investigation of TiO2 based Mixed-metal Oxide Catalysts for the Production of Hydrogen. by. Si Luo. Doctor of Philosophy. in. Chemistry. Stony Brook University. 2017. The environmental impacts of fossil fuel consumption and the resulting global warming have attracted increasing attention to technologies and fuels that are both sustainable and renewable in the 21st century. To date, hydrogen has been proposed as an encouraging candidate of the next generation of chemical fuels, which meets all demands for carbon free and efficient chemistries that could be produced from a variety of sources. However, despite tremendous efforts, there is a clear need to develop new catalysts for the production of hydrogen through catalytic processes that are sustainable, such as in the photocatalytic splitting of water (PCS: H2O → H2 + 0.5O2) and the water-gas shift process (WGS: CO + H2O → H2 + CO2). This thesis is primarily motivated by this challenge and has focused on the photochemical and thermal production of H2 by the employment of novel TiO2 based catalysts. TiO2 is one of the most widely studied photocatalysts in all history, due to its relatively high activity, robust stability, safety and low cost. In this thesis, several TiO2-based mixed metal oxide nano catalysts (CeOx-TiO2, Ru-TiO2, Ga-TiO2) have been synthesized with carefully controlled morphology/structure and with inclusion of co-catalysts (Pt). These novel materials were comprehensively characterized to better understand their morphology, crystal structure, and electronic properties in an attempt to unravel phenomena responsible for high catalytic performance for the production of H2 from H2O. We have discovered the importance of low-dimensional metal oxide and interfacial stabilized nano-scaled mixed metal oxides for H2 production, while learning how best to tune such structure to optimize both thermal and photochemical conversion. Optimized structure and/or composition have been identified for TiO2 modified in different ways by another metal oxide (CeOx) or with dopants (Ga, Ru). In addition, we have also studied the water gas shift reaction on several TiO2 supported catalysts, where similar concepts can be applied. Advanced In situ characterization enabled the investigation of the catalyst structure, surface chemical intermediates and active species under reaction conditions. The influence of metal-oxide, oxide-oxide interactions has been further revealed for both the water-gas shift and the photocatalytic splitting of water.

Au/MxOy/TiO2 catalysts for CO oxidation: promotional effect of main-group, transition, and rare-earth metal oxide additives.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Zhen; Overbury, Steven; Dai, Sheng

Au/TiO2 catalysts are active for CO oxidation, but they suffer from high-temperature sintering of the gold particles, and few attempts have been made to promote or stabilize Au/TiO2. Our recent communication addressed these issues by loading gold onto Al2O3/TiO2 prepared via surface-sol-gel processing of Al(sec-OC4H9)3 on TiO2. In our current full paper, Au/Al2O3/TiO2 catalysts were prepared alternatively by thermal decomposition of Al(NO3)3 on TiO2 followed by loading gold, and the influences of the decomposition temperature and Al2O3 content were systematically surveyed. This facile method was subsequently extended to the preparation of a battery of metal oxide-modified Au/TiO2 catalysts virtually notmore » reported. It was found that Au/TiO2 modified by CaO, NiO, ZnO, Ga2O3, Y2O3, ZrO2, La2O3, Pr2O3, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Dy2O3, Ho2O3, Er2O3, or Yb2O3 could retain significant activity at ambient temperature even after aging in O2-He at 500 C, whereas unmodified Au/TiO2 lost its activity. Moreover, some 200 C-calcined promoted catalysts showed high activity even at about -100 C. The deactivation and regeneration of some of these new catalysts were studied. This work furnished novel catalysts for further fundamental and applied research.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yung, Matthew M.; Starace, Anne K.; Mukarakate, Calvin

Here in this work, Ni/ZSM-5 catalysts with varied nickel loadings were evaluated for their ability to produce aromatic hydrocarbons by upgrading of pine pyrolysis vapors. The effect of catalyst pretreatment by hydrogen reduction was also investigated. Results indicate that the addition of nickel increases the yield of aromatic hydrocarbons while simultaneously increasing the conversion of oxygenates, relative to ZSM-5, and these effects are more pronounced with increasing nickel loading. Additionally, while initial activity differences were observed between the oxidized and reduced forms of nickel on ZSM-5 (i.e., NiO/ZSM-5 versus Ni/ZSM-5), the activity of both catalysts converges with increasing time onmore » stream. These reaction results coupled with characterization of pristine and spent catalysts suggest that the catalysts reach similar active states during catalytic pyrolysis, regardless of pretreatment, as NiO undergoes in situ reduction to Ni by biomass pyrolysis vapors. This reduction of NiO to Ni was confirmed by reaction results and characterization by NH 3 temperature-programmed desorption, temperature-programmed reduction, and X-ray diffraction. This finding is significant in that the ability to reduce or eliminate the need for a pre-reaction H 2 reduction of Ni-modified zeolite catalysts could reduce process complexity and operating costs in a biorefinery-based vapor-phase upgrading process to produce biomass-derived fuels and chemicals. The ability to monitor catalyst activity in real time with a molecular beam mass spectrometer used to measure uncondensed, hot pyrolysis vapors allows for an improved understanding of the mechanism for improved activity with Ni addition to ZSM-5, which is attributed to the ability to prevent deactivation by deposition of coke and capping of zeolite micropores.« less

Biomass Catalytic Pyrolysis on Ni/ZSM-5: Effects of Nickel Pretreatment and Loading

DOE PAGES

Yung, Matthew M.; Starace, Anne K.; Mukarakate, Calvin; ...

2016-04-25

Here in this work, Ni/ZSM-5 catalysts with varied nickel loadings were evaluated for their ability to produce aromatic hydrocarbons by upgrading of pine pyrolysis vapors. The effect of catalyst pretreatment by hydrogen reduction was also investigated. Results indicate that the addition of nickel increases the yield of aromatic hydrocarbons while simultaneously increasing the conversion of oxygenates, relative to ZSM-5, and these effects are more pronounced with increasing nickel loading. Additionally, while initial activity differences were observed between the oxidized and reduced forms of nickel on ZSM-5 (i.e., NiO/ZSM-5 versus Ni/ZSM-5), the activity of both catalysts converges with increasing time onmore » stream. These reaction results coupled with characterization of pristine and spent catalysts suggest that the catalysts reach similar active states during catalytic pyrolysis, regardless of pretreatment, as NiO undergoes in situ reduction to Ni by biomass pyrolysis vapors. This reduction of NiO to Ni was confirmed by reaction results and characterization by NH 3 temperature-programmed desorption, temperature-programmed reduction, and X-ray diffraction. This finding is significant in that the ability to reduce or eliminate the need for a pre-reaction H 2 reduction of Ni-modified zeolite catalysts could reduce process complexity and operating costs in a biorefinery-based vapor-phase upgrading process to produce biomass-derived fuels and chemicals. The ability to monitor catalyst activity in real time with a molecular beam mass spectrometer used to measure uncondensed, hot pyrolysis vapors allows for an improved understanding of the mechanism for improved activity with Ni addition to ZSM-5, which is attributed to the ability to prevent deactivation by deposition of coke and capping of zeolite micropores.« less

Methanol steam reforming promoted by molten salt-modified platinum on alumina catalysts.

PubMed

Kusche, Matthias; Agel, Friederike; Ní Bhriain, Nollaig; Kaftan, Andre; Laurin, Mathias; Libuda, Jörg; Wasserscheid, Peter

2014-09-01

We herein describe a straight forward procedure to increase the performance of platinum-on-alumina catalysts in methanol steam reforming by applying an alkali hydroxide coating according to the "solid catalyst with ionic liquid layer" (SCILL) approach. We demonstrate by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed desorption (TPD) studies that potassium doping plays an important role in the catalyst activation. Moreover, the hygroscopic nature and the basicity of the salt modification contribute to the considerable enhancement in catalytic performance. During reaction, a partly liquid film of alkali hydroxides/carbonates forms on the catalyst/alumina surface, thus significantly enhancing the availability of water at the catalytically active sites. Too high catalyst pore fillings with salt introduce a considerable mass transfer barrier into the system as indicated by kinetic studies. Thus, the optimum interplay between beneficial catalyst modification and detrimental mass transfer effects had to be identified and was found on the applied platinum-on-alumina catalyst at KOH loadings around 7.5 mass%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced Fe dispersion via "pinning" effect of thiocyanate ion on ferric ion in Fe-N-S-doped catalyst as an excellent oxygen reduction reaction electrode

NASA Astrophysics Data System (ADS)

Shu, Chengyong; Chen, Yuanzhen; Yang, Xiao-Dong; Liu, Yan; Chong, Shaokun; Fang, Yuan; Liu, Yongning; Yang, Wei-Hua

2018-02-01

In this study, by using thiocyanate as an iron ion dispersing agent, the pinning effect of thiocyanate ion (SCN-) enables the high dispersion of Fe3+ in a nitrogen-doped carbon polymer and significantly promotes ORR catalysis in both acidic and alkaline media. It shows 47.3 A g-1 kinetic ORR current density in 0.1 M H2SO4 solution at 0.8 V vs. RHE. In addition, SCN- can dope into the base material and modify the surface of catalysts, which generates strong cyanide N functional groups. Additionally, it also has a higher BET surface area and more uniform granularity, which accounts for the enhancement in mass transport.

An Investigation of Methyl Viologen Functionalized Reduced Graphene Oxide: Chitosan as a Support for Pt Nanoparticles Towards Ethanol Electrooxidation

NASA Astrophysics Data System (ADS)

Ekrami-Kakhki, Mehri-Saddat; Farzaneh, Nahid; Abbasi, Sedigheh; Beitollahi, Hadi; Ekrami-Kakhki, Seyed Ali

2018-05-01

In this research, graphene oxide was prepared by a modified Hummers' method, and then functionalized with 1, 1'-dimethyl-4, 4'-bipyridinium dichloride (MV), and chitosan (CH) to get a MV-RGO-CH support. Pt nanoparticles were prepared on this support to get Pt/MV-RGO-CH catalyst. The morphology and microstructure of Pt/MV-RGO-CH catalyst were characterized with transmission electron microscopy image and X-ray diffraction analysis. The electrocatalytic activity of the prepared catalyst towards ethanol oxidation was investigated by carbon monoxide stripping voltammetry, cyclic voltammetry, and electrochemical impedance spectroscopy techniques. The effects of some experimental parameters such as scan rate, ethanol concentration, and temperature were investigated for ethanol electrooxidation at Pt/MV-RGO-CH catalyst. Durability of the catalyst was also investigated. The electrocatalytic performance of Pt/MV-RGO-CH catalyst for ethanol oxidation was compared with those of Pt/CH and Pt/MV-RGO catalysts. The higher electrocatalytic performance of Pt/MV-RGO-CH than Pt/CH and Pt/MV-RGO catalysts towards ethanol electrooxidation indicated that Pt/MV-RGO-CH could be a promising catalyst for application in direct ethanol fuel cells.

Investigation on the light alkanes aromatization over Zn and Ga modified HZSM-5 catalysts in the presence of methane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Qingyin; Zhang, Fengqi; Jarvis, Jack

The catalytic co-aromatization of methane and paraffin-rich raffinate oil was investigated along with hexane, heptane and octane as its model compounds over zinc and gallium modified ZSM-5 zeolite catalysts. The benzene, toluene and xylene (BTX) components derived from light alkane aromatization were highly promoted with the assistance of methane. The co-existence of Zn and Ga metal species has a positive effect on the formation of BTX components, whereas the individual metal loaded catalyst resulted in the production of heavy aromatics, suggesting that zinc and gallium have a synergistic effect on the formation of BTX under the methane environment. When concernedmore » with gaseous analysis, the introduced methane might interact with smaller intermediates and then transform into larger hydrocarbons. From the DRIFT observation, it was witnessed that the interaction between light alkane and methane occurred on the surface of the charged Zn-Ga/ZSM-5 catalyst. According to the comprehensive catalyst characterizations, the excellent catalytic performance may be closely associated with greatly dispersed metal species on the zeolite support, improved microporous characteristic, moderate Bronsted and increased Lewis acidic sites during the paraffin-rich liquid feedstock aromatization under methane environment. This research provides a promising pathway for the highly effective and profitable utilization of petrochemical resources and natural gas.« less

Analyzing the electrooxidation of ethylene glycol and glucose over platinum-modified gold electrocatalysts in alkaline electrolyte using in-situ infrared spectroscopy

NASA Astrophysics Data System (ADS)

Mahoney, Elizabeth G.; Sheng, Wenchao; Cheng, Mei; Lee, Kevin X.; Yan, Yushan; Chen, Jingguang G.

2016-02-01

Platinum modified gold (Pt/Au) catalysts are evaluated for the electrooxidation of ethylene glycol (EG) and glucose (Glc). The Pt/Au catalysts are synthesized on an Au disk and supported Au/C particles through the galvanic displacement of a copper monolayer with Pt. The Pt/Au catalysts are compared to monometallic Pt and Au catalysts for the oxidation of EG and Glc in alkaline electrolyte. The Pt/Au disk has an onset potential for these reactions that is similar to Pt and is lower than Au. The supported catalysts are less active toward the electrooxidation of EG and Glc than the corresponding disk electrodes, but the Pt/Au/C also has an onset potential similar to Pt/C. In-situ FTIR is used to analyze the C-C bond scission in both reactions on the surfaces of Pt, Au, and Pt/Au disks. While the Pt/Au disk is found to have a low onset potential for the oxidation of EG, it does not produce as much CO2 as bulk Pt. On the other hand, the FTIR results show that CO2 is produced for the oxidation of Glc on the Pt/Au disk. These results show promise for the possibility of decreasing the amount of Pt needed for the electrooxidation of polyol molecules.

Anode catalysts for direct ethanol fuel cells utilizing directly solar light illumination.

PubMed

Chu, Daobao; Wang, Shuxi; Zheng, Peng; Wang, Jian; Zha, Longwu; Hou, Yuanyuan; He, Jianguo; Xiao, Ying; Lin, Huashui; Tian, Zhaowu

2009-01-01

Shine a light: A PtNiRu/TiO(2) anode catalyst for direct ethanol fuel cells shows photocatalytic activity. The peak current density for ethanol oxidation under solar light illumination is 2-3 times greater than that in the absence of solar light. Ethanol is oxidized by light-generated holes, and the electrons are collected by the TiO(2) support to generate the oxidation current.Novel PtNiRu/TiO(2) anode catalysts for direct ethanol fuel cells (DEFCs) were prepared from PtNiRu nanoparticles (1:1:1 atomic ratios) and a nanoporous TiO(2) film by a sol-gel and electrodeposition method. The performances of the catalysts for ethanol oxidation were investigated by cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. The results indicate a remarkable enhancement of activity for ethanol oxidation under solar light illumination. Under solar light illumination, the generated oxidation peak current density is 24.6 mA cm(-2), which is about 2.5 times higher than that observed without solar light (9.9 mA cm(-2)). The high catalytic activity of the PtNiRu/TiO(2) complex catalyst for the electrooxidation of ethanol may be attributed to the modified metal/nanoporous TiO(2) film, and the enhanced electrooxidation of ethanol under solar light may be due to the photogeneration of holes in the modified nanoporous TiO(2) film.

The effect of Fe-Rh alloying on CO hydrogenation to C 2+ oxygenates

DOE PAGES

Palomino, Robert; Magee, Joseph W.; Llorca, Jordi; ...

2015-05-20

A combination of reactivity and structural studies using X-ray diffraction (XRD), pair distribution function (PDF), and transmission electron microscopy (TEM) was used to identify the active phases of Fe-modified Rh/TiO 2 catalysts for the synthesis of ethanol and other C 2+ oxygenates from CO hydrogenation. XRD and TEM confirm the existence of Fe–Rh alloys for catalyst with 1–7 wt% Fe and ~2 wt% Rh. Rietveld refinements show that FeRh alloy content increases with Fe loading up to ~4 wt%, beyond which segregation to metallic Fe becomes favored over alloy formation. Catalysts that contain Fe metal after reduction exhibit some carburizationmore » as evidenced by the formation of small amounts of Fe 3C during CO hydrogenation. Analysis of the total Fe content of the catalysts also suggests the presence of FeO x also increased under reaction conditions. Reactivity studies show that enhancement of ethanol selectivity with Fe loading is accompanied by a significant drop in CO conversion. Comparison of the XRD phase analyses with selectivity suggests that higher ethanol selectivity is correlated with the presence of Fe–Rh alloy phases. As a result, the interface between Fe and Rh serves to enhance the selectivity of ethanol, but suppresses the activity of the catalyst which is attributed to the blocking or modifying of Rh active sites.« less

Investigation on the light alkanes aromatization over Zn and Ga modified HZSM-5 catalysts in the presence of methane

DOE PAGES

Li, Qingyin; Zhang, Fengqi; Jarvis, Jack; ...

2018-03-16

The catalytic co-aromatization of methane and paraffin-rich raffinate oil was investigated along with hexane, heptane and octane as its model compounds over zinc and gallium modified ZSM-5 zeolite catalysts. The benzene, toluene and xylene (BTX) components derived from light alkane aromatization were highly promoted with the assistance of methane. The co-existence of Zn and Ga metal species has a positive effect on the formation of BTX components, whereas the individual metal loaded catalyst resulted in the production of heavy aromatics, suggesting that zinc and gallium have a synergistic effect on the formation of BTX under the methane environment. When concernedmore » with gaseous analysis, the introduced methane might interact with smaller intermediates and then transform into larger hydrocarbons. From the DRIFT observation, it was witnessed that the interaction between light alkane and methane occurred on the surface of the charged Zn-Ga/ZSM-5 catalyst. According to the comprehensive catalyst characterizations, the excellent catalytic performance may be closely associated with greatly dispersed metal species on the zeolite support, improved microporous characteristic, moderate Bronsted and increased Lewis acidic sites during the paraffin-rich liquid feedstock aromatization under methane environment. This research provides a promising pathway for the highly effective and profitable utilization of petrochemical resources and natural gas.« less

BBD Optimization of K-ZnO Catalyst Modification Process for Heterogeneous Transesterification of Rice Bran Oil to Biodiesel

NASA Astrophysics Data System (ADS)

Kabo, K. S.; Yacob, A. R.; Bakar, W. A. W. A.; Buang, N. A.; Bello, A. M.; Ruskam, A.

2016-07-01

Environmentally benign zinc oxide (ZnO) was modified with 0-15% (wt.) potassium through wet impregnation and used in transesterification of rice bran oil (RBO) to form biodiesel. The catalyst was characterized by X-Ray powder Diffraction (XRD), its basic sites determined by back titration and Response Surface Methodology (RSM) Box-Behnken Design (BBD) was used to optimize the modification process variables on the basic sites of the catalyst. The transesterification product, biodiesel was analyzed by Nuclear Magnetic Resonance (NMR) spectroscopy. The result reveals K-modified ZnO with highly increased basic sites. Quadratic model with high regression R2 = 0.9995 was obtained from the ANOVA of modification process, optimization at maximum basic sites criterion gave optimum modification conditions of K-loading = 8.5% (wt.), calcination temperature = 480 oC and time = 4 hours with response and basic sites = 8.14 mmol/g which is in close agreement with the experimental value of 7.64 mmol/g. The catalyst was used and a value of 95.53% biodiesel conversion was obtained and effect of potassium leaching was not significant in the process

Ga and In modified ceria as supports for cobalt-catalyzed Fischer-Tropsch synthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gnanamani, Muthu Kumaran; Jacobs, Gary; Shafer, Wilson D.

Ga- and In-modified ceria (Ce 0.8Ga 0.2O 2, Ce 0.8In 0.2O 2) materials were used as supports for cobalt-catalyzed Fischer-Tropsch synthesis (FTS). The addition of Ga to ceria was found to improve CO conversion for cobalt-catalyzed FTS, while the addition of In tended to decrease it. A similar trend was observed with the Ag-promoted cobalt/ceria catalysts. Doping of ceria with Ga or In decreased methane and increased the selectivity to olefins and alcohols for Ag-promoted cobalt/ceria. The sum of the products of olefins and alcohols for various catalysts exhibited a decreasing trend as follows: Ag-Co/Ce-Ga > Ag-Co/Ce-In > Ag-Co/Ce. Resultsmore » of H 2-TPR-XANES showed that adding of Ga or In to ceria increases the fraction of Ce 3+ in the surface shell for both unpromoted and Ag-promoted catalysts in the range of temperature typical of catalyst activation. In conclusion, this partially reduced ceria plays an important role in controlling the product selectivity of cobalt-catalyzed FT synthesis.« less

Ga and In modified ceria as supports for cobalt-catalyzed Fischer-Tropsch synthesis

DOE PAGES

Gnanamani, Muthu Kumaran; Jacobs, Gary; Shafer, Wilson D.; ...

2017-08-24

Ga- and In-modified ceria (Ce 0.8Ga 0.2O 2, Ce 0.8In 0.2O 2) materials were used as supports for cobalt-catalyzed Fischer-Tropsch synthesis (FTS). The addition of Ga to ceria was found to improve CO conversion for cobalt-catalyzed FTS, while the addition of In tended to decrease it. A similar trend was observed with the Ag-promoted cobalt/ceria catalysts. Doping of ceria with Ga or In decreased methane and increased the selectivity to olefins and alcohols for Ag-promoted cobalt/ceria. The sum of the products of olefins and alcohols for various catalysts exhibited a decreasing trend as follows: Ag-Co/Ce-Ga > Ag-Co/Ce-In > Ag-Co/Ce. Resultsmore » of H 2-TPR-XANES showed that adding of Ga or In to ceria increases the fraction of Ce 3+ in the surface shell for both unpromoted and Ag-promoted catalysts in the range of temperature typical of catalyst activation. In conclusion, this partially reduced ceria plays an important role in controlling the product selectivity of cobalt-catalyzed FT synthesis.« less

Sol-gel 3-glycidoxypropyltriethoxysilane finishing on different fabrics: The role of precursor concentration and catalyst on the textile performances and cytotoxic activity.

PubMed

Plutino, M R; Colleoni, C; Donelli, I; Freddi, G; Guido, E; Maschi, O; Mezzi, A; Rosace, G

2017-11-15

In this paper, the influence of 3-glycidoxypropyltriethoxysilane (GPTES) based organic-inorganic coatings on the properties of treated textile fabrics was studied. All experimental results were deeply analyzed and thereafter correlated with the employed silica precursor concentration and with the presence of the BF 3 OEt 2 (Boron trifluoride diethyl etherate), used as epoxy ring opening catalyst. SEM analysis, FT-IR spectroscopy, X-ray Photoelectron Spectroscopy (XPS), thermogravimetric analysis (TGA) and washing fastness tests of the sol-gel treated cotton fabric samples were firstly exploited in order to characterize the morphological and structural features of the achieved coatings. Finally, the influence of the resulting nanohybrid coatings was explored in terms of abrasion resistance, tensile strength and elongation properties of treated cotton, polyester and silk fabrics. The catalyst amounts seem to strongly improve the formation of coatings, but still they do not influence the wear resistance of treated textile fabrics to the same extent. Indeed, it was found that increasing catalyst/GPTES ratio leads to a more cross linked inorganic 3D-network. GPTES itself was not found to affect the bulk properties of the selected textile and the resulting coatings were not so rigid to hardly modify the mechanical properties of the treated samples. Finally, it is worth mentioning that in all case the obtained 3-glycidoxypropyltriethoxysilane-based chemical finishing have shown no cytotoxic effects on human skin cells. Copyright © 2017 Elsevier Inc. All rights reserved.

Propylene epoxidation over biogenic Au/TS-1 catalysts by Cinnamomum camphora extract in the presence of H2 and O2

NASA Astrophysics Data System (ADS)

Du, Mingming; Huang, Jiale; Sun, Daohua; Li, Qingbiao

2016-03-01

The Au/TS-1 catalysts with different Au nanoparticles (NPs) sizes ranging from 3.1 to 8.4 nm but the same Au loading of 0.5 wt% were prepared by Cinnamomum camphora (CC) extract, and were used for propylene epoxidation. The results showed that the interaction between Au and TS-1 support surface is important for propylene epoxidation and much smaller Au NPs (<3 nm) are the dominant active sites. After reaction of 100 h, there is no decreasing in both the activity and the PO selectivity for the Au/TS-1 catalysts, and only 1.8 wt% of the carbonaceous deposits on the surface of the catalyst after reaction, suggesting that the desorption of the product from the modified catalysts surface by residual biomolecules is much easier.

In situ DRIFTS investigation of NH3-SCR reaction over CeO2/zirconium phosphate catalyst

NASA Astrophysics Data System (ADS)

Zhang, Qiulin; Fan, Jie; Ning, Ping; Song, Zhongxian; Liu, Xin; Wang, Lanying; Wang, Jing; Wang, Huimin; Long, Kaixian

2018-03-01

A series of ceria modified zirconium phosphate catalysts were synthesized for selective catalytic reduction of NO with ammonia (NH3-SCR). Over 98% NOx conversion and 98% N2 selectivity were obtained by the CeO2/ZrP catalyst with 20 wt.% CeO2 loading at 250-425 °C. The interaction between CeO2 and zirconium phosphate enhanced the redox abilities and surface acidities of the catalysts, resulting in the improvement of NH3-SCR activity. The in situ DRIFTS results indicated that the NH3-SCR reaction over the catalysts followed both Eley-Rideal and Langmuir-Hinshelwood mechanisms. The amide (sbnd NH2) groups and the NH4+ bonded to Brønsted acid sites were the important intermediates of Eley-Rideal mechanism.

Effect of water and alkali modifications on ETS-10 for the cycloaddition of CO2 to propylene oxide.

PubMed

Doskocil, Eric J

2005-02-17

Sodium oxide (NaOx) impregnated Engelhard Titanosilicate-10 (ETS-10) molecular sieve catalysts were prepared to enhance the basicity associated with ETS-10 and subsequently investigated for the cycloaddition of carbon dioxide to propylene oxide to produce propylene carbonate. For dry NaOx-modified ETS-10 catalysts that contained no adsorbed water, a maximum yield of propylene carbonate was achieved at a loading of 2.0 excess NaOx species per unit cell. However, the greatest enhancements in the rate of reaction were observed when small amounts of water were adsorbed onto the unmodified ETS-10 catalyst immediately prior to reaction. Surface-bound water appears to enhance the surface Bronsted acidity of the unmodified ETS-10 catalyst via the formation of surface -OH groups at lower water loadings, producing a surface of better-tuned acid-base bifunctional characteristics for the cycloaddition reaction. At levels of hydration greater than 12.5% by mass, the yield of propylene carbonate was further enhanced, but at a smaller rate than that observed at lower rehydration levels, which is more indicative of an enhanced transport effect. Adsorption microcalorimetry of carbon dioxide indicated that, at loadings less than 2.0 NaOx per unit cell, the total uptake of the CO2 adsorption sites required for the reaction were less than in the parent ETS-10 material. However, at higher levels of NaOx occlusion, where the total uptake and strength of the adsorption sites exceeded those observed for the as-received ETS-10 material, the cycloaddition activity of this catalyst suffered due to the reduced pore volume and surface area. It appears that precise tuning of both the surface acidity and basicity is crucial in creating an effective acid-base bifunctional ETS-10 catalyst for the cycloaddition reaction investigated.

A Novel Methodology for the Synthesis of Acyloxy Castor Polyol Esters: Low Pour Point Lubricant Base Stocks.

PubMed

Kamalakar, Kotte; Mahesh, Goli; Prasad, Rachapudi B N; Karuna, Mallampalli S L

2015-01-01

Castor oil, a non-edible oil containing hydroxyl fatty acid, ricinoleic acid (89.3 %) was chemically modified employing a two step procedure. The first step involved acylation (C(2)-C(6) alkanoic anhydrides) of -OH functionality employing a green catalyst, Kieselguhr-G and solvent free medium. The catalyst after reaction was filtered and reused several times without loss in activity. The second step is esterification of acylated castor fatty acids with branched mono alcohol, 2-ethylhexanol and polyols namely neopentyl glycol (NPG), trimethylolpropane (TMP) and pentaerythritol (PE) to obtain 16 novel base stocks. The base stocks when evaluated for different lubricant properties have shown very low pour points (-30 to -45°C) and broad viscosity ranges 20.27 cSt to 370.73 cSt, higher viscosity indices (144-171), good thermal and oxidative stabilities, and high weld load capacities suitable for multi-range industrial applications such as hydraulic fluids, metal working fluids, gear oil, forging and aviation applications. The study revealed that acylated branched mono- and polyol esters rich in monounsaturation is desirable for developing low pour point base stocks.

Calcium oxide-modified mesoporous silica loaded onto ferriferrous oxide core: Magnetically responsive mesoporous solid strong base.

PubMed

Li, Tian-Tian; Liu, Yu; Qi, Shi-Chao; Liu, Xiao-Qin; Huang, Li; Sun, Lin-Bing

2018-05-03

The design of new type of solid strong base with ideal activity, stability, and reusability is strongly urged by the growing demand of green chemistry and sustainable development. In this study, a new type of mesoporous solid strong base, denoted as CaO/mSiO 2 /Fe 3 O 4 , is successfully fabricated by successively coating SiO 2 onto Fe 3 O 4 magnetic nanoparticles and loading CaO into the mesoporous SiO 2 . Compared with a series of other typical solid bases, the CaO/mSiO 2 /Fe 3 O 4 exhibits higher activity towards the synthesis of dimethyl carbonate by the transesterification of ethylene carbonate and methanol. The activity of the CaO/mSiO 2 /Fe 3 O 4 is not observed to decrease obviously even after sextic catalyst recirculation, and in particular, the recovery of the catalyst without quality loss is very convenient due to the good magnetic responsiveness of the Fe 3 O 4 cores. Copyright © 2018. Published by Elsevier Inc.

Low Temperature Catalyst for NH3 Removal

NASA Technical Reports Server (NTRS)

Monje, Oscar; Melendez, Orlando

2013-01-01

Air revitalization technologies maintain a safe atmosphere inside spacecraft by the removal of C02, ammonia (NH3), and trace contaminants. NH3 onboard the International Space Station (ISS) is produced by crew metabolism, payloads, or during an accidental release of thermal control refrigerant. Currently, the ISS relies on removing NH3 via humidity condensate and the crew wears hooded respirators during emergencies. A different approach to cabin NH3 removal is to use selective catalytic oxidation (SCO), which builds on thermal catalytic oxidation concepts that could be incorporated into the existing TCCS process equipment architecture on ISS. A low temperature platinum-based catalyst (LTP-Catalyst) developed at KSC was used for converting NH3 to H20 and N2 gas by SCO. The challenge of implementing SCO is to reduce formation of undesirable byproducts like NOx (N20 and NO). Gas mixture analysis was conducted using FTIR spectrometry in the Regenerable VOC Control System (RVCS) Testbed. The RVCS was modified by adding a 66 L semi-sealed chamber, and a custom NH3 generator. The effect of temperature on NH3 removal using the LTP-Catalyst was examined. A suitable temperature was found where NH3 removal did not produce toxic NO, (NO, N02) and N20 formation was reduced.

UV resistance and dimensional stability of wood modified with isopropenyl acetate.

PubMed

Nagarajappa, Giridhar B; Pandey, Krishna K

2016-02-01

Chemical modification of Rubberwood (Hevea brasiliensis Müll.Arg) with isopropenyl acetate (IPA) in the presence of anhydrous aluminum chloride as a catalyst has been carried out under solvent free conditions. The level of modification was estimated by determining the weight percent gain and modified wood was characterized by FTIR-ATR and CP/MAS (13)C NMR spectroscopy. The effect of catalyst concentration on WPG was studied. UV resistance, moisture adsorption and dimensional stability of modified wood were evaluated. UV resistance of modified wood was evaluated by exposing unmodified and modified wood to UV irradiation in a QUV accelerated weathering tester. Unmodified wood showed rapid color changes and degradation of lignin upon exposure to UV light. Chemical modification of wood polymers with IPA was effective in reducing light induced color changes (photo-yellowing) at wood surfaces. In contrast to unmodified wood, modified wood exhibited bleaching. FTIR analysis of modified wood exposed to UV light indicated stabilization of wood polymers against UV degradation. Modified wood showed good dimensional stability and hydrophobicity. Thermogravimetric analysis showed that modification with IPA improved thermal stability of wood. Improved dimensional stability and UV resistance of modified wood indicates IPA as a promising reagent since there is no acid byproduct of reaction as observed in case of other esterification reactions. Copyright © 2015 Elsevier B.V. All rights reserved.

π-Clamp-mediated cysteine conjugation

NASA Astrophysics Data System (ADS)

Zhang, Chi; Welborn, Matthew; Zhu, Tianyu; Yang, Nicole J.; Santos, Michael S.; van Voorhis, Troy; Pentelute, Bradley L.

2016-02-01

Site-selective functionalization of complex molecules is one of the most significant challenges in chemistry. Typically, protecting groups or catalysts must be used to enable the selective modification of one site among many that are similarly reactive, and general strategies that selectively tune the local chemical environment around a target site are rare. Here, we show a four-amino-acid sequence (Phe-Cys-Pro-Phe), which we call the ‘π-clamp’, that tunes the reactivity of its cysteine thiol for site-selective conjugation with perfluoroaromatic reagents. We use the π-clamp to selectively modify one cysteine site in proteins containing multiple endogenous cysteine residues. These examples include antibodies and cysteine-based enzymes that would be difficult to modify selectively using standard cysteine-based methods. Antibodies modified using the π-clamp retained binding affinity to their targets, enabling the synthesis of site-specific antibody-drug conjugates for selective killing of HER2-positive breast cancer cells. The π-clamp is an unexpected approach to mediate site-selective chemistry and provides new avenues to modify biomolecules for research and therapeutics.

Continuous Heterogeneous Photocatalysis in Serial Micro-Batch Reactors.

PubMed

Pieber, Bartholomäus; Shalom, Menny; Antonietti, Markus; Seeberger, Peter H; Gilmore, Kerry

2018-01-29

Solid reagents, leaching catalysts, and heterogeneous photocatalysts are commonly employed in batch processes but are ill-suited for continuous-flow chemistry. Heterogeneous catalysts for thermal reactions are typically used in packed-bed reactors, which cannot be penetrated by light and thus are not suitable for photocatalytic reactions involving solids. We demonstrate that serial micro-batch reactors (SMBRs) allow for the continuous utilization of solid materials together with liquids and gases in flow. This technology was utilized to develop selective and efficient fluorination reactions using a modified graphitic carbon nitride heterogeneous catalyst instead of costly homogeneous metal polypyridyl complexes. The merger of this inexpensive, recyclable catalyst and the SMBR approach enables sustainable and scalable photocatalysis. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improving the durability of methanol oxidation reaction electro-catalysts through the modification of carbon architectures

NASA Astrophysics Data System (ADS)

Wood, Kevin N.

Carbon materials represent one of the largest areas of studied research today, having integrated applications stretching from energy production and storage to medical use and far beyond. One of these many intriguing applications is fuel cells, which offers the promise of clean electricity through a direct electrochemical energy conversion process. Unfortunately, at the present time the cost per watt-hour produced by fuel cells is more expensive than conventional methods of energy production/storage (i.e. combustion engines, batteries, etc.). Under the umbrella of fuel cell systems, methanol is a promising fuel source because of its high energy density and convenience of direct liquid fuel operation. In this field, recent advancements are bringing direct methanol fuel cells (DMFCs) closer to commercial viability. However, just as in other fuel cell systems, further improvements are greatly needed, particularly in the area of catalyst durability. This need for improved durability has led to increased research activity focused on improving catalyst stability and utilization. This thesis explores one of the most promising areas of enhancing catalyst-support interactions; namely, modification of carbon support architectures. Through the use of heteroatom modifiers, such as nitrogen, fuel cell support systems can be enhanced in such a way as to improve metal nucleation and growth, catalyst durability and catalytic activity. To this end, this thesis employs advanced characterization techniques to study the changes in catalyst particle morphology before and after nitrogen modification of the support structure. These results clearly show the beneficial effects of nitrogen moieties on carbon structures and help elucidate the effects of nitrogen on the stability of supported catalytic nanoparticles systems. Similarly, the novel concept of post-modifying commercially available supported catalysts with nitrogen ion implantation gives further insight into the behavior of modified support structures. This result shows a method by which current industry leading benchmarks can be improved, in some cases by up to 100%. This thesis also explores the intriguing prospect of heteroatom modification beyond the effects of just nitrogen. Specifically, the consequences of halide functionalization are explored and shown to significantly improve durability, even to a greater extent than nitrogen modification. In total these results give great promise for the future of fuel cell technology and the field of carbon modification in general. While the techniques and results presented in this thesis are employed to study durability in direct methanol fuel cells, the benefits of heteroatom modified carbon structures can be applied to other polymer electrolyte fuel cells and beyond. Many other devices and applications, including batteries, supercapacitors, hydrogen storage, and even biosensing and drug delivery can benefit from the work discussed within these pages.

Synthesis of a Ni2P/Ni12P5 bi-phase nanocomposite for the efficient catalytic reduction of 4-nitrophenol based on the unique n-n heterojunction effects.

PubMed

Tian, Feng-Yu; Hou, Dongfang; Zhang, Wei-Min; Qiao, Xiu-Qing; Li, Dong-Sheng

2017-10-24

A novel heterostructure catalyst of Ni 2 P/Ni 12 P 5 has been fabricated through a simple solvothermal method by modifying the molar ratio of the initial raw materials. The products are characterized by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HRTEM), nitrogen adsorption and X-ray photoelectron spectroscopy (XPS). It is found that the two phases, Ni 2 P and Ni 12 P 5 , are interlaced with one another in the as-formed nanocomposite, resulting in more interfaces. The bi-phase catalyst exhibits a markedly enhanced catalytic activity in the reduction of 4-nitrophenol, as compared to that of single Ni 2 P or Ni 12 P 5 . The enhanced catalytic activity can be attributed to the unique n-n series effects, which result in the increased ease of electron transfer over the Ni 2 P/Ni 12 P 5 bi-phase catalyst.

Carbon-Nanotube-Supported Bio-Inspired Nickel Catalyst and Its Integration in Hybrid Hydrogen/Air Fuel Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gentil, Solène; Lalaoui, Noémie; Dutta, Arnab

A biomimetic nickel bis-diphosphine complex incorporating the amino-acid arginine in the outer coordination sphere, was immobilized on modified single-wall carbon nanotubes (SWCNTs) through electrostatic interactions. The sur-face-confined catalyst is characterized by a reversible 2-electron/2-proton redox process at potentials close to the equibrium potential of the H+/H2 couple. Consequently, the functionalized redox nanomaterial exhibits reversible electrocatalytic activity for the H2/2H+ interconversion over a broad range of pH. This system exhibits catalytic bias, analogous to hydrogenases, resulting in high turnover frequencies at low overpotentials for electrocatalytic H2 oxida-tion between pH 0 and 7. This allowed integrating such bio-inspired nanomaterial together with amore » multicopper oxi-dase at the cathode side in a hybrid bioinspired/enzymatic hydrogen fuel cell. This device delivers ~2 mW cm–2 with an open-circuit voltage of 1.0 V at room temperature and pH 5, which sets a new efficiency record for a bio-related hydrogen fuel cell with base metal catalysts.« less

Catalytic conversion of corncob and corncob pretreatment hydrolysate to furfural in a biphasic system with addition of sodium chloride.

PubMed

Qing, Qing; Guo, Qi; Zhou, Linlin; Wan, Yilun; Xu, Youqing; Ji, Huilong; Gao, Xiaohang; Zhang, Yue

2017-02-01

Catalytic conversion of corncob pretreatment hydrolysate and raw corncob into furfural in a modified biphasic system by SO 4 2- /SnO 2 - MMT solid catalyst has been developed. The influence of the organic solvent type, organic to water phase ratio, sodium chloride concentration, reaction temperature and time on the furfural production were comparatively evaluated. The results showed that furfural yields of 81.7% and 66.1% were achieved at 190°C for 15mins and 190°C for 20mins, respectively, for corncob pretreatment hydrolysate and raw corncob by this solid catalyst. The solid catalyst used in this study exhibited good stability and high efficiency applied in the modified biphasic system in addition to excellent recyclability. The proposed catalytic system displayed high performance for catalytic conversion of lignocellulosic biomass into important platform chemicals and has great potential in industrial application. Copyright © 2016 Elsevier Ltd. All rights reserved.

A novel method for synthesis of phosphomolybdic acid-modified Pd/C catalysts for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Zhu, Mingyuan; Gao, Xiaoling; Luo, Guangqin; Dai, Bin

2013-03-01

This manuscript reports a convenient method for immobilizing phosphomolybdic acid (HPMo) on polyaniline (PAN-) functionalized carbon supports. The obtained HPMo-PAN-C sample is used as the support to prepare a Pd/HPMo-PAN-C catalyst. The samples are characterized by Fourier transform infrared spectroscopy, transmission electron microscopy and X-ray diffraction analysis. The results suggest that HPMo retains its Keggin structure and that the presence of HPMo reduces the average particle size of the Pd nano-particles in the obtained Pd/HPMo-PAN-C catalyst. Electro-chemical measurements in 0.5 M HClO4 solution reveal that the Pd/HPMo-PAN-C catalyst has higher catalytic activity for oxygen reduction reactions than does a Pd/C catalyst prepared using a similar procedure. The stability of the Pd/HPMo-PAN-C catalyst is evaluated by multiple-cycle voltammetry techniques; the mass catalytic activity decreases by only 10% after 100 scanning cycles.

Promotion of redox and stability features of doped Ce-W-Ti for NH3-SCR reaction over a wide temperature range

NASA Astrophysics Data System (ADS)

Zhao, Kun; Han, Weiliang; Lu, Gongxuan; Lu, Jiangyin; Tang, Zhicheng; Zhen, Xinping

2016-08-01

In this study, transition metals Co, Mn, and Cu were introduced into a Ce-W-Ti catalyst to promote low-temperature catalytic activity. Among these metal-modified M/Ce-W-Ti catalysts (M represents Co, Mn, or Cu), the Cu/Ce-W-Ti catalyst with an optimized Cu content of 5 wt.% exhibited more than 90% conversion of nitrogen oxide (NOx) in the selective catalytic reduction by NH3 over a wide temperature range (260-400 °C). This catalyst likewise exhibited higher resistance to SO2 gas and water vapor under severe test conditions. On the basis of the characterization results by powder X-ray diffraction and X-ray photoelectron spectroscopy, we concluded that the superior catalytic properties of the Cu/Ce-W-Ti catalyst could be attributed to the highly dispersed Cu species, which increased the contents of Ce3+ species and adsorbed oxygen species in the catalysts. In addition, the NH3 temperature-programmed desorption results demonstrated that the Cu species doped into the Ce-W-Ti catalysts optimized surface acid content.

Catalyst activity maintenance study for the liquid phase dimethyl ether process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peng, X.D.; Toseland, B.A.; Underwood, R.P.

1995-12-31

The co-production of dimethyl ether (DME) and methanol from syngas is a process of considerable commercial attractiveness. DME coproduction can double the productivity of a LPMEOH process when using coal-derived syngas. This in itself may offer chemical producers and power companies increased flexibility and more profitable operation. DME is also known as a clean burning liquid fuel; Amoco and Haldor-Topsoe have recently announced the use of DME as an alternative diesel fuel. Moreover, DME can be an interesting intermediate in the production of chemicals such as olefins and vinyl acetate. The current APCl liquid phase dimethyl ether (LPDME) process utilizesmore » a physical mixture of a commercial methanol synthesis catalyst and a dehydration catalyst (e.g., {gamma}-alumina). While this arrangement provides a synergy that results in much higher syngas conversion per pass compared to the methanol-only process, the stability of the catalyst system suffers. The present project is aimed at reducing catalyst deactivation both by understanding the cause(s) of catalyst deactivation and by developing modified catalyst systems. This paper describes the current understanding of the deactivation mechanism.« less

Vertical Carbon Nanotube Device in Nanoporous Templates

NASA Technical Reports Server (NTRS)

Sands, Timothy (Inventor); Fisher, Timothy Scott (Inventor); Bashir, Rashid (Inventor); Maschmann, Matthew Ralph (Inventor)

2014-01-01

A modified porous anodic alumina template (PAA) containing a thin CNT catalyst layer directly embedded into the pore walls. CNT synthesis using the template selectively catalyzes SWNTs and DWNTs from the embedded catalyst layer to the top PAA surface, creating a vertical CNT channel within the pores. Subsequent processing allows for easy contact metallization and adaptable functionalization of the CNTs and template for a myriad of applications.

Mössbauer study of modified iron-molybdenum catalysts for methanol oxidation

NASA Astrophysics Data System (ADS)

Ivanov, K. I.; Mitov, I. G.; Krustev, St. V.; Boyanov, B. S.

2010-03-01

The preparation and catalytic properties of mixed Fe-Mo-W catalysts toward methanol oxidation are investigated. Mössbauer spectroscopy, X-ray diffraction and chemical studies revealed the formation of two types of solid solutions with compositions Fe2(MoxW1-xO4)3 and (MoxW1-x)O3. The solid solutions formed are characterized by high activity and selectivity upon methanol oxidation and are of interest in view of their practical application. Sodium-doped iron-molybdenum catalysts are also investigated and the NaFe(MoO4)2 formation was established.

Influence of the support of CoMo sulfide catalysts and of the addition of potassium and platinum on the catalytic performances for the hydrodeoxygenation of carbonyl, carboxyl, and guaiacol-type molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Centeno, A.; Laurent, E.; Delmon, B.

1995-07-01

The present work corresponds to part of a program aimed at upgrading oil obtained by pyrolysis of biomass by hydrotreatment (hydrodeoxygenation HDO). CoMo sulfide catalysts, nonsupported, supported on different supports (alumina, carbon, silica), or modified by K or Pt, were used. The authors used a model reacting mixture containing compounds representative of the molecules that must react to permit a primary stabilisation of the pyrolytic oil: 4-methy lacetophenone (4-MA), diethylsebacate (DES), and guaiacol (GUA). In the reaction of the carbonyl group of the 4-MA it is shown that no important role is played by any acid-base mechanism; dispersion determines themore » activity. Acidity of the support influences the formation of active sites for decarboxylation and hydrogenation of the carboxyl group of DES. It was confirmed that guaiacol-type molecules lead to coking reactions. The role of acidity in the mechanism of these reactions is confirmed, but the modifications made in the catalysts in this work are still not sufficient to control coke deposition. The catalysts supported on carbon lead to the direct elimination of the methoxyl group of the guaiacol. Carbon, on the whole, seems to be a promising support. This work suggests that appropriate modifications of the hydrotreating catalysts can lead to a more effective process for stabilisation of the bio-oils by reaction with hydrogen. 55 refs., 3 figs., 5 tabs.« less

Nano Catalysts for Diesel Engine Emission Remediation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Narula, Chaitanya Kumar; Yang, Xiaofan; Debusk, Melanie Moses

2012-06-01

The objective of this project was to develop durable zeolite nanocatalysts with broader operating temperature windows to treat diesel engine emissions to enable diesel engine based equipment and vehicles to meet future regulatory requirements. A second objective was to improve hydrothermal durability of zeolite catalysts to at least 675 C. The results presented in this report show that we have successfully achieved both objectives. Since it is accepted that the first step in NO{sub x} conversion under SCR (selective catalytic reduction) conditions involves NO oxidation to NO{sub 2}, we reasoned that catalyst modification that can enhance NO oxidation at low-temperaturesmore » should facilitate NO{sub x} reduction at low temperatures. Considering that Cu-ZSM-5 is a more efficient catalyst than Fe-ZSM-5 at low-temperature, we chose to modify Cu-ZSM-5. It is important to point out that the poor low-temperature efficiency of Fe-ZSM-5 has been shown to be due to selective absorption of NH{sub 3} at low-temperatures rather than poor NO oxidation activity. In view of this, we also reasoned that an increased electron density on copper in Cu-ZSM-5 would inhibit any bonding with NH{sub 3} at low-temperatures. In addition to modified Cu-ZSM-5, we synthesized a series of new heterobimetallic zeolites, by incorporating a secondary metal cation M (Sc{sup 3+}, Fe{sup 3+}, In{sup 3+}, and La{sup 3+}) in Cu exchanged ZSM-5, zeolite-beta, and SSZ-13 zeolites under carefully controlled experimental conditions. Characterization by diffuse-reflectance ultra-violet-visible spectroscopy (UV-Vis), X-ray powder diffraction (XRD), extended X-ray absorption fine structure spectroscopy (EXAFS) and electron paramagnetic resonance spectroscopy (EPR) does not permit conclusive structural determination but supports the proposal that M{sup 3+} has been incorporated in the vicinity of Cu(II). The protocols for degreening catalysts, testing under various operating conditions, and accelerated aging conditions were provided by our collaborators at John Deere Power Systems. Among various zeolites reported here, CuFe-SSZ-13 offers the best NO{sub x} conversion activity in 150-650 C range and is hydrothermally stable when tested under accelerated aging conditions. It is important to note that Cu-SSZ-13 is now a commercial catalyst for NO{sub x} treatment on diesel passenger vehicles. Thus, our catalyst performs better than the commercial catalyst under fast SCR conditions. We initially focused on fast SCR tests to enable us to screen catalysts rapidly. Only the catalysts that exhibit high NO{sub x} conversion at low temperatures are selected for screening under varying NO{sub 2}:NO{sub x} ratio. The detailed tests of CuFe-SSZ-13 show that CuFe-SSZ-13 is more effective than commercial Cu-SSZ-13 even at NO{sub 2}:NO{sub x} ratio of 0.1. The mechanistic studies, employing stop-flow diffuse reflectance FTIR spectroscopy (DRIFTS), suggest that high concentration of NO{sup +}, generated by heterobimetallic zeolites, is probably responsible for their superior low temperature NO{sub x} activity. The results described in this report clearly show that we have successfully completed the first step in a new emission treatment catalyst which is synthesis and laboratory testing employing simulated exhaust. The next step in the catalyst development is engine testing. Efforts are in progress to obtain follow-on funding to carry out scale-up and engine testing to facilitate commercialization of this technology.« less

New insides in the characterization of HDS industrial catalysts by HAADF-STEM

NASA Astrophysics Data System (ADS)

Del Angel, Paz; Ponce, Arturo; Arellano, Josefina; Yacaman, Miguel J.; Hernandez-Pichardo, Martha; Montoya, J. Ascencion; Escobar, Jose

2015-03-01

Hydrodesulfurization (HDS) catalysts are of great importance in the petroleum industry. Transition metal sulphides catalysts of Ni(Co)Mo(W)/Al2O3 are widely used for hydrotreating reactions, like hydrodenitrogenation and HDS. One of the main issue in these catalysts is to understand the mechanism of the reaction, where MoS2 plays the most important role in the catalytic activity. We studied an industrial NiMo/Alumina sulfide catalyst highly active by using aberration-corrected HAADF-STEM techniques. The used catalysts was a state-of- the art commercial nickel-molybdenum alumina-supported formulation, including organic agent modifier. This type of material belongs to a novel family of catalysts specially designed for ultra-low sulfur production from straight-run gas oil (SRGO), cycle oil, coker gas oil, or their combinations at operating conditions of commercial interest in hydrotreating units at industrial scale. Aberration corrected HAADF-STEM allowed to observe the nanostructure and location of MoS2 and his interaction with the alumina. The results indicate that the MoS2 is highly dispersed on the alumina, however the location of Ni is one of the task of this kind of catalyst.

Efficient degradation of H2S over transition metal modified TiO2 under VUV irradiation: Performance and mechanism

NASA Astrophysics Data System (ADS)

Liu, Gaoyuan; Ji, Jian; Hu, Peng; Lin, Sixin; Huang, Haibao

2018-03-01

Odor pollution causes great harm to the atmospheric environment and human health. H2S, as an odor gas, is highly toxic and corrosive and thus requires removal efficiently. In this study, TiO2 catalysts modified by transition metals including Mn, Cu, Ni and Co, were prepared using a modified sol-gelatin method and tested under UV-PCO or VUV-PCO process. H2S degradation was great enhanced in VUV-PCO compared with conventional UV-PCO. Among the catalysts, 1 wt% Mn-TiO2 showed the highest removal efficiency of 89.9%, which is 30 times higher than that under 254 nm UV irradiation. Residual ozone in the outlet can be completely eliminated by Mn-TiO2. Photocatalytic oxidation, photolysis and ozone-assisted catalytic oxidation all involved in the VUV-PCO process and their contribution were determined by H2S removal efficiency.

Mesoporous Aluminosilicate Catalysts for the Selective Isomerization of n-Hexane: The Roles of Surface Acidity and Platinum Metal.

PubMed

Musselwhite, Nathan; Na, Kyungsu; Sabyrov, Kairat; Alayoglu, Selim; Somorjai, Gabor A

2015-08-19

Several types of mesoporous aluminosilicates were synthesized and evaluated in the catalytic isomerization of n-hexane, both with and without Pt nanoparticles loaded into the mesopores. The materials investigated included mesoporous MFI and BEA type zeolites, MCF-17 mesoporous silica, and an aluminum modified MCF-17. The acidity of the materials was investigated through pyridine adsorption and Fourier Transform-Infrared Spectroscopy (FT-IR). It was found that the strong Brönsted acid sites in the micropores of the zeolite catalysts facilitated the cracking of hexane. However, the medium strength acid sites on the Al modified MCF-17 mesoporous silica greatly enhanced the isomerization reaction. Through the loading of different amounts of Pt into the mesopores of the Al modified MCF-17, the relationship between the metal nanoparticles and acidic sites on the support was revealed.

Synthesis of fatty acid methyl ester from palm oil (Elaeis guineensis) with Ky(MgCa)2xO3 as heterogeneous catalyst.

PubMed

Olutoye, M A; Lee, S C; Hameed, B H

2011-12-01

Fatty acid methyl esters (FAME) were produced from palm oil using eggshell modified with magnesium and potassium nitrates to form a composite, low-cost heterogeneous catalyst for transesterification. The catalyst, prepared by the combination of impregnation/co-precipitation was calcined at 830 °C for 4 h. Transesterification was conducted at a constant temperature of 65 °C in a batch reactor. Design of experiment (DOE) was used to optimize the reaction parameters, and the conditions that gave highest yield of FAME (85.8%) was 5.35 wt.% catalyst loading at 4.5 h with 16:1 methanol/oil molar ratio. The results revealed that eggshell, a solid waste, can be utilized as low-cost catalyst after modification with magnesium and potassium nitrates for biodiesel production. Copyright © 2011 Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xue, Teng; Lin, Zhaoyang; Chiu, Chin-Yi

Metallic nanoparticles are emerging as an exciting class of heterogeneous catalysts with the potential advantages of exceptional activity, stability, recyclability, and easier separation than homogeneous catalysts. The traditional colloid nanoparticle syntheses usually involve strong surface binding ligands that could passivate the surface active sites and result in poor catalytic activity. The subsequent removal of surface ligands could reactivate the surface but often leads to metal ion leaching and/or severe Ostwald ripening with diminished catalytic activity or poor stability. Molecular ligand engineering represents a powerful strategy for the design of homogeneous molecular catalysts but is insufficiently explored for nanoparticle catalysts tomore » date. We report a systematic investigation on molecular ligand modulation of palladium (Pd) nanoparticle catalysts. Our studies show that β-functional groups of butyric acid ligand on Pd nanoparticles can significantly modulate the catalytic reaction process to modify the catalytic activity and stability for important aerobic reactions. With a β-hydroxybutyric acid ligand, the Pd nanoparticle catalysts exhibit exceptional catalytic activity and stability with an unsaturated turnover number (TON) >3000 for dehydrogenative oxidation of cyclohexenone to phenol, greatly exceeding that of homogeneous Pd(II) catalysts (TON, ~30). This study presents a systematic investigation of molecular ligand modulation of nanoparticle catalysts and could open up a new pathway toward the design and construction of highly efficient and robust heterogeneous catalysts through molecular ligand engineering.« less

Novel synthesis of highly durable and active Pt catalyst encapsulated in nitrogen containing carbon for polymer electrolyte membrane fuel cell

NASA Astrophysics Data System (ADS)

Lee, Hyunjoon; Sung, Yung-Eun; Choi, Insoo; Lim, Taeho; Kwon, Oh Joong

2017-09-01

Novel synthesis of a Pt catalyst encapsulated in a N-containing carbon layer for use in a polymer electrolyte membrane fuel cell is described in this study. A Pt-aniline complex, formed by mixing Pt precursor and aniline monomer, was used as the source of Pt, C, and N. Heat treatment of the Pt-aniline complex with carbon black yielded 5 nm Pt nanoparticles encapsulated by a N-containing carbon layer originating from aniline carbonization. The synthesized Pt catalyst exhibited higher mass specific activity to oxygen reduction reaction than that shown by conventional Pt/C catalyst because pyridinic N with graphitic carbon in the carbon layer provided active sites for oxygen reduction reaction in addition to those provided by Pt. In single cell testing, initial performance of the synthesized catalyst was limited because the thick catalyst layer increased resistance related to mass transfer. However, it was observed that the carbon layer successfully prevented Pt nanoparticles from growing via agglomeration and Ostwald ripening under fuel cell operation, thereby improving durability. Furthermore, a mass specific performance of the synthesized catalyst higher than that of a conventional Pt/C catalyst was achieved by modifying the synthesized catalyst's layer thickness.

Improved Anode for a Direct Methanol Fuel Cell

NASA Technical Reports Server (NTRS)

Valdez, Thomas; Narayanan, Sekharipuram

2005-01-01

A modified chemical composition has been devised to improve the performance of the anode of a direct methanol fuel cell. The main feature of the modified composition is the incorporation of hydrous ruthenium oxide into the anode structure. This modification can reduce the internal electrical resistance of the cell and increase the degree of utilization of the anode catalyst. As a result, a higher anode current density can be sustained with a smaller amount of anode catalyst. These improvements can translate into a smaller fuel-cell system and higher efficiency of conversion. Some background information is helpful for understanding the benefit afforded by the addition of hydrous ruthenium oxide. The anode of a direct methanol fuel cell sustains the electro-oxidation of methanol to carbon dioxide in the reaction CH3OH + H2O--->CO2 + 6H(+) + 6e(-). An electrocatalyst is needed to enable this reaction to occur. The catalyst that offers the highest activity is an alloy of approximately equal numbers of atoms of the noble metals platinum and ruthenium. The anode is made of a composite material that includes high-surface-area Pt/Ru alloy particles and a proton-conducting ionomeric material. This composite is usually deposited onto a polymer-electrolyte (proton-conducting) membrane and onto an anode gas-diffusion/current-collector sheet that is subsequently bonded to the proton-conducting membrane by hot pressing. Heretofore, the areal density of noble-metal catalyst typically needed for high performance has been about 8 mg/cm2. However, not all of the catalyst has been utilized in the catalyzed electro-oxidation reaction. Increasing the degree of utilization of the catalyst would make it possible to improve the performance of the cell for a given catalyst loading and/or reduce the catalyst loading (thereby reducing the cost of the cell). The use of carbon and possibly other electronic conductors in the catalyst layer has been proposed for increasing the utilization of the catalyst by increasing electrical connectivity between catalyst particles. However, the relatively low density of carbon results in thick catalyst layers that impede the mass transport of methanol to the catalytic sites. Also, the electrical conductivity of carbon is less than 1/300th of typical metals. Furthermore, the polymer-electrolyte membrane material is acidic and most metals are not chemically stable in contact with it. Finally, a material that conducts electrons (but not protons) does not contribute to the needed transport of protons produced in the electro-oxidation reaction.

New catalyst supports prepared by surface modification of graphene- and carbon nanotube structures with nitrogen containing carbon coatings

NASA Astrophysics Data System (ADS)

Oh, Eun-Jin; Hempelmann, Rolf; Nica, Valentin; Radev, Ivan; Natter, Harald

2017-02-01

We present a new and facile method for preparation of nitrogen containing carbon coatings (NCC) on the surface of graphene- and carbon nanotubes (CNT), which has an increased electronic conductivity. The modified carbon system can be used as catalyst support for electrocatalytic applications, especially for polymer electrolyte membrane fuel cells (PEMFC). The surface modification is performed by impregnating carbon structures with a nitrogen containing ionic liquid (IL) with a defined C:N ratio, followed by a thermal treatment under ambient conditions. We investigate the influence of the main experimental parameters (IL amount, temperature, substrate morphology) on the formation of the NCC. Additionally, the structure and the chemical composition of the resulting products are analyzed by electron microscopic techniques (SEM, TEM), energy disperse X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS) and hot extraction analysis. The modified surface has a nitrogen content of 29 wt% which decreases strongly at temperatures above 600 °C. The new catalyst supports are used for the preparation of PEMFC anodes which are characterized by polarization measurements and electrochemical impedance spectroscopy (EIS). Compared to unmodified graphene and CNT samples the electronic conductivity of the modified systems is increased by a factor of 2 and shows improved mass transport properties.

Regulation of the catalytic behavior of pullulanases chelated onto nickel (II)-modified magnetic nanoparticles.

PubMed

Wang, Jianfeng; Liu, Zhongmei; Zhou, Zhemin

2017-06-01

Chelating of pullulanases onto nickel (II)-modified magnetic nanoparticles results in one-step purification and immobilization of pullulanase, and facilitates the commercial application of pullulanase in industrial scale. To improve the catalytic behavior, especially the operational stability, of the nanocatalyst in consecutive batch reactions, we prepared various iminodiacetic acid-modified magnetic nanoparticles differed in surface polarity and spacer length, on which the His6-tagged pullulanases were chelated via nickel ions, and then studied the correlation between the MNPs surface property and the corresponding catalyst behavior. When pullulanases were chelated onto the surface-modified MNPs, the thermostability of all pullulanase derivatives were lower than that of free counterpart, being not relevant to the protein orientation guided by the locality of the His6-tag, but related to the MNPs basal surface polarity and the grafted spacer length. After chelating of pullulanases onto MNPs, there were changes observed in the pH-activity profile and the apparent Michaelis constant toward pullulan. The changing tendencies were mainly dependent on the His6-tagged pullulanase orientation, and the changing extents were tuned by the spacer length. The reusability of pullulanase immobilized by N-terminal His6-tag was higher than that of pullulanase immobilized by C-terminal His6-tag. Moreover, the reusability of the immobilized pullulanase tested increased till grafting polyether amine-400 as spacer-arm, therefore the N-terminal His6-tagged pullulanase chelating MNPs grafted polyether amine-400 gave the best reusability, which retained 60% of initial activity after 18 consecutive cycles with a total reaction time of 9h. Additionally, the correlation analysis of the catalyst behaviors indicated that the reusability was independent from other catalytic properties such as thermostability and substrate affinity. All the results revealed that the catalyst behavior can be mainly controlled by the His6-tagged pullulanase orientation than by the MNPs surface property which can tune the catalyst function. Copyright © 2017. Published by Elsevier Inc.

Trimerization of aromatic nitriles

NASA Technical Reports Server (NTRS)

Hsu, L. C. (Inventor)

1977-01-01

Triazine compounds and cross-linked polymer compositions were made by heating aromatic nitriles to a temperature in the range of about 100 C to about 700 C, in the presence of a catalyst or mixture of catalysts. Aromatic nitrile-modified (terminated and/or appended) imide, benzimidazole, imidazopyrrolone, quinoxaline, and other condensation type prepolymers or their precopolymers were made which were trimerized with or without a filler by the aforementioned catalytic trimerization process.

Synthesis of Improved Antileishmanial and Antitrypanosomal Drugs, Treatment and Prophylaxis

DTIC Science & Technology

1988-02-01

methyl-8-nitroquinoline was hydrogenated using Raney nickel catalyst to give the corresponding 8-aminoquinoline J_ in 84$ yield as described under... nickel catalyst using a procedure (slightly modified) developed under a prior contract (10). The crude product was chromatographed over silica gel...8-Amino-6-methoxy-4-methylquinoline (1): - The title compd was prepared by the reduction of 6-methoxy-4-methyl-8-nitroquinoline (16 g) with Raney

Composite catalysts supported on modified carbon substrates and methods of making the same

DOEpatents

Popov, Branko N [Columbia, SC; Subramanian, Nalini [Kennesaw, GA; Colon-Mercado, Hector R [Columbia, SC

2009-11-17

A method of producing a composite carbon catalyst is generally disclosed. The method includes oxidizing a carbon precursor (e.g., carbon black). Optionally, nitrogen functional groups can be added to the oxidized carbon precursor. Then, the oxidized carbon precursor is refluxed with a non-platinum transitional metal precursor in a solution. Finally, the solution is pyrolyzed at a temperature of at least about 500.degree. C.

Carbon-Nanotube-Supported Bio-Inspired Nickel Catalyst and Its Integration in Hybrid Hydrogen/Air Fuel Cells.

PubMed

Gentil, Solène; Lalaoui, Noémie; Dutta, Arnab; Nedellec, Yannig; Cosnier, Serge; Shaw, Wendy J; Artero, Vincent; Le Goff, Alan

2017-02-06

A biomimetic nickel bis-diphosphine complex incorporating the amino acid arginine in the outer coordination sphere was immobilized on modified carbon nanotubes (CNTs) through electrostatic interactions. The functionalized redox nanomaterial exhibits reversible electrocatalytic activity for the H 2 /2 H + interconversion from pH 0 to 9, with catalytic preference for H 2 oxidation at all pH values. The high activity of the complex over a wide pH range allows us to integrate this bio-inspired nanomaterial either in an enzymatic fuel cell together with a multicopper oxidase at the cathode, or in a proton exchange membrane fuel cell (PEMFC) using Pt/C at the cathode. The Ni-based PEMFC reaches 14 mW cm -2 , only six-times-less as compared to full-Pt conventional PEMFC. The Pt-free enzyme-based fuel cell delivers ≈2 mW cm -2 , a new efficiency record for a hydrogen biofuel cell with base metal catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Combinatorial Search for High-Activity Hydrogen Catalysts Based on Transition-Metal-Embedded Graphitic Carbons

DOE PAGES

Choi, Woon Ih; Wood, Brandon C.; Schwegler, Eric; ...

2015-09-22

Transition metal (TM) atoms in porphyrin–like complexes play important roles in many protein and enzymetic systems, where crystal–field effects are used to modify d–orbital levels. Inspired by the tunable electronic structure of these motifs, a high–throughput computational search for synthetic hydrogen catalysts is performed based on a similar motif of TM atoms embedded into the lattice of graphene. Based on an initial list of 300 possible embedding geometries, binders, and host atoms, descriptors for stability and catalytic activity are applied to extract ten promising candidates for hydrogen evolution, two of which are expected to exhibit high activity for hydrogen oxidation.more » In several instances, the active TM atoms are earth–abundant elements that show no activity in the bulk phase, highlighting the importance of the coordination environment in tuning the d–orbitals. In conclusion, it is found that the most active candidates involve a hitherto unreported surface reaction pathway that involves a Kubas–complex intermediate, which significantly lowers the kinetic barrier associated with hydrogen dissociation and association.« less

A Study of Iron-Nitrogen-Carbon Fuel Cell Catalysts: Chemistry - Nanostructure - Performance

NASA Astrophysics Data System (ADS)

Workman, Michael J., Jr.

Fuel cells have the potential to be a pollution-free, low-cost, and energy efficient alternative to the internal combustion engine for transportation and small-scale stationary power applications. The current state of fuel cell technology has already achieved two of these three lofty goals. The remaining barrier to wide-scale deployment is the high cost, which is primarily caused by dependence on large amounts of platinum to catalyze the energy conversion reactions. To overcome this barrier and facilitate the integration of fuel cells into mainstream applications, research into a new class of catalyst materials that do not require platinum is needed. There has been a significant amount of research effort directed toward the development of platinum-group metal free (PGM-free) catalysts, yet there is a lack of consensus on both the engineering parameters necessary to improve the technology and the fundamental science that would facilitate rational design. I have engaged in research on PGM-free catalysts based on inexpensive and abundant reagents, specifically: nicarbazin and iron. Catalysts made from these precursors have previously proven to be among the best PGM-free catalysts, but their continued advancement suffered from the same lack of understanding that besets all catalysts in this class. The work I have performed address both engineering concerns and fundamental underlying principles. I present results demonstrating correlations between physical structure, chemical speciation, and synthesis parameters, as well as addressing active site chemistry and likely locations. My research presented herein introduces new morphology analysis techniques and elucidates several key structure-to-property characteristics of catalysts derived from iron and nicarbazin. I discuss the development and application of a new length-scale specific surface analysis technique that allows for analysis of well-defined size ranges from a few nm to several microns. The existing technique of focused ion beam tomography is modified and optimized for platinum-group metal free catalyst layers, facilitating direct observation of catalyst integration into catalyst layers. I present evidence supporting the hypothesis that atomically dispersed iron coordinated with nitrogen are the dominant active sites in these catalysts. Further, that the concentration of surface oxides in the carbon structure, which can be directly influenced by synthesis parameters, correlates with both the concentration of active sites in the material and with fuel cell performance. Catalyst performance is hindered by the addition of carbon nanotubes and by the presence of metallic iron. Evidence consistent with the catalytic active sites residing in the graphitic plane is also presented.

Synthesis, characterization and application of a nano-manganese-catalyst as an efficient solid catalyst for solvent free selective oxidation of ethylbenzene, cyclohexene, and benzylalcohol

NASA Astrophysics Data System (ADS)

Habibi, Davood; Faraji, Ali Reza

2013-07-01

The object of this study is to synthesize the heterogeneous Mn-nano-catalyst (MNC) which has been covalently anchored on a modified nanoscaleSiO2/Al2O3, and characterized by FT-IR, UV-Vis, CHN elemental analysis, EDS, TEM, and EDX. The method is efficient for the highly selective oxidation of ethylbenzene, cyclohexene, and benzylalcohol without the need to any solvents, using tert-butyl hydroperoxide (TBHP) as an oxidant. Oxidation of ethylbenzene, cyclohexene, and benzylalcohol gave acetophenone, 2-cyclohexene-1-one and benzaldehyde, respectively, as major products. Reaction conditions have been optimized by considering the effect of various factors such as reaction time, amounts of substrates and oxidant, Mn-nano-catalyst and application of various solvents.

Development of dynamic kinetic resolution on large scale for (±)-1-phenylethylamine.

PubMed

Thalén, Lisa K; Bäckvall, Jan-E

2010-09-13

Candida antarctica lipase B (CALB) and racemization catalyst 4 were combined in the dynamic kinetic resolution (DKR) of (±)-1-phenylethylamine (1). Several reaction parameters have been investigated to modify the method for application on multigram scale. A comparison of isopropyl acetate and alkyl methoxyacetates as acyl donors was carried out. It was found that lower catalyst loadings could be used to obtain (R)-2-methoxy-N-(1-phenylethyl)acetamide (3) in good yield and high ee when alkyl methoxyacetates were used as acyl donors compared to when isopropyl acetate was used as the acyl donor. The catalyst loading could be decreased to 1.25 mol % Ru-catalyst 4 and 10 mg CALB per mmol 1 when alkyl methoxyacetates were used as the acyl donor.

Glucose oxidase immobilization on different modified surfaces of platinum nanowire for application in glucose detection

NASA Astrophysics Data System (ADS)

Thanh Tuyen Le, Thi; Duy Tran, Phu; Pham, Xuan Tung; Hien Tong, Duy; Chien Dang, Mau

2010-09-01

In this work, the surface of platinum (Pt) nanowires was modified by using several chemicals, including a compound of gelatin gel with SiO2, polyvinyl alcohol (PVA) with Prussian blue (PB) mediator and cysteamine self-assembled monolayers (SAM). Then, glucose oxidase (GOD) enzyme was immobilized on the modified surfaces of Pt nanowire electrodes by using techniques of electrochemical adsorption and chemical binding. The GOD immobilized Pt nanowires were used for application in glucose detection by performing a cyclic voltammetry measurement. The detection results showed that GOD was immobilized on all of the tested surfaces and the highest glucose detection sensitivity of 60 μM was obtained when the Pt nanowires were modified by PVA with PB mediator. Moreover, the sensors showed very high current response when the Pt nanowires were modified with the cysteamine SAM. The stability and catalyst activity of GOD are also reported here. For instance, the catalyst activity of GOD retained about 60% of its initial value after it was stored at 4 °C in a 100 mM PBS buffer solution with a pH of 7.2 for a period of 30 days.

Complex dynamics and enhanced photosensitivity in a modified Belousov-Zhabotinsky reaction

NASA Astrophysics Data System (ADS)

Li, Nan; Zhao, Jinpei; Wang, Jichang

2008-06-01

This study presents an experimental investigation of nonlinear dynamics in a modified Belousov-Zhabotinsky (BZ) reaction, in which the addition of 1,4-benzoquinone induced various complex behaviors such as mixed-mode oscillations and consecutive period-adding bifurcations. In addition, the presence of 1,4-benzoquinone significantly enhanced the photosensitivity of the ferroin-catalyzed BZ system, in which light-induced transitions between simple and complex oscillations have been achieved. Mechanistic study suggests that the influence of benzoquinone may arise from its interactions with the metal catalyst ferroin/ferriin, where cyclic voltammograms illustrate that the presence of benzoquinone causes an increase in the redox potential of ferroin/ferriin couple, which may consequently alternate the oxidation and reduction paths of the catalyst.

Cresol Izomerization in the Presence of Acid Catalysts

NASA Astrophysics Data System (ADS)

Tarasov, A. L.; Dunaev, S. F.; Kustov, L. M.

2018-02-01

It is shown for toluene oxidation with nitrous oxide that modifying HZSM-5 zeolite with zinc oxide nanoparticles considerably improves the selectivity and yield of cresols. It is found that a 2% ZnO/HZSM-5 composite catalyst also exhibits enhanced and stable activity at high temperatures. For the o-cresol isomerization reaction, this modification of HZSM-5 zeolite greatly reduces the contribution from disproportionation and cracking reactions proceeding with formation of phenol, C6-C9 aromatic hydrocarbons, and xylenols. The regularities of their formation in the presence of the studied catalysts are determined using the results from thermodynamic calculations for the equilibrium concentrations of cresol isomers.

Biodiesel synthesis via transesterification of lipid Chlorophyta cultivated in walne rich carbon medium using KOH/Zeolite catalyst

NASA Astrophysics Data System (ADS)

Dianursanti, Hayati, Siti Zahrotul; Putri, Dwini Normayulisa

2017-11-01

Microalgae from the Chlorophyta division such as Nannochloropsis oculata and Chlorella vulgaris are highly potential to be developed as biodiesel feedstocks because they have a high oil content up to 58%. Biodiesel is produced by transesterification of triglycerides and alcohols with the aid of homogeneous catalysts such as KOH. However, the use of KOH catalysts produces soaps in the biodiesel synthesis. Heterogeneous catalysts are known to solve this problem. One of them is natural zeolite. Zeolite can be used as a catalyst and as a support catalyst. Loading KOH on the zeolite surface is expected to increase alkalinity in KOH/Zeolite catalysts so as to increase the activity of KOH/Zeolite catalyst in transesterification of triglyceride with methanol. In this experimental lipid of microalgae will be used for produced biodiesel via transesterification reaction with methanol and KOH/Zeolite as a catalyst heterogeneous at 60 °C for 3h and utilized catalyst modificated KOH/Zeolite with variation 0.5 M, 1 M and 1.5 M KOH. The modified zeolite was then analyzed by XRF, XRD and BET. The result showed that the yield of biodiesel from lipid N.oculata was 81,09% by 0.5KOH/Zeolite catalyst, 86,53% by 1KOH/Zeolite catalyst, 1,5KOH/Zeolite and 88,13% by 1.5KOH/Zeolit, while the biodiesel produced from lipid C.vulgaris was 59.29% by 0.5KOH/Zeolite, 82.27% by 1KOH/Zeolite and 83.72% by 1.5KOH/Zeolite.

Carbon-supported, selenium-modified ruthenium-molybdenum catalysts for oxygen reduction in acidic media.

PubMed

Guinel, Maxime J-F; Bonakdarpour, Arman; Wang, Biao; Babu, Panakkattu K; Ernst, Frank; Ramaswamy, Nagappan; Mukerjee, Sanjeev; Wieckowski, Andrzej

2009-07-20

The stability and oxygen reduction activity of two carbon-supported catalyst materials are reported. The catalysts, Se/Ru and Se/(Ru-Mo), were prepared by using a chemical reduction method. The catalyst nanoparticles were evenly dispersed onto globular amorphous carbon supports, and their average size was ca. 2.4 nm. Thermal treatment at 500 °C for 2 h in an inert argon atmosphere resulted in coarsening of the nanoparticles, and also in some decrease of their activity. A gradual reduction of activity was also observed for Se/Ru during potential-cycle experiments. However, the incorporation of small amounts of Mo into the Se/Ru catalysts considerably improved the stability of the catalyst against dissolution. The Mo-containing samples showed excellent oxygen reduction activities even after cycling the potential 1000 times between 0.7 and 0.9 V. Furthermore, they showed excellent fuel-cell behavior. The performance of the Se/Ru catalysts is greatly improved by the addition of small amounts of elemental Mo. Possible mechanisms responsible for the improvement of the activity are discussed. Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic Transfer Hydrogenation of Furfural to 2-Methylfuran and 2-Methyltetrahydrofuran over Bimetallic Copper-Palladium Catalysts.

PubMed

Chang, Xin; Liu, An-Feng; Cai, Bo; Luo, Jin-Yue; Pan, Hui; Huang, Yao-Bing

2016-12-08

The catalytic transfer hydrogenation of furfural to the fuel additives 2-methylfuran (2-MF) and 2-methyltetrahydrofuran (2-MTHF) was investigated over various bimetallic catalysts in the presence of the hydrogen donor 2-propanol. Of all the as-prepared catalysts, bimetallic Cu-Pd catalysts showed the highest catalytic activities towards the formation of 2-MF and 2-MTHF with a total yield of up to 83.9 % yield at 220 °C in 4 h. By modifying the Pd ratios in the Cu-Pd catalyst, 2-MF or 2-MTHF could be obtained selectively as the prevailing product. The other reaction conditions also had a great influence on the product distribution. Mechanistic studies by reaction monitoring and intermediate conversion revealed that the reaction proceeded mainly through the hydrogenation of furfural to furfuryl alcohol, which was followed by deoxygenation to 2-MF in parallel to deoxygenation/ring hydrogenation to 2-MTHF. Finally, the catalyst showed a high reactivity and stability in five catalyst recycling runs, which represents a significant step forward toward the catalytic transfer hydrogenation of furfural. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Lidong; Zhou, Lu; Ould-Chikh, Samy

Surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. The evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanningmore » transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core–shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. As a result, these catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Lidong; Zhou, Lu; Ould-Chikh, Samy

The surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. Moreover, the evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annularmore » dark-field scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core–shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. The catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.« less

A Cu-Zn nanoparticle promoter for selective carbon dioxide reduction and its application in visible-light-active Z-scheme systems using water as an electron donor.

PubMed

Yin, Ge; Sako, Hiroshi; Gubbala, Ramesh V; Ueda, Shigenori; Yamaguchi, Akira; Abe, Hideki; Miyauchi, Masahiro

2018-04-17

Selective carbon dioxide photoreduction to produce formic acid was achieved under visible light irradiation using water molecules as electron donors, similar to natural plants, based on the construction of a Z-scheme light harvesting system modified with a Cu-Zn alloy nanoparticle co-catalyst. The faradaic efficiency of our Z-scheme system for HCOOH generation was over 50% under visible light irradiation.

Controlled surface segregation leads to efficient coke-resistant nickel/platinum bimetallic catalysts for the dry reforming of methane

DOE PAGES

Li, Lidong; Zhou, Lu; Ould-Chikh, Samy; ...

2015-02-03

Surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. The evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanningmore » transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core–shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. As a result, these catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.« less

Site-Selective Modification of Cellulose Nanocrystals with Isophorone Diisocyanate and Formation of Polyurethane-CNC Composites.

PubMed

Girouard, Natalie M; Xu, Shanhong; Schueneman, Gregory T; Shofner, Meisha L; Meredith, J Carson

2016-01-20

The unequal reactivity of the two isocyanate groups in an isophorone diisocyante (IPDI) monomer was exploited to yield modified cellulose nanocrystals (CNCs) with both urethane and isocyanate functionality. The chemical functionality of the modified CNCs was verified with ATR-FTIR analysis and elemental analysis. The selectivity for the secondary isocyanate group using dibutyl tin dilaurate (DBTDL) as the reaction catalyst was confirmed with (13)C NMR. The modified CNCs showed improvements in the onset of thermal degradation by 35 °C compared to the unmodified CNCs. Polyurethane composites based on IPDI and a trifunctional polyether alcohol were synthesized using unmodified (um-CNC) and modified CNCs (m-CNC). The degree of nanoparticle dispersion was qualitatively assessed with polarized optical microscopy. It was found that the modification step facilitated superior nanoparticle dispersion compared to the um-CNCs, which resulted in increases in the tensile strength and work of fracture of over 200% compared to the neat matrix without degradation of elongation at break.

Thermal conductivity of catalyst layer of polymer electrolyte membrane fuel cells: Part 1 - Experimental study

NASA Astrophysics Data System (ADS)

Ahadi, Mohammad; Tam, Mickey; Saha, Madhu S.; Stumper, Jürgen; Bahrami, Majid

2017-06-01

In this work, a new methodology is proposed for measuring the through-plane thermal conductivity of catalyst layers (CLs) in polymer electrolyte membrane fuel cells. The proposed methodology is based on deconvolution of bulk thermal conductivity of a CL from measurements of two thicknesses of the CL, where the CLs are sandwiched in a stack made of two catalyst-coated substrates. Effects of hot-pressing, compression, measurement method, and substrate on the through-plane thermal conductivity of the CL are studied. For this purpose, different thicknesses of catalyst are coated on ethylene tetrafluoroethylene (ETFE) and aluminum (Al) substrates by a conventional Mayer bar coater and measured by scanning electron microscopy (SEM). The through-plane thermal conductivity of the CLs is measured by the well-known guarded heat flow (GHF) method as well as a recently developed transient plane source (TPS) method for thin films which modifies the original TPS thin film method. Measurements show that none of the studied factors has any effect on the through-plane thermal conductivity of the CL. GHF measurements of a non-hot-pressed CL on Al yield thermal conductivity of 0.214 ± 0.005 Wṡm-1ṡK-1, and TPS measurements of a hot-pressed CL on ETFE yield thermal conductivity of 0.218 ± 0.005 Wṡm-1ṡK-1.

Carefully designed oxygen-containing functional groups and defects of porous carbon spheres with UV-O3 treatment and their enhanced catalytic performance

NASA Astrophysics Data System (ADS)

Han, Weiliang; Huang, Xiaosheng; Lu, Gongxuan; Tang, Zhicheng

2018-04-01

In this paper, the support surface properties (surface oxygen-containing functional groups and structure defects) of porous carbon spheres (PCSs) were carefully designed by as UV assisted O3 technology. CO catalytic oxidation reactions performed over the supported Pd-Ce catalysts on modified porous carbon spheres. Results illustrated that the Pd-Ce/PCSs catalysts exhibited high CO catalytic activity, which were increased at first, and then decreased with UV assistant-O3 treatment time. The Pd-Ce/PCSs-30 catalyst exhibited superior activity and T100 was only 15 °C. Moreover, the Pd-Ce/PCSs-30 catalyst obtained an excellent stability, and 100% CO conversion could be maintained as the time on stream evolutes up to 16h in the presence of H2O in the feed. Based on characterization results, there were two main factors: (a) the surface area and pore volume were decreased with UV-O3 treatment, leading to the enhancement of Pd-Ce particle size, and the decrease of Pd-Ce nanoparticle dispersion and mass transfer efficiency, as well as the decrease of catalytic activity of Pd-Ce/PCSs, (b) the surface oxygen content and defect sites of PCSs were raised by UV-O3 treatment, which could improve surface loading of Pd, Ce and enhance Pdsbnd Osbnd Ce bonding interactions, thereby increasing the activity of Pd-Ce/PCSs.

Molecular ligand modulation of palladium nanocatalysts for highly efficient and robust heterogeneous oxidation of cyclohexenone to phenol

DOE PAGES

Xue, Teng; Lin, Zhaoyang; Chiu, Chin-Yi; ...

2017-01-06

Metallic nanoparticles are emerging as an exciting class of heterogeneous catalysts with the potential advantages of exceptional activity, stability, recyclability, and easier separation than homogeneous catalysts. The traditional colloid nanoparticle syntheses usually involve strong surface binding ligands that could passivate the surface active sites and result in poor catalytic activity. The subsequent removal of surface ligands could reactivate the surface but often leads to metal ion leaching and/or severe Ostwald ripening with diminished catalytic activity or poor stability. Molecular ligand engineering represents a powerful strategy for the design of homogeneous molecular catalysts but is insufficiently explored for nanoparticle catalysts tomore » date. We report a systematic investigation on molecular ligand modulation of palladium (Pd) nanoparticle catalysts. Our studies show that β-functional groups of butyric acid ligand on Pd nanoparticles can significantly modulate the catalytic reaction process to modify the catalytic activity and stability for important aerobic reactions. With a β-hydroxybutyric acid ligand, the Pd nanoparticle catalysts exhibit exceptional catalytic activity and stability with an unsaturated turnover number (TON) >3000 for dehydrogenative oxidation of cyclohexenone to phenol, greatly exceeding that of homogeneous Pd(II) catalysts (TON, ~30). This study presents a systematic investigation of molecular ligand modulation of nanoparticle catalysts and could open up a new pathway toward the design and construction of highly efficient and robust heterogeneous catalysts through molecular ligand engineering.« less

Heterogeneous base catalysts for edible palm and non-edible Jatropha-based biodiesel production

PubMed Central

2014-01-01

Background Transesterification catalyzed by solid base catalyst is a brilliant technology for the noble process featuring the fast reaction under mild reacting condition in biodiesel production. Heterogeneous base catalysts are generally more reactive than solid acid catalysts which require extreme operating condition for high conversion and biodiesel yield. In the present study, synthesis of biodiesel was studied by using edible (palm) or non-edible (Jatropha) feedstock catalyzed by heterogeneous base catalysts such as supported alkali metal (NaOH/Al2O3), alkaline-earth metal oxide (MgO, CaO and SrO) and mixed metal oxides catalysts (CaMgO and CaZnO). Results The chemical characteristic, textural properties, basicity profile and leaching test of synthesized catalysts were studied by using X-ray diffraction, BET measurement, TPD-CO2 and ICP-AES analysis, respectively. Transesterification activity of solid base catalysts showed that > 90% of palm biodiesel and > 80% of Jatropha biodiesel yield under 3 wt.% of catalyst, 3 h reaction time, methanol to oil ratio of 15:1 under 65°C. This indicated that other than physicochemical characteristic of catalysts; different types of natural oil greatly influence the catalytic reaction due to the presence of free fatty acids (FFAs). Conclusions Among the solid base catalysts, calcium based mixed metal oxides catalysts with binary metal system (CaMgO and CaZnO) showed capability to maintain the transesterification activity for 3 continuous runs at ~ 80% yield. These catalysts render high durability characteristic in transesterification with low active metal leaching for several cycles. PMID:24812574

Chemically Modified Metal Oxide Nanostructure for Photoelectrochemical Water Splitting

NASA Astrophysics Data System (ADS)

Wang, Gongming

Hydrogen gas is chemical fuel with high energy density, and represents a clean, renewable and carbon-free burning fuel, which has the potential to solve the more and more urgent energy crisis in today's society. Inspired by natural photosynthesis, artificial photosynthesis to generate hydrogen energy has attracted a lot of attentions in the field of chemistry, physics and material. Photoelectrochemical water splitting based on semiconductors represents a green and low cost method to generate hydrogen fuel. However, the current overall efficiency of solar to hydrogen is quite low, due to some intrinsic limitations such as bandgap, diffusion distance, carrier lifetime and photostability of semiconductors. Although nanostructured semiconductors can improve their photoelectrochemical water splitting performance to some extent, by increasing electrolyte accessible area and shortening minority carrier diffusion distance, nanostructure engineering cannot change their intrinsic electronic properties. Recent development in chemically modified nanostructures such as surface catalyst decoration, element doping, plasmonic modification and interfacial hetero-junction design have led to significant advancement in the photoelectrochemical water splitting, by improving surface reaction kinetics and charge separation, transportation and collection efficiency. In this thesis, I will give a detailed discussion on the chemically modified metal oxide nanostructures for photoelectrocemical hydrogen generation, with a focus on the element doping, hydrogen treatment and catalyst modification. I have demonstrated nitrogen doping on ZnO and Ti doping on hematite can improve their photoelectrochemical performance. In addition, we found hydrogen treatment is a general and effective method to improve the photocatalytic performance, by increasing their carrier desities. Hydrogen treatment has been demonstrated on TiO2, WO3 and BiVO4. In the end, we also used electrochemical catalyt to modify these metal oxide photoelectrode for waste water treatment and chemical fuel generation.

Anchoring of Cu(II) onto surface of porous metal-organic framework through post-synthesis modification for the synthesis of benzimidazoles and benzothiazoles

NASA Astrophysics Data System (ADS)

Kardanpour, Reihaneh; Tangestaninejad, Shahram; Mirkhani, Valiollah; Moghadam, Majid; Mohammadpoor-Baltork, Iraj; Zadehahmadi, Farnaz

2016-03-01

Efficient synthesis of various benzimidazoles and benzothiazoles under mild conditions catalyzed by Cu(II) anchored onto UiO-66-NH2 metal organic framework is reported. In this manner, first, the aminated UiO-66 was modified with thiophene-2-carbaldehyde and then the prepared Schiff base was reacted with CuCl2. The prepared catalyst was characterized by FT-IR, UV-vis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 adsorption, inductively coupled plasma atomic emission spectroscopy (ICP-AES) and field emission scanning electron microscopy (FE-SEM). The UiO-66-NH2-TC-Cu was applied as a highly efficient catalyst for synthesis of benzimidazole and benzothiazole derivatives by the reaction of aldehydes with 1,2-diaminobenzene or 2-aminothiophenol. The Cu(II)-containing MOF was reused several times without any appreciable loss of its efficiency.

Determination of kjeldahl nitrogen in fertilizers by AOAC official methods 978.02: effect of copper sulfate as a catalyst.

PubMed

Abrams, Dean; Metcalf, David; Hojjatie, Michael

2014-01-01

In AOAC Official Method 955.04, Nitrogen (Total) in Fertilizers, Kjeldahl Method, fertilizer materials are analyzed using mercuric oxide or metallic mercury HgO or Hg) as a catalyst. AOAC Official Methods 970.02, Nitrogen (Total) in Fertilizers is a comprehensive total nitrogen (including nitrate nitrogen) method adding chromium metal. AOAC Official Method 978.02, Nitrogen (Total) in Fertilizers is a modified comprehensive nitrogen method used to measure total nitrogen in fertilizers with two types of catalysts. In this method, either copper sulfate or chromium metal is added to analyze for total Kjeldahl nitrogen. In this study, the part of AOAC Official Method 978.02 that is for nitrate-free fertilizer products was modified. The objective was to examine the necessity of copper sulfate as a catalyst for the nitrate-free fertilizer products. Copper salts are not environmentally friendly and are considered pollutants. Products such as ammonium sulfate, diammonium phosphate, monoammonium phosphate, urea-containing fertilizers such as isobutylene diurea (IBDU), and urea-triazone fertilizer solutions were examined. The first part of the study was to measure Kjeldahl nitrogen as recommended by AOAC Official Method 978.02. The second part of the study was to exclude the addition of copper sulfate from AOAC Official Method 978.02 to examine the necessity of copper sulfate as a catalyst in nitrate-free fertilizers, which was the primary objective. Our findings indicate that copper sulfate can be eliminated from the method with no significant difference in the results for the nitrogen content of the fertilizer products.

Catalytic ozonation of paracetamol using commercial and Pt-supported nanocomposites of Al2O3: The impact of ultrasound.

PubMed

Ziylan-Yavaş, Asu; Ince, Nilsun H

2018-01-01

The study is the assessment of commercial γ-Al 2 O 3 and its sonolytically modified nanocomposite in catalytic ozonation of paracetamol (PCT), which is an emerging water contaminant and a highly reactive compound with ozone. The results showed that commercial alumina was ineffective regardless of the solution pH, due to the low affinity of the catalyst surface for PCT and the high reactivity of the solute with molecular ozone. The modified catalyst, which was synthesized by decoration of the original surface with nanoparticles of platinum provided considerable improvement in the performance of the catalyst, particularly in mineralization of the target compound. The presence of OH scavenging agents in solution markedly retarded the rate of PCT oxidation and organic carbon decay, to signal the importance of radical-mediated reaction mechanisms on the degradation of the compound. Finally, the attempt to accelerate the reactions by running them in the presence of ultrasound was found inadequate for the early oxidation, but highly adequate for the longer mineralization process. The failure was attributed to the diffusion of a large fraction of ozone into the gaseous cavity bubbles (reduced probability of direct reactions) and the extreme conditions of cavitation collapse that partially damaged the catalyst surface. The success (in mineralization) was explained by the shift of the reaction site from the bulk solution (poor adsorption on catalyst surfaces) to the solid surface and the gaseous cavity bubbles (via enhanced hydrophobicity), both being considerably more active reaction media. Copyright © 2017 Elsevier B.V. All rights reserved.

Catalyst and process development for the H/sub 2/ preparation from future fuel cell feedstocks. Quarterly progress report, October 1, 1978-December 31, 1978

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yarrington, R M; Feins, I R; Hwang, H S

1979-01-01

The work done under this contract in the last quarter of 1978 was concerned with Phase I, which involved preliminary catalyst and process evaluation. The processes under study are hydrogen assisted steam reforming (HASR), catalytic partial oxidation (CPO), and autothermal steam reforming (ATR). Existing Engelhard test units were modified to carry out preliminary runs using the first two processes. Technical analysis to support work in this area consisted of heat and material balances constrained by equilibrium considerations. In a third task, the steam reforming of methanol to produce hydrogen was studied over two commercial low-temperature shift catalysts. Aging runs indicatedmore » good initial performance on both catalysts, but methanol conversion started to decline after a few hundred hours on stream.« less

Removal of gas phase low-concentration toluene over Mn, Ag and Ce modified HZSM-5 catalysts by periodical operation of adsorption and non-thermal plasma regeneration.

PubMed

Wang, Wenzheng; Wang, Honglei; Zhu, Tianle; Fan, Xing

2015-07-15

Ag/HZSM-5, Mn/HZSM-5, Ce/HZSM-5, Ag-Mn/HZSM-5 and Ce-Mn/HZSM-5 were prepared by impregnation method. Both their adsorption capacity and catalytic activity were investigated for the removal of gas phase low-concentration toluene by periodical operation of adsorption and non-thermal plasma regeneration. Results show that catalysts loaded with Ag (Ag/HZSM-5 and Ag-Mn/HZSM-5) had larger adsorption capacity for toluene than the other catalysts. And Ag-Mn/HZSM-5 displayed the best catalytic performance for both toluene oxidation by non-thermal plasma and byproducts suppression. On the other hand, the deactivated catalyst can be fully regenerated by calcining in air stream when its adsorption capacity and catalytic activity of the Ag-Mn/HZSM-5 catalyst was found to be decreased after 10 cycles of periodical adsorption and non-thermal regeneration. Copyright © 2015. Published by Elsevier B.V.

The effect of activated carbon support surface modification on characteristics of carbon nanospheres prepared by deposition precipitation of Fe-catalyst

NASA Astrophysics Data System (ADS)

Kristianto, H.; Arie, A. A.; Susanti, R. F.; Halim, M.; Lee, J. K.

2016-11-01

In this study the effect of activated carbon support modification to synthesis of CNSs was observed. Modification of activated carbon was done by using nitric acid. The effect of modification was analyzed from its FTIR spectra. The Fe catalysts were deposited on to the support by using urea deposition precipitation method at various initial catalysts concentration. CNSs was synthesized by utilizing cooking palm oil as renewable carbon source, and pyrolized at 700°C for 1 hour under nitrogen atmosphere. The products obtained then analyzed using SEM-EDS, TEM, XRD, and Raman spectroscopy. The modification of activated carbon support had increased the oxygen functional group. This increase resulted on increase of metal catalysts deposited on activated carbon surface. Peak of C (100) was observed, while ID/IG of samples were obtained around 0.9, which is commonly obtained for CNSs. High catalysts loading on modified activated carbon support caused decomposition of CNSs and formation carbon onion.

Engineered catalytic biofilms: Site-specific enzyme immobilization onto E. coli curli nanofibers.

PubMed

Botyanszki, Zsofia; Tay, Pei Kun R; Nguyen, Peter Q; Nussbaumer, Martin G; Joshi, Neel S

2015-10-01

Biocatalytic transformations generally rely on purified enzymes or whole cells to perform complex transformations that are used on industrial scale for chemical, drug, and biofuel synthesis, pesticide decontamination, and water purification. However, both of these systems have inherent disadvantages related to the costs associated with enzyme purification, the long-term stability of immobilized enzymes, catalyst recovery, and compatibility with harsh reaction conditions. We developed a novel strategy for producing rationally designed biocatalytic surfaces based on Biofilm Integrated Nanofiber Display (BIND), which exploits the curli system of E. coli to create a functional nanofiber network capable of covalent immobilization of enzymes. This approach is attractive because it is scalable, represents a modular strategy for site-specific enzyme immobilization, and has the potential to stabilize enzymes under denaturing environmental conditions. We site-specifically immobilized a recombinant α-amylase, fused to the SpyCatcher attachment domain, onto E. coli curli fibers displaying complementary SpyTag capture domains. We characterized the effectiveness of this immobilization technique on the biofilms and tested the stability of immobilized α-amylase in unfavorable conditions. This enzyme-modified biofilm maintained its activity when exposed to a wide range of pH and organic solvent conditions. In contrast to other biofilm-based catalysts, which rely on high cellular metabolism, the modified curli-based biofilm remained active even after cell death due to organic solvent exposure. This work lays the foundation for a new and versatile method of using the extracellular polymeric matrix of E. coli for creating novel biocatalytic surfaces. © 2015 Wiley Periodicals, Inc.

Status and prospects in higher alcohols synthesis from syngas.

PubMed

Luk, Ho Ting; Mondelli, Cecilia; Ferré, Daniel Curulla; Stewart, Joseph A; Pérez-Ramírez, Javier

2017-03-06

Higher alcohols are important compounds with widespread applications in the chemical, pharmaceutical and energy sectors. Currently, they are mainly produced by sugar fermentation (ethanol and isobutanol) or hydration of petroleum-derived alkenes (heavier alcohols), but their direct synthesis from syngas (CO + H 2 ) would comprise a more environmentally-friendly, versatile and economical alternative. Research efforts in this reaction, initiated in the 1930s, have fluctuated along with the oil price and have considerably increased in the last decade due to the interest to exploit shale gas and renewable resources to obtain the gaseous feedstock. Nevertheless, no catalytic system reported to date has performed sufficiently well to justify an industrial implementation. Since the design of an efficient catalyst would strongly benefit from the establishment of synthesis-structure-function relationships and a deeper understanding of the reaction mechanism, this review comprehensively overviews syngas-based higher alcohols synthesis in three main sections, highlighting the advances recently made and the challenges that remain open and stimulate upcoming research activities. The first part critically summarises the formulations and methods applied in the preparation of the four main classes of materials, i.e., Rh-based, Mo-based, modified Fischer-Tropsch and modified methanol synthesis catalysts. The second overviews the molecular-level insights derived from microkinetic and theoretical studies, drawing links to the mechanisms of Fischer-Tropsch and methanol syntheses. Finally, concepts proposed to improve the efficiency of reactors and separation units as well as to utilise CO 2 and recycle side-products in the process are described in the third section.

Boosting Chemical Stability, Catalytic Activity, and Enantioselectivity of Metal-Organic Frameworks for Batch and Flow Reactions.

PubMed

Chen, Xu; Jiang, Hong; Hou, Bang; Gong, Wei; Liu, Yan; Cui, Yong

2017-09-27

A key challenge in heterogeneous catalysis is the design and synthesis of heterogeneous catalysts featuring high catalytic activity, selectivity, and recyclability. Here we demonstrate that high-performance heterogeneous asymmetric catalysts can be engineered from a metal-organic framework (MOF) platform by using a ligand design strategy. Three porous chiral MOFs with the framework formula [Mn 2 L(H 2 O) 2 ] are prepared from enantiopure phosphono-carboxylate ligands of 1,1'-biphenol that are functionalized with 3,5-bis(trifluoromethyl)-, bismethyl-, and bisfluoro-phenyl substituents at the 3,3'-position. For the first time, we show that not only chemical stability but also catalytic activity and stereoselectivity of the MOFs can be tuned by modifying the ligand structures. Particularly, the MOF incorporated with -CF 3 groups on the pore walls exhibits enhanced tolerance to water, weak acid, and base compared with the MOFs with -F and -Me groups. Under both batch and flow reaction systems, the CF 3 -containing MOF demonstrated excellent reactivity, selectivity, and recyclability, affording high yields and enantioselectivities for alkylations of indoles and pyrrole with a range of ketoesters or nitroalkenes. In contrast, the corresponding homogeneous catalysts gave low enantioselectivity in catalyzing the tested reactions.

Silicon Photoelectrode Thermodynamics and Hydrogen Evolution Kinetics Measured by Intensity-Modulated High-Frequency Resistivity Impedance Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anderson, Nicholas C.; Carroll, Gerard M.; Pekarek, Ryan T.

Here, we present an impedance technique based on light intensity-modulated high-frequency resistivity (IMHFR) that provides a new way to elucidate both the thermodynamics and kinetics in complex semiconductor photoelectrodes. We apply IMHFR to probe electrode interfacial energetics on oxide-modified semiconductor surfaces frequently used to improve the stability and efficiency of photoelectrochemical water splitting systems. Combined with current density-voltage measurements, the technique quantifies the overpotential for proton reduction relative to its thermodynamic potential in Si photocathodes coated with three oxides (SiO x, TiO 2, and Al 2O 3) and a Pt catalyst. In pH 7 electrolyte, the flatband potentials of TiOmore » 2- and Al 2O 3-coated Si electrodes are negative relative to samples with native SiO x, indicating that SiO x is a better protective layer against oxidative electrochemical corrosion than ALD-deposited crystalline TiO 2 or Al 2O 3. Adding a Pt catalyst to SiO x/Si minimizes proton reduction overpotential losses but at the expense of a reduction in available energy characterized by a more negative flatband potential relative to catalyst-free SiO x/Si.« less

Porous metal-organic framework Cu3(BTC)2 as catalyst used in air-cathode for high performance of microbial fuel cell.

PubMed

Tian, Pei; Liu, Di; Li, Kexun; Yang, Tingting; Wang, Junjie; Liu, Yi; Zhang, Song

2017-11-01

Metal-organic framework Cu 3 (BTC) 2 , prepared by an easy hydrothermal method, was used as the oxygen-based catalyst in microbial fuel cell (MFC). The maximum power density of Cu 3 (BTC) 2 modified air-cathode MFC was 1772±15mWm -2 , almost 1.8 times higher than the control. BET results disclosed high specific surface area of 2159.7m 2 g -1 and abundant micropores structure. Regular octahedron and porous surface of Cu 3 (BTC) 2 were observed in SEM. XPS testified the existence of divalent copper in the extended 3D frameworks, which importantly acted as the Lewis-acid sites or redox centers in ORR. Additionally, the total resistance decreased by 42% from 17.60 to 10.24Ω compared with bare AC electrode. The rotating disk electrode test results showed a four-electron transfer pathway for Cu 3 (BTC) 2 , which was crucial for electrochemical catalytic activity. All the structural and electrochemical advantages make Cu 3 (BTC) 2 a promising catalyst for ORR in MFC. Copyright © 2017. Published by Elsevier Ltd.

Novel yolk-shell-structured Fe3O4@γ-AlOOH nanocomposite modified with Pd nanoparticles as a recyclable catalyst with excellent catalytic activity

NASA Astrophysics Data System (ADS)

Cui, Xueliang; Zheng, Yunfeng; Tian, Meng; Dong, Zhengping

2017-09-01

A novel yolk-shell-structured material (Fe3O4@γ-AlOOH-YSMs) with hierarchical γ-AlOOH flakes as the mesoporous shell and Fe3O4 nanoparticles (NPs) in the hollow core was prepared by using Fe3O4@SiO2 NPs as the seeds as well as NaAlO2 and urea as the precursor. The prepared Fe3O4@γ-AlOOH-YSMs were used as a catalyst support for fabricating a Pd/Fe3O4@γ-AlOOH-YSMs nanocatalyst with no obvious aggregation of the Pd NPs. The Pd/Fe3O4@γ-AlOOH-YSMs nanocatalyst was utilized for the catalytic reduction of the widely used and highly toxic 4-nitrophenol, rhodamine B, methylene blue, and methyl orange; and showed excellent catalytic activity as compared with other noble-metal-based catalysts. Furthermore, the Pd/Fe3O4@γ-AlOOH-YSMs nanocatalyst also can be easily separated from the reaction mixture and reused for at least ten times without any obvious decrease in the catalytic activity, indicating its reusability and stability.

Silicon Photoelectrode Thermodynamics and Hydrogen Evolution Kinetics Measured by Intensity-Modulated High-Frequency Resistivity Impedance Spectroscopy

DOE PAGES

Anderson, Nicholas C.; Carroll, Gerard M.; Pekarek, Ryan T.; ...

2017-10-05

Here, we present an impedance technique based on light intensity-modulated high-frequency resistivity (IMHFR) that provides a new way to elucidate both the thermodynamics and kinetics in complex semiconductor photoelectrodes. We apply IMHFR to probe electrode interfacial energetics on oxide-modified semiconductor surfaces frequently used to improve the stability and efficiency of photoelectrochemical water splitting systems. Combined with current density-voltage measurements, the technique quantifies the overpotential for proton reduction relative to its thermodynamic potential in Si photocathodes coated with three oxides (SiO x, TiO 2, and Al 2O 3) and a Pt catalyst. In pH 7 electrolyte, the flatband potentials of TiOmore » 2- and Al 2O 3-coated Si electrodes are negative relative to samples with native SiO x, indicating that SiO x is a better protective layer against oxidative electrochemical corrosion than ALD-deposited crystalline TiO 2 or Al 2O 3. Adding a Pt catalyst to SiO x/Si minimizes proton reduction overpotential losses but at the expense of a reduction in available energy characterized by a more negative flatband potential relative to catalyst-free SiO x/Si.« less

Production of aromatic hydrocarbons via catalytic pyrolysis of biomass over fe-modified HZSM-5 zeolites

USDA-ARS?s Scientific Manuscript database

Iron modified HZSM-5 catalysts were prepared by partial ion exchange of NH4ZSM-5 with Fe (II) at three different loadings (1.4, 2.8 and 4.2 wt%), and their effectiveness for producing aromatic hydrocarbons from cellulose, cellobiose, lignin and switchgrass by catalytic pyrolysis were screened using ...

Strategies for the synthesis of supported gold palladium nanoparticles with controlled morphology and composition.

PubMed

Hutchings, Graham J; Kiely, Christopher J

2013-08-20

The discovery that supported gold nanoparticles are exceptionally effective catalysts for redox reactions has led to an explosion of interest in gold nanoparticles. In addition, incorporating a second metal as an alloy with gold can enhance the catalyst performance even more. The addition of small amounts of gold to palladium, in particular, and vice versa significantly enhances the activity of supported gold-palladium nanoparticles as redox catalysts through what researchers believe is an electronic effect. In this Account, we describe and discuss methodologies for the synthesis of supported gold-palladium nanoparticles and their use as heterogeneous catalysts. In general, three key challenges need to be addressed in the synthesis of bimetallic nanoparticles: (i) control of the particle morphology, (ii) control of the particle size distribution, and (iii) control of the nanoparticle composition. We describe three methodologies to address these challenges. First, we discuss the relatively simple method of coimpregnation. Impregnation allows control of particle morphology during alloy formation but does not control the particle compositions or the particle size distribution. Even so, we contend that this method is the best preparation method in the catalyst discovery phase of any project, since it permits the investigation of many different catalyst structures in one experiment, which may aid the identification of new catalysts. A second approach, sol-immobilization, allows enhanced control of the particle size distribution and the particle morphology, but control of the composition of individual nanoparticles is not possible. Finally, a modified impregnation method can allow the control of all three of these crucial parameters. We discuss the effect of the different methodologies on three redox reactions: benzyl alcohol oxidation, toluene oxidation, and the direct synthesis of hydrogen peroxide. We show that the coimpregnation method provides the best reaction selectivity for benzyl alcohol oxidation and the direct synthesis of hydrogen peroxide. However, because of the reaction mechanism, the sol-immobilzation method gives very active and selective catalysts for toluene oxidation. We discuss the possible nature of the preferred active structures of the supported nanoparticles for these reactions. This paper is based on the IACS Heinz Heinemann Award Lecture entitled "Catalysis using gold nanoparticles" which was given in Munich in July 2012.

Porous carbon derived from disposable shaddock peel as an excellent catalyst toward VO2+/VO2+ couple for vanadium redox battery

NASA Astrophysics Data System (ADS)

Liu, J.; Wang, Z. A.; Wu, X. W.; Yuan, X. H.; Hu, J. P.; Zhou, Q. M.; Liu, Z. H.; Wu, Y. P.

2015-12-01

Functional porous carbon (PC) derived from bio-friendly shaddock peel has been firstly explored as catalyst for vanadium redox flow battery (VRB). The prepared PC is micro-mesoporous with high BET surface area of 882.7 m2 g-1, has some surface oxygen-containing functional groups, and is doped with N and P heteroatoms. These three factors greatly favor the electrochemical reactions of VO2+/VO2+ on the PC modified glass carbon (PC-GC). Compared with the naked GC and graphite modified GC, the PC-GC presents a lower peak separation (66 mV), higher anodic current density (17.1 mA cm-2) and cathodic current density (15.0 mA cm-2). The VRB using PC modified graphite felt (GF) as positive electrode demonstrates an enhanced voltage efficiency of 82.7% at the current density of 60 mA cm-2, and a better rate performance than that from the virginal GF.

United States Air Force Shale Oil to Fuels. Phase II.

DTIC Science & Technology

1981-11-01

and modified so that any off-gas from the LPS, stripper column, product drums, spent caustic drums, and sample ports would be sent to the caustic ...product, or in the spent caustic . After the desalted Paraho shale oil was processed in Production Run No. 2, the catalyst bed was flushed with light cycle...58 20 First-Stage Hydrotreating of Occidental Shale Oil -- Spent Catalyst Analysis - Run 1 ....... 59 21 First-Stage Hydrotreating of Occidental

Recent Advances in Catalyst Accelerated Stress Tests for Polymer Electrolyte Membrane Fuel Cells

DOE PAGES

Stariha, Sarah; Macauley, Natalia; Sneed, Brian T.; ...

2018-03-15

The U.S. Department of Energy (DOE) set the 2020 durability target for polymer electrolyte membrane fuel cell transportation applications at 5000 hours. Since it is impractical to test every fuel cell for this length of time, there is ever increasing interest in developing accelerated stress tests (ASTs) that can accurately simulate the material component degradation in the membrane electrode assembly (MEA) observed under automotive operating conditions, but over a much shorter time frame. In this study, a square-wave catalyst AST was examined that shows a 5X time acceleration factor over the triangle-wave catalyst AST and a 25X time acceleration factormore » over the modified wet drive-cycle catalyst durability protocol, significantly decreasing the testing time. These acceleration factors were correlated to the platinum (Pt) particle size increase and associated decrease in electrochemical surface area (ECSA). This square-wave AST has been adopted by the DOE as a standard protocol to evaluate catalyst durability. We also compare three catalyst-durability protocols using state-of-the-art platinum-cobalt catalysts supported on high surface area carbon (SOA Pt-Co/HSAC) in the cathode catalyst layer. The results for each of the three tests showed both catalyst particle size increase and transition metal leaching. Moreover the acceleration factors for the alloy catalysts were smaller due to Co leaching being the predominant mechanism of voltage decay in ~5 nm PtCo/C catalysts. Finally, an extremely harsh carbon corrosion AST was run using the same SOA Pt-Co/HSAC catalyst. This showed minimal change in particle size and a low percentage Co loss from the cathode catalyst particles, despite a significant loss in catalyst layer thickness and cell performance. The carbon corrosion rates during these various ASTs were directly measured by monitoring the CO 2 emission from the cathode, further confirming the ability of the square-wave AST to evaluate the electro-catalyst independently of the support.« less

Recent Advances in Catalyst Accelerated Stress Tests for Polymer Electrolyte Membrane Fuel Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stariha, Sarah; Macauley, Natalia; Sneed, Brian T.

The U.S. Department of Energy (DOE) set the 2020 durability target for polymer electrolyte membrane fuel cell transportation applications at 5000 hours. Since it is impractical to test every fuel cell for this length of time, there is ever increasing interest in developing accelerated stress tests (ASTs) that can accurately simulate the material component degradation in the membrane electrode assembly (MEA) observed under automotive operating conditions, but over a much shorter time frame. In this study, a square-wave catalyst AST was examined that shows a 5X time acceleration factor over the triangle-wave catalyst AST and a 25X time acceleration factormore » over the modified wet drive-cycle catalyst durability protocol, significantly decreasing the testing time. These acceleration factors were correlated to the platinum (Pt) particle size increase and associated decrease in electrochemical surface area (ECSA). This square-wave AST has been adopted by the DOE as a standard protocol to evaluate catalyst durability. We also compare three catalyst-durability protocols using state-of-the-art platinum-cobalt catalysts supported on high surface area carbon (SOA Pt-Co/HSAC) in the cathode catalyst layer. The results for each of the three tests showed both catalyst particle size increase and transition metal leaching. Moreover the acceleration factors for the alloy catalysts were smaller due to Co leaching being the predominant mechanism of voltage decay in ~5 nm PtCo/C catalysts. Finally, an extremely harsh carbon corrosion AST was run using the same SOA Pt-Co/HSAC catalyst. This showed minimal change in particle size and a low percentage Co loss from the cathode catalyst particles, despite a significant loss in catalyst layer thickness and cell performance. The carbon corrosion rates during these various ASTs were directly measured by monitoring the CO 2 emission from the cathode, further confirming the ability of the square-wave AST to evaluate the electro-catalyst independently of the support.« less

Adsorption and oxidation of SO₂in a fixed-bed reactor using activated carbon produced from oxytetracycline bacterial residue and impregnated with copper.

PubMed

Zhou, Baohua; Yu, Lei; Song, Hanning; Li, Yaqi; Zhang, Peng; Guo, Bin; Duan, Erhong

2015-02-01

The SO₂removal ability (including adsorption and oxidation ability) of activated carbon produced from oxytetracycline bacterial residue and impregnated with copper was investigated. The activated carbon produced from oxytetracycline bacterial residue and modified with copper was characterized by x-ray diffraction, scanning electron microscopy, and energy-dispersive spectroscopy. The effects of the catalysts, SO₂concentration, weight hourly space velocity, and temperature on the SO₂adsorption and oxidation activity were evaluated. Activated carbon produced from oxytetracycline bacterial residue and used as catalyst supports for copper oxide catalysts provided high catalytic activity for the adsorbing and oxidizing of SO₂from flue gases.

Visible-Light Responsive Catalysts Using Quantum Dot-Modified TiO2 for Air and Water Purification

NASA Technical Reports Server (NTRS)

Coutts, Janelle L.; Hintze, Paul E.; Clausen, Christian A.; Richards, Jeffrey T.

2014-01-01

Photocatalysis, the oxidation or reduction of contaminants by light-activated catalysts, utilizing titanium dioxide (TiO2) as the catalytic substrate has been widely studied for trace contaminant control in both air and water applications. The interest in this process is due primarily to its low energy consumption and capacity for catalyst regeneration. Titanium dioxide requires ultraviolet light for activation due to its relatively large band gap energy of 3.2 eV. Traditionally, Hg-vapor fluorescent light sources are used in PCO reactors; however, the use of mercury precludes the use of this PCO technology in a spaceflight environment due to concerns over crew Hg exposure.

A facile way to fabricate manganese phosphate self-assembled carbon networks as efficient electrochemical catalysts for real-time monitoring of superoxide anions released from HepG2 cells.

PubMed

Cai, Xuan; Shi, Libo; Sun, Wenqian; Zhao, Hongli; Li, Hong; He, Haiyan; Lan, Minbo

2018-04-15

Quantification of superoxide anions (O 2 •- ) is significant in the monitoring of many serious diseases and the design of enzyme-mimic catalysts plays the main role in the development of non-enzymatic O 2 •- sensors. Herein, we proposed a facile self-assembly process to synthesize manganese phosphate modified carbon networks using three kinds of widely-used carbon materials (MWCNTs, NGS and GO) as pillar connectors. Characterizations demonstrate that manganese phosphate is widely dispersed inside and on the surface of carbon networks without visible morphology. Meanwhile, all three kinds of synthesized catalysts were successfully immobilized on the screen-printed carbon electrodes to evaluate the electrochemical performance of fabricated sensors. The results indicate that sensors based on Mn x (PO 4 ) y modified MWCNTs exhibit high sensitivity with an extremely low detection limit of 0.127μM (S/N = 3) and a wide liner range of 0-1.817mM (R 2 = 0.998). We further employed the recommended sensors in the real-time monitoring of HepG2 cells released O 2 •- under the stimulating of Zymosan (20mg/mL). Noticeably, the proposed sensors exhibit not only sensitive response but also stable current steps upon different addition of Zymosan. The calculated concentrations of cell-released O 2 •- vary from 6.772 to 24.652pM cell -1 for the Zymosan amount used in this work. The established novel sensors display low background current and signal noises, thus holding unique advantages in the trace analysis of O 2 •- in biological samples and in vivo environment. Copyright © 2017 Elsevier B.V. All rights reserved.

A framework for the analysis of the security of supply of utilising carbon dioxide as a chemical feedstock.

PubMed

Fraga, Eric S; Ng, Melvin

2015-01-01

Recent developments in catalysts have enhanced the potential for the utilisation of carbon dioxide as a chemical feedstock. Using the appropriate energy efficient catalyst enables a range of chemical pathways leading to desirable products. In doing so, CO2 provides an economically and environmentally beneficial source of C1 feedstock, while improving the issues relating to security of supply that are associated with fossil-based feedstocks. However, the dependence on catalysts brings other supply chains into consideration, supply chains that may also have security of supply issues. The choice of chemical pathways for specific products will therefore entail an assessment not only of economic factors but also the security of supply issues for the catalysts. This is a multi-criteria decision making problem. In this paper, we present a modified 4A framework based on the framework suggested by the Asian Pacific Energy Research centre for macro-economic applications. The 4A methodology is named after the criteria used to compare alternatives: availability, acceptability, applicability and affordability. We have adapted this framework for the consideration of alternative chemical reaction processes using a micro-economic outlook. Data from a number of sources were collected and used to quantify each of the 4A criteria. A graphical representation of the assessments is used to support the decision maker in comparing alternatives. The framework not only allows for the comparison of processes but also highlights current limitations in the CCU processes. The framework presented can be used by a variety of stakeholders, including regulators, investors, and process industries, with the aim of identifying promising routes within a broader multi-criteria decision making process.

New Method to Synthesize Highly Active and Durable Chemically Ordered fct-PtCo Cathode Catalyst for PEMFCs.

PubMed

Jung, Won Suk; Popov, Branko N

2017-07-19

In the bottom-up synthesis strategy performed in this study, the Co-catalyzed pyrolysis of chelate-complex and activated carbon black at high temperatures triggers the graphitization reaction which introduces Co particles in the N-doped graphitic carbon matrix and immobilizes N-modified active sites for the oxygen reduction reaction (ORR) on the carbon surface. In this study, the Co particles encapsulated within the N-doped graphitic carbon shell diffuse up to the Pt surface under the polymer protective layer and forms a chemically ordered face-centered tetragonal (fct) Pt-Co catalyst PtCo/CCCS catalyst as evidenced by structural and compositional studies. The fct-structured PtCo/CCCS at low-Pt loading (0.1 mg Pt cm -2 ) shows 6% higher power density than that of the state-of-the-art commercial Pt/C catalyst. After the MEA durability test of 30 000 potential cycles, the performance loss of the catalyst is negligible. The electrochemical surface area loss is less than 40%, while that of commercial Pt/C is nearly 80%. After the accelerated stress test, the uniform catalyst distribution is retained and the mean particle size increases approximate 1 nm. The results obtained in this study indicated that highly stable compositional and structural properties of chemically ordered PtCo/CCCS catalyst contribute to its exceptional catalyst durability.

Ultrasonic-assisted hydrothermal synthesis and catalytic behavior of a novel SAPO-34/Clinoptilolite nanocomposite catalyst for high propylene demand in MTO process

NASA Astrophysics Data System (ADS)

Moradiyan, Eshagh; Halladj, Rouein; Askari, Sima; Moghimpour Bijani, Parisa

2017-08-01

SAPO-34 as a catalyst has high selectivity and hydrothermal stability, but it is rapidly deactivated by the formation of coke in its micropores. Evaluating the natural Clinoptilolite capability as a binder in nanocomposite catalysts is of interest because of its low cost, and accelerating the reaction. The SAPO-34/Clinoptilolite (S/C) nanocomposite catalysts were synthesized via ultrasonic-assisted hydrothermal method using Clinoptilolite as a binder. Subsequent performance of the catalyst was investigated in the methanol to olefins (MTO) reaction. The structures of synthesized nanocomposite were characterized with several methods such as XRD, XRF, FESEM, TEM, NH3-TPD, FT-IR, and nitrogen adsorption techniques. The modified Clinoptilolite was attained using nitric acid treatment. Although the physicochemical analysis indicated that HNO3-treatment decreases the crystallinity of the Clinoptilolite, the specific surface area of natural zeolite enhances considerably from 20.07 to 187.8 m2/g. The nanocomposite catalysts showed high selectivity toward light olefins with 100% conversion and 90% selectivity to light olefins as desired products at 450 °C. Nanocomposite with the additional diffusion paths for mass transfer provided by binder-filled space ascend to higher catalytic lifetimes in compare with free SAPO-34 catalyst.

A comparative study on the quality of bio-oil derived from green macroalga Enteromorpha clathrata over metal modified ZSM-5 catalysts.

PubMed

Wang, Shuang; Cao, Bin; Liu, Xinlin; Xu, Lujiang; Hu, Yamin; Afonaa-Mensah, Stephen; Abomohra, Abd El-Fatah; He, Zhixia; Wang, Qian; Xu, Shannan

2018-05-01

The green macroalga Enteromorpha clathrata was pyrolyzed with or without catalysts at the temperature of 550 °C for producing high-quality bio-oil. The ZSM-5 and 1,2,3 mmol Mg-Ce/ZSM-5 catalysts were introduced to investigate the yields and components distribution of bio-oil. Increase of bio-oil production was obtained with the use of ZSM-5 and 1,2,3 mmol Mg-Ce/ZSM-5 catalysts. The 1 mmol Mg-Ce/ZSM-5 catalyst exhibited more promising property for promoting the relative content of C 5 -C 7 compounds, and decreasing the relative content of acids in bio-oil. The results suggested that E. clathrata had potential as pyrolysis feedstocks for producing the high-quality bio-oil with large amounts of C 5 -C 7 compounds and low relative content of acids when the 1 mmol Mg-Ce/ZSM-5 catalyst was used. Furthermore, the physicochemical properties of ZSM-5 and 1 mmol Mg-Ce/ZSM-5 catalysts were investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and temperature-programmed desorption of ammonia. Copyright © 2018 Elsevier Ltd. All rights reserved.

Transient studies of low temperature catalysts for methane conversion. Final report, [September 1992--March 1996

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wolf, E.E.

1996-09-30

The objective of this project is to use transient techniques to study gas surface interactions during the oxidative conversion of methane. Two groups of catalysts were studied: a double oxide of vanadium and phosphate or VPO, and double oxides of Ni, Co and Rh and lanthana. The objective of the studies involving the VPO catalyst was to understand gas-surface interactions leading to the formation of formaldehyde. In the second group of catalysts, involving metallo-oxides, the main objective was to study the gas-surface interactions that determine the selectivity to C{sub 2} hydrocarbons or synthesis gas. Transient techniques were used to studymore » the methane-surface interactions and the role of lattice oxygen. The selection of the double oxides was made on the hypothesis that the metal oxide would provide an increase interaction with methane whereas the phosphate or lanthanide would provide the sites for oxygen adsorption. The hypothesis behind this selection of catalysts was that increasing the methane interaction with the catalysts would lower the reaction temperature and thus increase the selectivity to the desired products over the total oxidation reaction. In both groups of catalysts the role of Li as a modifier of the selectivity was also studied in detail.« less

Substantially Stabilized Superacid Incorporated SBA-15 with Calcium Bridging for Selective Esterification of Glycerol

NASA Astrophysics Data System (ADS)

Hoo, P. Y.; Abdullah, A. Z.; Shuit, S. H.; Teoh, Y. P.; Ng, Q. H.; Kunasundari, B.

2018-03-01

The exploitation of the super acidity of heteropolyacids incorporated heterogeneous catalysts was only feasible if the heterogeneity of these catalysts was assured. To maintain the catalyst heterogeneity in polar medium, a novel two-step modification method was proposed to synthesize the highly active, yet stable heterogeneous catalyst, catered for selective esterification of monoglyceride. The surficial, structural and acidity properties of the modified catalysts were investigated via crucial characterization methods (N2 BET, HRTEM, and FTIR). The collective evidences verified the predicted formation of calcium oxides (CaO) on the mesopores surfaces of the SBA-15 support after the first modification, and the successful subsequent 12-tungstophosphoric acid (HPW) functionalization. The superior stability of the synthesized catalysts (10wt%-HPW/CaSBA-15) was demonstrated (negligible change in both conversion – 75% and yield – 70%), without the need for catalyst regeneration. Such result was attributed to the strong interaction between HPW and SBA-15 via calcium bridging. Being alkaline in nature, calcium oxides in the inner pores readily reacted with highly acidic HPW introduced in the subsequent wetness incipient step, forming insoluble HPW acid sites on inner pore walls of SBA-15 via the calcium bridging. This modification deemed promising and other alkaline metals should be explored in the future.

Nanosized CuO and ZnO catalyst supported on titanium chip for conversion of carbon dioxide to methyl alcohol.

PubMed

Seo, Hyeong-Seok; Park, Chul-Min; Kim, Ki-Joong; Jeong, Woon-Jo; Chung, Min-Chul; Jung, Sang-Chul; Kim, Sang-Chai; Ahn, Ho-Geun

2013-08-01

In order to reutilize spent metallic titanium chips (TC) as catalyst support or photocatalytic materials, the surface of the TC was modified by thermal treatment under air atmosphere. TC-supported nanosized CuO and ZnO catalysts were prepared by impregnation (IMP) and co-precipitation (CP) method, respectively. The catalytic activity for CO2 hydrogenation to CH3OH was investigated using a flow-typed reactor under various reaction pressures. The crystals of CuO and ZnO was well formed on TC. CO2 conversion, CH3OH selectivity, and CH3OH yield were obtained as a function of time on stream over CuO-ZnO/TC catalysts. Conversion of CO2 to CH3OH over CuO-ZnO/TC catalyst by CP method and CuO/ZnO/TC catalyst by IMP method were ca. 16% and ca. 12%, respectively. Conversion of CO2 over CuO-ZnO/TC catalyst by CP method was increased with increasing reaction temperature in the range of 15-30 atm. Maximum selectivity and yield to CH3OH over CuO-ZnO/TC at 250 degrees C were ca. 90% at 20 atm and ca. 18.2% at 30 atm, respectively.

Fabrication of three-dimensional buckypaper catalyst layer with Pt nanoparticles supported on polyelectrolyte functionalized carbon nanotubes for proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Zhu, Shiyao; Zheng, Junsheng; Huang, Jun; Dai, Ningning; Li, Ping; Zheng, Jim P.

2018-07-01

Polyelectrolyte poly(diallyldimethylammonium chloride) (PDDA) functionalized carbon nanotubes (CNTs) supported Pt electrocatalyst was synthesized as a substitute for commonly used Pt/C and Pt/CNTs (modified by harsh acid-oxidation treatment) catalysts. In addition, this catalyst was fabricated as the cathode catalyst layer (CL) with a unique double-layered structure for proton exchange membrane fuel cells (PEMFCs). Thermogravimetric analysis shows an enhanced thermal stability of Pt/PDDA-CNTs. The Pt/PDDA-CNTs catalyst with an average Pt particle size of ∼3.1 nm exhibits the best electrocatalytic activity and a significantly enhanced electrochemical stability. Scanning electron microscope, energy dispersive spectrometer and mercury intrusion porosimetry results demonstrate the gradient distribution of Pt content and pore size along the thickness of buckypaper catalyst layer (BPCL). The accelerated degradation test results of BPCLs indicate that this gradient structure can ensure a high Pt utilization in the BPCLs (up to 90%) and further improve the catalyst durability. In addition, the membrane electrode assembly (MEA) fabricated with cathode BPCL-PDDA shows the best single cell performance and long-term stability, and a reduction of Pt loading can be achieved. The feasibility of BPCL for improving the Pt utilization is also demonstrated by the cathode cyclic voltammetry in MEA.

Selective degradation of organic dyes by a resin modified Fe-based metal-organic framework under visible light irradiation

NASA Astrophysics Data System (ADS)

Araya, Tirusew; Chen, Chun-cheng; Jia, Man-ke; Johnson, David; Li, Ruiping; Huang, Ying-ping

2017-02-01

Metal organic frameworks (MOFs), a new class of porous crystalline materials have attracted attention because of potential applications in environmental remediation. In this work, an Fe-based MOF, FeBTC (BTC = 1,3,5-tricarboxylic acid), was successfully modified with Amberlite IRA-200 resin to yield a novel heterogeneous photocatalyst, A@FeBTC. The modification resulted in higher photocatalytic activity than FeBTC under the same conditions. After 60 min of visible light illumination (λ ≥ 420 nm) 99% of rhodamine B was degraded. The modification lowers the zeta potential, enhancing charge-based selective adsorption and subsequent photocatalytic degradation of cationic dye pollutants. The composite also improved catalyst stability and recyclability by significantly reducing loss of iron leaching. Photoluminescence studies show that introduction of the resin reduces the recombination rate of photogenerated charge carriers thereby improving the photocatalytic activity of the composite. Finally, a plausible photocatalytic reaction mechanism is proposed.

Heterogeneous Microtesla SABRE Enhancement of 15 N NMR Signals.

PubMed

Kovtunov, Kirill V; Kovtunova, Larisa M; Gemeinhardt, Max E; Bukhtiyarov, Andrey V; Gesiorski, Jonathan; Bukhtiyarov, Valerii I; Chekmenev, Eduard Y; Koptyug, Igor V; Goodson, Boyd M

2017-08-21

The hyperpolarization of heteronuclei via signal amplification by reversible exchange (SABRE) was investigated under conditions of heterogeneous catalysis and microtesla magnetic fields. Immobilization of [IrCl(COD)(IMes)], [IMes=1,3-bis(2,4,6-trimethylphenyl), imidazole-2-ylidene; COD=cyclooctadiene] catalyst onto silica particles modified with amine linkers engenders an effective heterogeneous SABRE (HET-SABRE) catalyst that was used to demonstrate a circa 100-fold enhancement of 15 N NMR signals in 15 N-pyridine at 9.4 T following parahydrogen bubbling within a magnetic shield. No 15 N NMR enhancement was observed from the supernatant liquid following catalyst separation, which along with XPS characterization supports the fact that the effects result from SABRE under heterogeneous catalytic conditions. The technique can be developed further for producing catalyst-free agents via SABRE with hyperpolarized heteronuclear spins, and thus is promising for biomedical NMR and MRI applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface Immobilization of Molecular Electrocatalysts for Energy Conversion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bullock, R. Morris; Das, Atanu K.; Appel, Aaron M.

2017-03-22

Electrocatalysts are critically important for a secure energy future, as they facilitate the conversion between electrical energy and chemical energy. Molecular catalysts offer precise control of their structure, and the ability to modify the substituents to understand structure-reactivity relationships that are more difficult to achieve with heterogeneous catalysts. Molecular electrocatalysts can be immobilized on surfaces by covalent bonds or through non-covalent interactions. Advantages of surface immobilization include the need for less catalyst, avoidance of bimolecular decomposition pathways, and easier determination of catalyst lifetime. Copper-catalyzed click reactions are often used to form covalent bonds to surfaces, and pi-pi stacking of pyrenemore » substituents appended to the ligand of a molecular complex is a frequently used method to achieve non-covalent surface immobilization. This mini-review highlights surface confinement of molecular electrocatalysts for reduction of O2, oxidation of H2O, production of H2, and reduction of CO2.« less

Graphitized hollow carbon spheres and yolk-structured carbon spheres fabricated by metal-catalyst-free chemical vapor deposition

DOE PAGES

Li, Xufan; Chi, Miaofang; Mahurin, Shannon Mark; ...

2016-01-18

Hard-sphere-templating method has been widely used to synthesize hollow carbon spheres (HCSs), in which the spheres were firstly coated with a carbon precursor, followed by carbonization and core removal. The obtained HCSs are generally amorphous or weakly graphitized (with the help of graphitization catalysts). In this work, we report on the fabrication of graphitized HCSs and yolk–shell Au@HCS nanostructures using a modified templating method, in which smooth, uniform graphene layers were grown on SiO 2 spheres or Au@SiO 2 nanoparticles via metal-catalyst-free chemical vapor deposition (CVD) of methane. Furthermore, our work not only provides a new method to fabricate high-quality,more » graphitized HCSs but also demonstrates a reliable approach to grow quality graphene on oxide surfaces using CVD without the presence of metal catalysts.« less

Aluminium and titanium modified mesoporous TUD-1: A bimetal acid catalyst for Biginelli reaction

NASA Astrophysics Data System (ADS)

Pasupathi, M.; Santhi, N.; Pachamuthu, M. P.; Alamelu Mangai, G.; Ragupathi, C.

2018-05-01

Using a simple, non-surfactant template triethanolamine (TEA), bimetal (Al3+ and Ti4+ ions) incorporated mesoporous catalyst AlTiTUD-1 (Si/Al+Ti = 50) was synthesized. The catalyst was characterized by XRD (Low and High angle), N2 Sorption, FTIR, SEM, TEM, DR UV Visible, and pyridine adsorbed FT-IR techniques. The XRD and N2 sorption studies confirmed its amorphous, mesoporous nature, which possessed a BET surface area of 590 m2 g-1 and pore diameter of 4.4 nm. The Al3+ and Ti4+ co-ordination within the TUD-1 was evaluated by DR UV-Vis. Pyridine adsorbed FTIR revealed both Bronsted (B) and Lewis (L) acidity, which is responsible for the catalytic activity. The acid catalyst showed a good catalytic performance in Biginelli type multicomponent coupling reaction for the substituted aldehydes, ethyl acetoacetate and thiourea to yield about 70% in reflux condition.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stariha, Sarah; Macauley, Natalia; Sneed, Brian T.

The U.S. Department of Energy (DOE) set the 2020 durability target for polymer electrolyte membrane fuel cell transportation applications at 5000 hours. Since it is impractical to test every fuel cell for this length of time, there is ever increasing interest in developing accelerated stress tests (ASTs) that can accurately simulate the material component degradation in the membrane electrode assembly (MEA) observed under automotive operating conditions, but over a much shorter time frame. In this study, a square-wave catalyst AST was examined that shows a 5X time acceleration factor over the triangle-wave catalyst AST and a 25X time acceleration factormore » over the modified wet drive-cycle catalyst durability protocol, significantly decreasing the testing time. These acceleration factors were correlated to the platinum (Pt) particle size increase and associated decrease in electrochemical surface area (ECSA). This square-wave AST has been adopted by the DOE as a standard protocol to evaluate catalyst durability. We also compare three catalyst-durability protocols using state-of-the-art platinum-cobalt catalysts supported on high surface area carbon (SOA Pt-Co/HSAC) in the cathode catalyst layer. The results for each of the three tests showed both catalyst particle size increase and transition metal leaching. Moreover the acceleration factors for the alloy catalysts were smaller due to Co leaching being the predominant mechanism of voltage decay in ~5 nm PtCo/C catalysts. Finally, an extremely harsh carbon corrosion AST was run using the same SOA Pt-Co/HSAC catalyst. This showed minimal change in particle size and a low percentage Co loss from the cathode catalyst particles, despite a significant loss in catalyst layer thickness and cell performance. The carbon corrosion rates during these various ASTs were directly measured by monitoring the CO 2 emission from the cathode, further confirming the ability of the square-wave AST to evaluate the electro-catalyst independently of the support.« less

Partial Oxidation of Hydrocarbons in a Segmented Bed Using Oxide-based Catalysts and Oxygen-conducting Supports

NASA Astrophysics Data System (ADS)

Smith, Mark W.

Two objectives for the catalytic reforming of hydrocarbons to produce synthesis gas are investigated herein: (1) the effect of oxygen-conducting supports with partially substituted mixed-metal oxide catalysts, and (2) a segmented bed approach using different catalyst configurations. Excess carbon deposition was the primary cause of catalyst deactivation, and was the focus of the experiments for both objectives. The formation and characterization of deposited carbon was examined after reaction for one of the selected catalysts to determine the quantity and location of the carbon on the catalyst surface leading to deactivation. A nickel-substituted barium hexaaluminate (BNHA), with the formula BaAl 11.6Ni0.4O18.8, and a Rh-substituted lanthanum zirconate pyrochlore (LCZR) with the formula La1.89Ca0.11 Zr1.89Rh0.11, were combined with two different doped ceria supports. These supports were gadolinium-doped ceria (GDC) and zirconium-doped ceria (ZDC). The active catalyst phases were combined with the supports in different ratios using different synthesis techniques. The catalysts were characterized using several different techniques and were tested under partial oxidation (POX) of n-tetradecane (TD), a diesel fuel surrogate. It was found that the presence of GDC and ZDC reduced the formation of carbon for both catalysts; the optimal ratio of catalyst to support was different for the hexaaluminate and the pyrochlore; a loading of 20 wt% of the pyrochlore with ZDC produced the most stable performance in the presence of common fuel contaminants (>50 h); and, the incipient wetness impregnation synthesis method of applying the active catalyst to the support produced more stable product yields than the catalyst prepared by a solid-state mixing technique. Different hexaaluminate and pyrochlore catalysts were used in different configurations in a segmented bed approach. The first strategy was to promote the indirect reforming mechanism by placing a combustion catalyst in the reactor inlet, followed by a reforming catalyst. This approach demonstrated that BNHA can be used in the reactor inlet to promote combustion with 1 wt% Rh-substituted pyrochlore in the reactor outlet, but the combustion catalyst should fill less than 50% of the reactor. The second approach placed specific catalysts in regions of the reactor that have conditions in which they are less likely to deactivate. This showed the most benefit in the use of a sulfur-tolerant noble metal catalyst in the reactor outlet. The carbon formation study was conducted on a 2 wt% Rh-substituted pyrochlore. POX of TD for various run times, followed by temperature programmed oxidation, revealed two different types of carbon deposits in the catalyst bed: carbon that burned off at relatively low temperature (LTC), and carbon that burned off at higher temperatures (HTC). The LTC reached a steady state level within two hours of reaction, and was determined not to lead to catalyst deactivation. The HTC continued to accumulate with time on stream. A mathematical expression was developed to predict the rate of formation of the HTC for a given set of reaction conditions (O/C = 1.25). This expression was modified from data from a test under different reaction conditions (O/C = 1.1) for one length of time, and was found to predict the carbon formation for a different run time within 3%.

Efficient catalytic cycloalkane oxidation employing a "helmet" phthalocyaninato iron(III) complex.

PubMed

Brown, Elizabeth S; Robinson, Jerome R; McCoy, Aaron M; McGaff, Robert W

2011-06-14

We have examined the catalytic activity of an iron(III) complex bearing the 14,28-[1,3-diiminoisoindolinato]phthalocyaninato (diiPc) ligand in oxidation reactions with three substrates (cyclohexane, cyclooctane, and indan). This modified metallophthalocyaninato complex serves as an efficient and selective catalyst for the oxidation of cyclohexane and cyclooctane, and to a far lesser extent indan. In the oxidations of cyclohexane and cyclooctane, in which hydrogen peroxide is employed as the oxidant under inert atmosphere, we have observed turnover numbers of 100.9 and 122.2 for cyclohexanol and cyclooctanol, respectively. The catalyst shows strong selectivity for alcohol (vs. ketone) formation, with alcohol to ketone (A/K) ratios of 6.7 and 21.0 for the cyclohexane and cyclooctane oxidations, respectively. Overall yields (alcohol + ketone) were 73% for cyclohexane and 92% for cyclooctane, based upon the total hydrogen peroxide added. In the catalytic oxidation of indan under similar conditions, the TON for 1-indanol was 10.1, with a yield of 12% based upon hydrogen peroxide. No 1-indanone was observed in the product mixture.

Structure and Dynamics of Individual Diastereomeric Complexes on Platinum: Surface Studies Related to Heterogeneous Enantioselective Catalysis.

PubMed

Dong, Yi; Goubert, Guillaume; Groves, Michael N; Lemay, Jean-Christian; Hammer, Bjørk; McBreen, Peter H

2017-05-16

The modification of heterogeneous catalysts through the chemisorption of chiral molecules is a method to create catalytic sites for enantioselective surface reactions. The chiral molecule is called a chiral modifier by analogy to the terms chiral auxiliary or chiral ligand used in homogeneous asymmetric catalysis. While there has been progress in understanding how chirality transfer occurs, the intrinsic difficulties in determining enantioselective reaction mechanisms are compounded by the multisite nature of heterogeneous catalysts and by the challenges facing stereospecific surface analysis. However, molecular descriptions have now emerged that are sufficiently detailed to herald rapid advances in the area. The driving force for the development of heterogeneous enantioselective catalysts stems, at the minimum, from the practical advantages they might offer over their homogeneous counterparts in terms of process scalability and catalyst reusability. The broader rewards from their study lie in the insights gained on factors controlling selectivity in heterogeneous catalysis. Reactions on surfaces to produce a desired enantiomer in high excess are particularly challenging since at room temperature, barrier differences as low as ∼2 kcal/mol between pathways to R and S products are sufficient to yield an enantiomeric ratio (er) of 90:10. Such small energy differences are comparable to weak interadsorbate interaction energies and are much smaller than chemisorption or even most physisorption energies. In this Account, we describe combined experimental and theoretical surface studies of individual diastereomeric complexes formed between chiral modifiers and prochiral reactants on the Pt(111) surface. Our work is inspired by the catalysis literature on the enantioselective hydrogenation of activated ketones on cinchona-modified Pt catalysts. Using scanning tunneling microscopy (STM) measurements and density functional theory (DFT) calculations, we probe the structures and relative abundances of non-covalently bonded complexes formed between three representative prochiral molecules and (R)-(+)-1-(1-naphthyl)ethylamine ((R)-NEA). All three prochiral molecules, 2,2,2-trifluoroacetophenone (TFAP), ketopantolactone (KPL), and methyl 3,3,3-trifluoropyruvate (MTFP), are found to form multiple complexation configurations around the ethylamine group of chemisorbed (R)-NEA. The principal intermolecular interaction is NH···O H-bonding. In each case, submolecularly resolved STM images permit the determination of the prochiral ratio (pr), pro-R to pro-S, proper to specific locations around the ethylamine group. The overall pr observed in experiments on large ensembles of KPL-(R)-NEA complexes is close to the er reported in the literature for the hydrogenation of KPL to pantolactone on (R)-NEA-modified Pt catalysts at 1 bar H 2 . The results of independent DFT and STM studies are merged to determine the geometries of the most abundant complexation configurations. The structures reveal the hierarchy of chemisorption and sometimes multiple H-bonding interactions operating in complexes. In particular, privileged complexes formed by KPL and MTFP reveal the participation of secondary CH···O interactions in stereocontrol. State-specific STM measurements on individual TFAP-(R)-NEA complexes show that complexation states interconvert through processes including prochiral inversion. The state-specific information on structure, prochirality, dynamics, and energy barriers delivered by the combination of DFT and STM provides insight on how to design better chiral modifiers.

Hydroxide catalysts for lignin depolymerization

DOEpatents

Beckham, Gregg T; Biddy, Mary J.; Kruger, Jacob S.; Chmely, Stephen C.; Sturgeon, Matthew

2017-10-17

Solid base catalysts and their use for the base-catalyzed depolymerization (BCD) of lignin to compounds such as aromatics are presented herein. Exemplary catalysts include layered double hydroxides (LDHs) as recyclable, heterogeneous catalysts for BCD of lignin.

Hydroxide catalysts for lignin depolymerization

DOEpatents

Beckham, Gregg T.; Biddy, Mary J.; Chmely, Stephen C.; Sturgeon, Matthew

2017-04-25

Solid base catalysts and their use for the base-catalyzed depolymerization (BCD) of lignin to compounds such as aromatics are presented herein. Exemplary catalysts include layered double hydroxides (LDHs) as recyclable, heterogeneous catalysts for BCD of lignin.

Electrode-Modified Zeolites - Electrode Microstructures Contained in and on a Heterogeneous Catalyst

DTIC Science & Technology

1988-07-15

zeolite Type Y and Pt supported on gamma-alumina. The electrolytic response of zeolite-supported Pt in the absence of added electrolyte salt for water or...character of metals at sizes where’ bulk metallic properties may not be exhibited. Furthermore, electrolyses are now allowed using loadings of catalysts which...in water until the filtrate tested negatively for Cl with AgNO 3; PtY was then dried a- 135 C. Equilibrium exchnge occurs at these low weight

Adhesion strength of norbornene-based self-healing agents to an amine-cured epoxy

NASA Astrophysics Data System (ADS)

Huang, Guang Chun; Lee, Jong Keun; Kessler, Michael R.; Yoon, Sungho

2009-07-01

Self-healing is triggered by crack propagation through embedded microcapsules in an epoxy matrix, which then release the liquid healing agent into the crack plane. Subsequent exposure of the healing agent to the chemical catalyst initiates ring-opening metathesis polymerization (ROMP) and bonding of the crack faces. In order to improve self-healing functionality, it is necessary to enhance adhesion of polymerized healing agent within the crack to the matrix resin. In this study, shear bond strength between different norbornene-based healing agents and an amine-cured epoxy resin was evaluated using the single lap shear test method (ASTM D3163, modified). The healing agents tested include endodicyclopentadiene (endo-DCPD), 5-ethylidene-2-norbornene (ENB) and DCPD/ENB blends. 5-Norbornene-2-methanol (NBM) was used as an adhesion promoter, containing hydroxyl groups to form hydrogen bonds with the amine-cured epoxy. A custom synthesized norbornene-based crosslinking agent was also added to improve adhesion for ENB by increasing the crosslinking density of the adhesive after ROMP. The healing agents were polymerized with varying loadings of the 1st generation Grubbs' catalyst at different reaction times and temperatures.

Catalysis of a 1,3-dipolar reaction by distorted DNA incorporating a heterobimetallic platinum(ii) and copper(ii) complex.

PubMed

Rivilla, Iván; de Cózar, Abel; Schäfer, Thomas; Hernandez, Frank J; Bittner, Alexander M; Eleta-Lopez, Aitziber; Aboudzadeh, Ali; Santos, José I; Miranda, José I; Cossío, Fernando P

2017-10-01

A novel catalytic system based on covalently modified DNA is described. This catalyst promotes 1,3-dipolar reactions between azomethine ylides and maleimides. The catalytic system is based on the distortion of the double helix of DNA by means of the formation of Pt(ii) adducts with guanine units. This distortion, similar to that generated in the interaction of DNA with platinum chemotherapeutic drugs, generates active sites that can accommodate N -metallated azomethine ylides. The proposed reaction mechanism, based on QM(DFT)/MM calculations, is compatible with thermally allowed concerted (but asynchronous) [π4s + π2s] mechanisms leading to the exclusive formation of racemic endo -cycloadducts.

From fundamental studies of reactivity on single crystals to the design of catalysts

NASA Astrophysics Data System (ADS)

H. Larsen, Jane; Chorkendorff, Ib

One of the prominent arguments for performing surface science studies have for many years been to improve and design new and better catalysts. Although surface science has provided the fundamental framework and tools for understanding heterogeneous catalysis until now there have been extremely few examples of actually designing new catalysts based solely on surface science studies. In this review, we shall demonstrate how a close collaboration between different fundamental disciplines like structural-, theoretical-and reactivity-studies of surfaces as well as a strong interaction with industry can have strong synergetic effects and how this was used to develop a new catalyst. As so often before the studies reviewed here were not initiated with the objective to solve a specific problem, but realizing that a new class of very stable two-dimensional alloys could be synthesized from otherwise immiscible metals made it possible to present a new solution to a specific problem in the industrial catalysis relating to methane activation in the steam reforming process. Methane is the main constituent of natural gas and it is an extremely important raw material for many large scale chemical processes such as production of hydrogen, ammonia, and methanol. In the steam reforming process methane and water are converted into a mixture of mainly hydrogen and carbon monoxide, the so-called synthesis gas. Industrially the steam reforming process usually takes place over a catalyst containing small nickel crystallites highly dispersed on a porous support material like aluminum/magnesium oxides in order to achieve a high active metal area. There is a general consensus that the rate limiting step of this process is the dissociative sticking of methane on the nickel surface. Driven by the desire to understand this step and hopefully be able to manipulate the reactivity, a large number of investigations of the methane/nickel interaction have been performed using nickel single crystals as model catalysts. The process has been investigated, both under thermal conditions and by using supersonic molecular beams elucidating the dynamical aspects of the interaction. The results obtained will be reviewed both with respect to the clean and modified nickel surfaces. Especially the two-dimensional gold-nickel alloy system will be considered since the fundamental results here have lead to the invention of a new nickel based catalyst, which is much more resistant to carbon formation than the conventional nickel catalysts. This may be one of the first examples of how fundamental research can lead to the invention of new catalysts. Other overlayer/alloy combinations, their stability, and reactivity are briefly discussed with respect to manipulation of the surface reactivity towards methane.

Understanding low temperature oxidation activity of nanoarray-based monolithic catalysts: from performance observation to structural and chemical insights

DOE PAGES

Du, Shoucheng; Tang, Wenxiang; Guo, Yanbing; ...

2016-12-30

Monolithic catalysts have been widely used in automotive, chemical, and energy relevant industries. Nano-array based monolithic catalysts have been developed, demonstrating high catalyst utilization efficiency and good thermal/mechanical robustness. Compared with the conventional wash-coat based monolithic catalysts, they have shown advances in precise and optimum microstructure control and feasibility in correlating materials structure with properties. Recently, the nano-array based monolithic catalysts have been studied for low temperature oxidation of automotive engine exhaust and exhibited interesting and promising catalytic activities. Here, this review focuses on discussing the key catalyst structural parameters that affect the catalytic performance from the following aspects, (1)more » geometric shape and crystal planes, (2) guest atom doping and defects, (3) array size and size-assisted active species loading, and (4) the synergy effect of metal oxide in composite nano-arrays. Prior to the discussion, an overview of the current status of synthesis and development of the nano-array based monolithic catalysts is introduced. The performance of these materials in low temperature simulated engine exhaust oxidation is also demonstrated. Finally, we hope this review will elucidate the science and chemistry behind the good oxidation performance of the nanoarray- based monolithic catalysts, and serve as a timely and useful research guide for rational design and further improvement of the nano-array based monolithic catalysts for automobile emission control.« less

Understanding low temperature oxidation activity of nanoarray-based monolithic catalysts: from performance observation to structural and chemical insights

DOE Office of Scientific and Technical Information (OSTI.GOV)

Du, Shoucheng; Tang, Wenxiang; Guo, Yanbing

Monolithic catalysts have been widely used in automotive, chemical, and energy relevant industries. Nano-array based monolithic catalysts have been developed, demonstrating high catalyst utilization efficiency and good thermal/mechanical robustness. Compared with the conventional wash-coat based monolithic catalysts, they have shown advances in precise and optimum microstructure control and feasibility in correlating materials structure with properties. Recently, the nano-array based monolithic catalysts have been studied for low temperature oxidation of automotive engine exhaust and exhibited interesting and promising catalytic activities. Here, this review focuses on discussing the key catalyst structural parameters that affect the catalytic performance from the following aspects, (1)more » geometric shape and crystal planes, (2) guest atom doping and defects, (3) array size and size-assisted active species loading, and (4) the synergy effect of metal oxide in composite nano-arrays. Prior to the discussion, an overview of the current status of synthesis and development of the nano-array based monolithic catalysts is introduced. The performance of these materials in low temperature simulated engine exhaust oxidation is also demonstrated. Finally, we hope this review will elucidate the science and chemistry behind the good oxidation performance of the nanoarray- based monolithic catalysts, and serve as a timely and useful research guide for rational design and further improvement of the nano-array based monolithic catalysts for automobile emission control.« less

Comparison of iridium- and ruthenium-based, Pt-surface-enriched, nanosize catalysts for the oxygen-reduction reaction

NASA Astrophysics Data System (ADS)

Kaplan, D.; Goor, M.; Alon, M.; Tsizin, S.; Burstein, L.; Rosenberg, Y.; Popov, I.; Peled, E.

2016-02-01

Pt-surface-enriched nanosize catalysts (Pt-SENS catalysts) with ruthenium and iridium cores, supported on XC72, were synthesized and characterized. The structure and composition of the catalysts are determined by Energy-Dispersive X-ray Spectroscopy (EDS), X-ray Photoelectron Spectroscopy (XPS), Scanning Transmission Electron Microscopy (STEM) and X-Ray Diffraction (XRD). Electrochemical characterization tests, including oxygen-reduction-catalysis activity and durability studies of catalysts are performed with the use of cyclic-voltammetry and rotating-disk-electrode (RDE) techniques at room temperature. The ORR activity of the homemade catalysts is also compared to ORR activity of commercial 50%Pt/C catalyst. It is determined that the Ir-based catalyst (Pt/Ir/XC72) shows higher ORR activity in terms of A g-1 of Pt (at 0.85 V vs. RHE) than the Ru-based catalyst (Pt/Ru/XC72) and the commercial 50%Pt/C. The Ru-based catalyst shows similar ORR activity in terms of A g-1 of Pt, to that of the commercial 50%Pt/C, but with much lower durability.

Recent Trends on Electrochemical Sensors Based on Ordered Mesoporous Carbon

PubMed Central

Walcarius, Alain

2017-01-01

The past decade has seen an increasing number of extensive studies devoted to the exploitation of ordered mesoporous carbon (OMC) materials in electrochemistry, notably in the fields of energy and sensing. The present review summarizes the recent achievements made in field of electroanalysis using electrodes modified with such nanomaterials. On the basis of comprehensive tables, the interest in OMC for designing electrochemical sensors is illustrated through the various applications developed to date. They include voltammetric detection after preconcentration, electrocatalysis (intrinsically due to OMC or based on suitable catalysts deposited onto OMC), electrochemical biosensors, as well as electrochemiluminescence and potentiometric sensors. PMID:28800106

Coupling of carboxylic groups onto the surface of polystyrene parts during fused filament fabrication

NASA Astrophysics Data System (ADS)

Nagel, Jürgen; Zimmermann, Philipp; Schubert, Oliver; Simon, Frank; Schlenstedt, Kornelia

2017-11-01

A method for the fabrication of polystyrene parts, modified with carboxylic groups during Fused Filament Fabrication (FFF), is being introduced. This method is based on the application of a thin layer of a reactive polymer carrying carboxylic groups on a substrate surface. A polystyrene film is printed on top of this layer. During contact between the hot melt and the reactive layer, a Friedel-Crafts type acylation using a green catalyst takes place, which attaches the reactive polymer to the polystyrene surface. The modified surface is homogeneous, hydrophilic and able to bind copper ions. The method could be used to fabricate unique parts of polystyrene with tailored surface functionalisation. It could be applied for laboratory use, e.g. for the manufacture of lab-on-a-chip devices.

Surface modification processes during methane decomposition on Cu-promoted Ni–ZrO2 catalysts

PubMed Central

Wolfbeisser, Astrid; Klötzer, Bernhard; Mayr, Lukas; Rameshan, Raffael; Zemlyanov, Dmitry; Bernardi, Johannes; Rupprechter, Günther

2015-01-01

The surface chemistry of methane on Ni–ZrO2 and bimetallic CuNi–ZrO2 catalysts and the stability of the CuNi alloy under reaction conditions of methane decomposition were investigated by combining reactivity measurements and in situ synchrotron-based near-ambient pressure XPS. Cu was selected as an exemplary promoter for modifying the reactivity of Ni and enhancing the resistance against coke formation. We observed an activation process occurring in methane between 650 and 735 K with the exact temperature depending on the composition which resulted in an irreversible modification of the catalytic performance of the bimetallic catalysts towards a Ni-like behaviour. The sudden increase in catalytic activity could be explained by an increase in the concentration of reduced Ni atoms at the catalyst surface in the active state, likely as a consequence of the interaction with methane. Cu addition to Ni improved the desired resistance against carbon deposition by lowering the amount of coke formed. As a key conclusion, the CuNi alloy shows limited stability under relevant reaction conditions. This system is stable only in a limited range of temperature up to ~700 K in methane. Beyond this temperature, segregation of Ni species causes a fast increase in methane decomposition rate. In view of the applicability of this system, a detailed understanding of the stability and surface composition of the bimetallic phases present and the influence of the Cu promoter on the surface chemistry under relevant reaction conditions are essential. PMID:25815163

Platinum assisted by carbon quantum dots for methanol electro-oxidation

NASA Astrophysics Data System (ADS)

Pan, Dan; Li, Xingwei; Zhang, Aofeng

2018-01-01

Various types of fuel cells as clean and portable power sources show a great attraction, especially direct methanol fuel cell (DMFC) having high energy density, low operating temperature and convenient fuel storage. However, the preparation of low-cost Pt-based catalysts with satisfactory catalytic performance still faces many challenges for its commercialization on large scale. Here, Pt catalysts assisted by carbon quantum dots (CQDs) are reported. The synergistic effect of carbon quantum dots and Pt metals is similar to a bi-component catalyst, such as PtRu. First, carbon quantum dots derived from Vulcan XC-72 carbon black are synthesized by mixed acid etching. Then, carbon black (Vulcan XC-72) is soaked in carbon quantum dots solution for several days to obtain carbon black modified by carbon quantum dots (XC-72-CQDs). Finally, Pt catalysts are supported on XC-72-CQDs (Pt/XC-72-CQDs) through a simple chemical reduction method. For methanol electro-oxidation reaction, the catalytic performance of Pt/XC-72-CQDs is compared with commercial PtRu/C (30% Pt + 15% Ru). Results show that a typical product (Pt/XC-72-CQDs5) exhibits a better catalytic activity than PtRu/C. In cyclic voltammetry test, the specific activity of Pt/XC-72-CQDs5 is 1.06 mA cm-2 Pt and 477.6 mA mg-1 Pt, while that of PtRu/C is 0.77 mA cm-2 Pt and 280.6 mA mg-1 Pt.

Exquisite Enzyme-Fenton Biomimetic Catalysts for Hydroxyl Radical Production by Mimicking an Enzyme Cascade.

PubMed

Zhang, Qi; Chen, Shuo; Wang, Hua; Yu, Hongtao

2018-03-14

Hydrogen peroxide (H 2 O 2 ) is a key reactant in the Fenton process. As a byproduct of enzymatic reaction, H 2 O 2 can be obtained via catalytical oxidation of glucose using glucose oxidase in the presence of O 2 . Another oxidation product (gluconic acid) can suitably adjust the microenvironmental pH contributing to the Fe 3+ /Fe 2+ cycle in the Fenton reaction. Enzymes are extremely efficient at catalyzing a variety of reactions with high catalytic activity, substrate specificity, and yields in living organisms. Inspired by the multiple functions of natural multienzyme systems, an exquisite nanozyme-modified α-FeOOH/porous carbon (PC) biomimetic catalyst constructed by in situ growth of glucose oxidase-mimicking Au nanoparticles and crystallization of adsorbed ferric ions within carboxyl into hierarchically PC is developed as an efficient enzyme-Fenton catalyst. The products (H 2 O 2 , ∼4.07 mmol·L -1 ) of the first enzymatic reaction are immediately used as substrates for the second Fenton-like reaction to generate the valuable • OH (∼96.84 μmol·L -1 ), thus mimicking an enzyme cascade pathway. α-FeOOH nanocrystals, attached by C-O-Fe bondings, are encapsulated into the mesoporous PC frameworks, facilitating the electron transfer between α-FeOOH and the PC support and greatly suppressing iron leaching. This study paves a new avenue for designing biomimetic enzyme-based Fenton catalysts mimicking a natural system for • OH production.

Electrostatic self-assembly of Fe3O4/GO nanocomposites and their application as an efficient Fenton-like catalyst for degradation of rhodamine B

NASA Astrophysics Data System (ADS)

Wang, Wenxia; He, Qi; Xiao, Kaijun; Zhu, Liang

2018-03-01

In the study, a two-major step involving a hydrothermal method and an electrostatic self-assembly method was adopted to synthesis Fe3O4/GO nanocomposites. The Fe3O4 nanoparticles were successfully modified with the 3-aminopropyltrimethoxy-silane and homogeneously deposited onto the surface of GO. They were used as Fenton-like catalyst to degrade Rhodamine B and displayed a higher activity compared with the pristine Fe3O4 nanoparticles, H2O2, Fe3O4/GO nanocomposite and Fe3O4/H2O2 system, demonstrating the synergistic effect between the superior adsorption properties of GO and the excellent catalytic activity of Fe3O4/H2O2 system. Besides, the possible catalytic mechanism and degradation pathway for RhB molecules by Fe3O4/GO nanocomposites and H2O2 was proposed based on the liquid chromatography-mass spectrometry (LC-MS) analysis. The result reveals that the •OH radicals should be the main actives species during catalytic degradation of RhB by the Fe3O4/GO/H2O2 system. In addition, the catalyst is reusable and shows efficiency up to 5 cycles. We believe the strategy in our work can provide insight into designing the novel catalysts for large-scale degradation of organic pollutants in the wastewater.

Pt/Cr and Pt/Ni catalysts for oxygen reduction reaction: to alloy or not to alloy?

PubMed

Escaño, Mary Clare; Gyenge, Elod; Nakanishi, Hiroshi; Kasai, Hideaki

2011-04-01

Bimetallic systems such as Pt-based alloys or non-alloys have exhibited interesting catalytic properties but pose a major challenge of not knowing a priori how the electronic and chemical properties will be modified relative to the parent metals. In this work, we present the origin of the changes in the reactivity of Pt/Cr and Pt/Ni catalysts, which have been of wide interest in fuel cell research. Using spin-polarized density functional theory calculations, we have shown that the modification of Pt surface reactivity in Pt/Ni is purely of geometric origin (strain). We have also found that the Pt-Ni bonding is very weak, which explains the observed instability of Pt-Ni catalysts under electrochemical measurements. On the other hand, Pt/Cr systems are governed by strong ligand effect (metal-metal interaction), which explains the experimentally observed reactivity dependence on the relative composition of the alloying components. The general characteristics of the potential energy curves for O2 dissociative adsorption on the bimetallic systems and the pure Pt clarify why the d-band center still works for Pt/Cr despite the strong Pt-Cr bonding and high spin polarization of Pt d-states. On the basis of the above clarifications, viable Pt-Cr and Pt-Ni structures, which involve nano-sized alloys and non-alloy bulk catalyst, which may strike higher than the currently observed oxidation reduction reaction activity are proposed.

Studies of Heterogenous Palladium and Related Catalysts for Aerobic Oxidation of Primary Alcohols

NASA Astrophysics Data System (ADS)

Ahmed, Maaz S.

Development of aerobic oxidation methods is of critical importance for the advancement of green chemistry, where the only byproduct produced is water. Recent work by our lab has produced an efficient Pd based heterogenous catalyst capable of preforming the aerobic oxidation of a wide spectrum of alcohols to either carboxylic acid or methyl ester. The well-defined catalyst PdBi 0.35Te0.23/C (PBT/C) catalyst has been shown to can perform the aerobic oxidation of alcohols to carboxylic acids in basic conditions. Additionally, we explored this catalyst for a wide range of alcohols and probed the nature of the selectivity of PBT/C for methyl esterification over other side products. Finally, means by which the catalyst operates with respect to oxidation states of the three components, Pd, Bi, and Te, was probed. Carboxylic acids are an important functional group due to their prevalence in various pharmaceutically active agents, agrochemicals, and commodity scale chemicals. The well-defined catalyst PBT/C catalyst was discovered to be effective for the oxidation of a wide spectrum of alcohols to carboxylic acid. The demonstrated substrate scope and functional group tolerance are the widest reported for an aerobic heterogeneous catalyst. Additionally, the catalyst has been implemented in a packed bed reactor with quantitative yield of benzoic acid maintained throughout a two-day run. Biomass derived 5-(hydroxymethyl)furfural (HMF) is also oxidized to 2,5-furandicarboxylic acid (FDCA) in high yield. Exploration of PBT/C for the oxidative methyl esterification was found to exhibit exquisite selectivity for the initial oxidation of primary alcohol instead of methanol, which is the bulk solvent. We explored this selectivity and conclude that it results from various substrate-surface interactions, which are not attainable by methanol. The primary alcohol can outcompete the methanol for binding on the catalyst surface through various interactions between the side chain of the alcohol solvent and the surface of the catalyst: (listed in order of strength) lone pair-surface (heterocyclic primary alcohols) > pi-surface (aryl primary alcohols) > van der Waals-surface (alkyl primary alcohols). These interactions were previously underappreciated in condensed phase heterogeneously catalyzed aerobic oxidations. Bi and Te serve as synergistic promoters that enhance both the rate and yield of the reactions relative to reactions employing Pd alone or Pd in combination with Bi or with Te as the sole promoter. We report X-ray absorption spectroscopic studies of the heterogenous catalyst. These methods show that the promoters undergo oxidation in preference to Pd, maintaining the Pd surface in the active metallic state and preventing inhibition by surface Pd-oxide formation. The data also suggest formation of a Pd-Te alloy phase that modifies the electronic properties of the Pd catalyst. Collectively, these results provide valuable insights into the synergistic benefits of multiple promoters in heterogeneous catalytic oxidation reactions.

Pt/SnO2-based CO-oxidation catalysts for long-life closed-cycle CO2 lasers

NASA Technical Reports Server (NTRS)

Schryer, David R.; Upchurch, Billy T.; Hess, Robert V.; Wood, George M.; Sidney, Barry D.; Miller, Irvin M.; Brown, Kenneth G.; Vannorman, John D.; Schryer, Jacqueline; Brown, David R.

1990-01-01

Noble-metal/tin-oxide based catalysts such as Pt/SnO2 have been shown to be good catalysts for the efficient oxidation of CO at or near room temperature. These catalysts require a reductive pretreatment and traces of hydrogen or water to exhibit their full activity. Addition of Palladium enhances the activity of these catalysts with about 15 to 20 percent Pt, 4 percent Pd, and the balance SnO2 being an optimum composition. Unfortunately, these catalysts presently exhibit significant decay due in part to CO2 retention, probably as a bicarbonate. Research on minimizing the decay in activity of these catalysts is currently in progress. A proposed mechanism of CO oxidation on Pt/SnO2-based catalysts has been developed and is discussed.

Multifunctional mesoporous silica catalyst

DOEpatents

Lin, Victor Shang-Yi; Tsai, Chih-Hsiang; Chen, Hung-Ting; Pruski, Marek; Kobayashi, Takeshi

2015-03-31

The present invention provides bifunctional silica mesoporous materials, including mesoporous silica nanoparticles ("MSN"), having pores modified with diarylammonium triflate and perfluoroaryl moieties, that are useful for the acid-catalyzed esterification of organic acids with organic alcohols.

Effect of high-temperature on the swellable organically-modified silica (SOMS) and its application to gas-phase hydrodechlorination of trichloroethylene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sohn, Hyuntae; Celik, Gokhan; Gunduz, Seval

Pd catalysts supported on swellable organically-modified silica (SOMS) and high-temperature-treated swellable organically-modified silica (H-SOMS) were characterized and tested for gas-phase hydrodechlorination (HDC) of trichloroethylene (TCE) conditions. The high-temperature treatment on SOMS resulted in an increase in surface area and pore diameter as well as significant improvement of Pd dispersion on H-SOMS with smaller Pd particle sizes compared to the Pd/SOMS catalyst. Although the high-temperature treatment led to some alteration of the SOMS polysiloxane network, the hydrophobicity and organic vapor adsorption characteristics of SOMS were preserved. The reduction and oxidation characteristics of Pd on SOMS and HSOMS were investigated in situmore » using XANES technique. It was found that the Pd sites in the pores of SOMS was accessible to small molecules such as H 2, facilitating the reduction of PdO x, whereas oxidation of metallic Pd was limited even at higher temperatures when O 2 was used. This effect was only observed over Pd/SOMS catalyst. For Pd/H-SOMS, because the pores were more widely open than Pd/SOMS, both reduction and oxidation of Pd were observed. Finally, the catalytic activity of Pd/H-SOMS for gas-phase HDC of TCE was significantly better than Pd/SOMS. When water was added to the reactant stream (TCE + H 2O), both Pd/SOMS and Pd/H-SOMS maintained its catalytic performances due to hydrophobic property of the supports.« less

Catalytic Hydrodeoxygenation of High Carbon Furylmethanes to Renewable Jet-fuel Ranged Alkanes over a Rhenium-Modified Iridium Catalyst.

PubMed

Liu, Sibao; Dutta, Saikat; Zheng, Weiqing; Gould, Nicholas S; Cheng, Ziwei; Xu, Bingjun; Saha, Basudeb; Vlachos, Dionisios G

2017-08-24

Renewable jet-fuel-range alkanes are synthesized by hydrodeoxygenation of lignocellulose-derived high-carbon furylmethanes over ReO x -modified Ir/SiO 2 catalysts under mild reaction conditions. Ir-ReO x /SiO 2 with a Re/Ir molar ratio of 2:1 exhibits the best performance, achieving a combined alkanes yield of 82-99 % from C 12 -C 15 furylmethanes. The catalyst can be regenerated in three consecutive cycles with only about 12 % loss in the combined alkanes yield. Mechanistically, the furan moieties of furylmethanes undergo simultaneous ring saturation and ring opening to form a mixture of complex oxygenates consisting of saturated furan rings, mono-keto groups, and mono-hydroxy groups. Then, these oxygenates undergo a cascade of hydrogenolysis reactions to alkanes. The high activity of Ir-ReO x /SiO 2 arises from a synergy between Ir and ReO x , whereby the acidic sites of partially reduced ReO x activate the C-O bonds of the saturated furans and alcoholic groups while the Ir sites are responsible for hydrogenation with H 2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gold-supported cerium-doped NiO x catalysts for water oxidation

DOE PAGES

Ng, Jia Wei Desmond; García-Melchor, Max; Bajdich, Michal; ...

2016-04-29

Here, the development of high-performance catalysts for the oxygen-evolution reaction (OER) is paramount for cost-effective conversion of renewable electricity to fuels and chemicals. Here we report the significant enhancement of the OER activity of electrodeposited NiO x films resulting from the combined effects of using cerium as a dopant and gold as a metal support. This NiCeO x–Au catalyst delivers high OER activity in alkaline media, and is among the most active OER electrocatalysts yet reported. On the basis of experimental observations and theoretical modelling, we ascribe the activity to a combination of electronic, geometric and support effects, where highlymore » active under-coordinated sites at the oxide support interface are modified by the local chemical binding environment and by doping the host Ni oxide with Ce. The NiCeO x–Au catalyst is further demonstrated in a device context by pairing it with a nickel–molybdenum hydrogen evolution catalyst in a water electrolyser, which delivers 50 mA consistently at 1.5 V over 24 h of continuous operation.« less

The Role of Lewis and Brønsted Acid Sites in NO Reduction with NH3 on Sulfur Modified TiO2-Supported V2O5 Catalyst

NASA Astrophysics Data System (ADS)

Zhao, Wei; Dou, Shengping; Zhong, Qin; Wu, Licheng; Wang, Qian; Wang, Aijian

2017-12-01

V2O5/S-doped TiO2 was prepared by the sol-gel and impregnation methods. The adsorption of NO, NH3, and O2 over the catalyst was studied by in situ DRIFTS spectroscopy to elucidate the reaction mechanism of the low-temperature selective catalytic reduction of NO with NH3. Exposing the catalyst to O2 and NO, three types of nitrates species appeared on the surface. The introduction of S to TiO2 could generate large amounts of acid sites for ammonia adsorption on the catalyst, which was believed to be an important role in the SCR reaction and hereby improved the catalytic activity. The results indicated two possible SCR reaction pathways for catalyst. One was that NO was absorbed to form nitrite species, which could react with NH3 on Lewis acid sites, producing N2 and H2O. Another way was that NH3 was adsorbed, then reacted with gas phase NO (E-R) and nitrite intermediates on the surface (L-H).

Industrial wastewater advanced treatment via catalytic ozonation with an Fe-based catalyst.

PubMed

Li, Xufang; Chen, Weiyu; Ma, Luming; Wang, Hongwu; Fan, Jinhong

2018-03-01

An Fe-based catalyst was used as a heterogeneous catalyst for the ozonation of industrial wastewater, and key operational parameters (pH and catalyst dosage) were studied. The results indicated that the Fe-based catalyst significantly improved the mineralization of organic pollutants in wastewater. TOC (total organic carbon) removal was high, at 78.7%, with a catalyst concentration of 200 g/L, but only 31.6% with ozonation alone. The Fe-based catalyst significantly promoted ozone decomposition by 70% in aqueous solution. Hydroxyl radicals (·OH) were confirmed to be existed directly via EPR (electron paramagnetic resonance) experiments, and ·OH were verified to account for about 34.4% of TOC removal with NaHCO 3 as a radical scavenger. Through characterization by SEM-EDS (field emission scanning electron microscope with energy-dispersive spectrometer), XRD (X-ray powder diffraction) and XPS (X-ray photoelectron spectroscopy), it was deduced that FeOOH on the surface of the catalyst was the dominant contributor to the catalytic efficiency. The catalyst was certified as having good stability and excellent reusability based on 50 successive operations and could be used as a filler simultaneously. Thereby, it is a promising catalyst for practical industrial wastewater advanced treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

New electrocatalysts for unitized regenerative fuel cell: Pt-Ir alloy deposited on the proton exchange membrane surface by impregnation-reduction method.

PubMed

Wan, Chieh-Hao; Wu, Chun-Lin; Lin, Meng-Tsun; Shih, Chihhsiong

2010-07-01

In this paper, a modified technique to prepare Pt-Ir catalyst layer on the proton exchange membrane (PEM) surface using the impregnation-reduction (IR) method is proposed to improve the electrocatalytic activity as well as the life cycle of the bifunctional oxygen electrode (BOE). The resulted electrocatalysts were characterized by the Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), Electron Probe Micro-Analysis (EPMA), and Transmission Electron Microscope (TEM). The electrocatalytic properties of the Pt-Ir layer on PEM surface for the oxygen reduction and water oxidation reactions as well as the life cycle of MEA were investigated. Experimental results showed that the Ir particles were dispersed densely in the platinum layer through the modified IR technique. The atomic ratio of Pt over Ir elements was 9:1, and the resulted thickness of the obtained Pt-Ir catalyst layer was about 1.0 microm. The Pt-Ir catalyst layer was composed of Pt layer doped with Ir nano-particles comprising nano Pt-Ir alloy phase. The large surface area of Ir core with Pt shell particles and the presence of nano Pt-Ir alloy phase led to a higher electrocatalytic activity of BOE. Due to the good binding between the Nafion membrane and the Pt-Ir alloy catalyst, as well as the composite structure of the resulted Pt-Ir, the life cycle of Unitized Regenerative Fuel Cell (URFC) is improved through this novel BOE.

Pt/SnO2-based CO-oxidation catalysts for CO2 lasers

NASA Technical Reports Server (NTRS)

Upchurch, Billy T.; Schryer, David R.; Hess, Robert V.; Brown, Kenneth G.; Van Norman, John D.

1990-01-01

The activity of Pt/SnO2-based CO-oxidation catalysts has been maximized by optimizing pretreatment conditions and catalyst formulation. The role of H2O in activating these catalysts and of CO2 retention in deactivating them has been determined as has the interaction of these catalysts with rare-isotope C(0-18) and (O-18)2.

Diethyl Ether Production during Catalytic Dehydration of Ethanol over Ru- and Pt- modified H-beta Zeolite Catalysts.

PubMed

Kamsuwan, Tanutporn; Praserthdam, Piyasan; Jongsomjit, Bunjerd

2017-01-01

In the present study, the catalytic dehydration of ethanol over H-beta zeolite (HBZ) catalyst with ruthenium (Ru-HBZ) and platinum (Pt-HBZ) modification was investigated. Upon the reaction temperature between 200 and 400°C, it revealed that ethanol conversion and ethylene selectivity increased with increasing temperature for both Ru and Pt modification. At lower temperature (200 to 250°C), diethyl ether (DEE) was the major product. It was found that Ru and Pt modification on HBZ catalyst can result in increased DEE yield at low reaction temperature due to increased ethanol conversion without a significant change in DEE selectivity. By comparing the DEE yield of all catalysts in this study, the Ru-HBZ catalyst apparently exhibited the highest DEE yield (ca. 47%) at 250°C. However, at temperature from 350 to 400°C, the effect of Ru and Pt was less pronounced on ethylene yield. With various characterization techniques, the effects of Ru and Pt modification on HBZ catalyst were elucidated. It revealed that Ru and Pt were present in the highly dispersed forms and well distributed in the catalyst granules. It appeared that the weak acid sites measured by NH 3 temperature-programmed desorption technique also decreased with Ru and Pt promotion. Thus, the increased DEE yields with the Ru and Pt modification can be attributed to the presence of optimal weak acid sites leading to increased intrinsic activity of the catalysts. It can be concluded that the modification of Ru and Pt on HBZ catalyst can improve the DEE yields by ca. 10%.

Heterogeneous Electrocatalyst of Palladium-Cobalt-Phosphorus on Carbon Support for Oxygen Reduction Reaction in High Temperature Proton Exchange Membrane Fuel Cells.

PubMed

You, Dae Jong; Pak, Chanho; Jin, Seon-Ah; Lee, Kang Hee; Kwon, Kyungjung; Choi, Kyoung Hwan; Heo, Pil Won; Jang, Hongchul; Kim, Jun Young; Kim, Ji Man

2016-05-01

Palladium-cobalt-phosphorus (PdCoP) catalysts supported on carbon (Ketjen Black) were investigated as a cathode catalyst for oxygen reduction reaction (ORR) in high temperature proton exchange membrane fuel cells (HT-PEMFCs). The PdCoP catalyst was synthesized via a modified polyol process in teflon-sealed reactor by microwave-heating. From X-ray diffraction and transmission electron microscopic analysis, the PdCoP catalyst exhibits a face-centered cubic structure, similar to palladium (Pd), which is attributed to form a good solid solution of Co atoms and P atoms in the Pd lattice. The PdCoP nanoparticles with average diameter of 2.3 nm were uniformly distributed on the carbon support. The electrochemical surface area (ECSA) and ORR activity of PdP, PdCo and PdCoP catalysts were measured using a rotating disk electrode technique with cyclic voltammetry and the linear sweep method. The PdCoP catalysts showed the highest performances for ECSA and ORR, which might be attributed both to formation of small nanoparticle by phosphorus atom and to change in lattice constant of Pd by cobalt atom. Furthermore, The HT-PEMFCs single cell performance employing PdCoP catalyst exhibited an enhanced cell performance compared to a single cell using the PdP and PdCo catalysts. This result indicates the importance of electric and geometric control of Pd alloy nanoparticles that can improve the catalytic activity. This synergistic combination of Co and P with Pd could provide the direction of development of non-Pt catalyst for fuel cell system.

Characterization and Modeling of Electrical Response of Electrode Catalyzed Reactions in AIGaN/GaN-Based Gas Sensors

NASA Astrophysics Data System (ADS)

Melby, Jacob H.

AlGaN/GaN high electron mobility transistors (HEMT) and AlGaN/GaN diodes have promise for use as hydrogen and hydrocarbon sensors for a variety of industrial, military, and commercial applications. These semiconductor-based sensors have a number of advantages over other sensor technologies, such as the ability to operate at high temperatures, in corrosive environments, or under ionizing radiation. The high sensitivity of these devices to hydrogen-containing gases is associated with polarization differences within the AlGaN/GaN heterostructure that give rise to the formation of a two-dimensional electron gas (2DEG); exposure of the device to hydrogen changes the density of the 2DEG, which can be detected in a HEMT or diode structure. Although sensitivity to a range of gases has been reported, the factors that influence the behavior of the sensors are not well studied. The overarching goals of the research that follows were to determine how gas exposure conditions affect sensor behavior, to characterize and model the relationship between the electrical response of the sensors and the external gaseous environment, and to investigate the effects of using different metal catalysts on sensor behavior. The heterostructures used in this work were grown via metalorganic vapor phase epitaxy (MOVPE). Schottky diode and transistor devices employing platinum-group (Pd, Pt, Rh, Ir, Ru, and Os) catalysts were fabricated to allow electrical sensitivity in the presence of hydrogen and hydrogen containing gases. The generation of atomic hydrogen on the catalyst surface results in the rapid formation of hydrogen dipoles at the metal-semiconductor interface, which produces a measurable electronic response. The electrical response of Pt-gated HEMT-based sensors were measured in a flowing gaseous stream consisting of hydrogen in a pure nitrogen diluent at ambient and elevated temperatures. The transistors exhibited excellent transfer characteristics for temperatures ranging from 25°C to 125°C. The absolute current change was measured as a function of hydrogen concentration and compared with simulated curves based on the Langmuir isotherm and four other modified isotherms at a sensor temperature of 125°C. The sensor response was found to monotonically increase for a wide range of hydrogen concentrations (500 ppb to 5 vol%). It was found that the Langmuir isotherm, which treats all hydrogen binding sites as equivalent, was inadequate to describe the sensor response. A simple two-state model involving two distinct hydrogen binding states that have previously been observed in surface studies was found to adequately describe the response of these sensors from 500 ppb to 5 vol% hydrogen in nitrogen. Other modified Langmuir models were also analyzed and compared with the two-state model. While the models based on modified isotherms all yielded good fits to the data, the simpler two-state model (based upon a weakly bound and strongly bound hydrogen atom) and the Sips model (with distribution of states skewed towards higher binding energies) more closely match results from surface studies of dissociative desorption of hydrogen on Pt. Either of these models should therefore serve as a reasonable foundation for understanding and modeling the response of AlGaN/GaN-based hydrogen sensors with Pt catalysts. The electrical response of a Pt-gated HEMT-based sensor was also measured in a flowing gaseous stream consisting of hydrogen in air at elevated temperatures. The sensor response was found to monotonically increase for a narrow range of hydrogen pressures (1000 ppm to 4 vol%). Oxygen is found to decrease sensor response magnitude and increase the sensor response time. A modified Langmuir isotherm was found to adequately describe the influence of oxygen on a Pt-gated HEMT-based sensor under a narrow range of conditions. Additional sensor measurements were conducted on AlGaN/GaN diode sensors employing a variety of platinum-group catalysts. The influence of oxygen on the sensor response was found to be highly dependent upon the chemistry of hydrogen-oxygen interaction on the catalyst interface. A sensor diode array was fabricated using a ternary Pdx CuyAu1-x-y composition spread alloy catalyst and tested in a flowing gaseous stream consisting of pure hydrogen in nitrogen at room temperature. The resulting diode sensitivity was mapped as a function of composition and revealed intriguing hot spots of hydrogen sensitivity. Numerous technological challenges prevented further exploration of the ternary alloy spread; however, the preliminary results of this structure suggest that a reduction in hydrogen binding energy on the surface can result in a substantial increase in hydrogen dipoles at the metal semiconductor interface. Sensitivity to methane and ethylene was demonstrated using AlGaN/GaN-based sensors. Detection of methane and ethylene require elevated temperatures to break the C-H bond and produce atomic hydrogen. The sensor response is significantly more complicated than hydrogen and not always well-behaved with respect to temperature and time. XPS measurements conducted at CMU indicate a buildup of carbon on the platinum surface upon hydrocarbon exposure, trending toward a saturated carbon content. Lastly, operation of a diode sensor was examined in-situ under high hydrostatic pressure (2000psi) in both pure water and helium. Numerous stability issues were addressed in the course of these experiments. The steady-state influence of hydrostatic pressures on the diode sensor was found to be negligible in the absence of hydrogen. Hydrogen sensitivity was demonstrated in pure water with a hydrogen overpressure for devices employing an epoxy membrane. The same diode device failed to detect a large methane overpressure in water at room temperature and water at 80°C.

Manipulating the Rate-Limiting Step in Water Oxidation Catalysis by Ruthenium Bipyridine–Dicarboxylate Complexes

DOE PAGES

Shaffer, David W.; Xie, Yan; Szalda, David J.; ...

2016-11-01

In order to gain a deeper mechanistic understanding of water oxidation by [(bda)Ru(L) 2] catalysts (bdaH 2 = [2,2'-bipyridine]-6,6'-dicarboxylic acid; L = pyridine-type ligand), a series of modified catalysts with one and two trifluoromethyl groups in the 4 position of the bda 2– ligand was synthesized and studied using stopped-flow kinetics. The additional $-$CF 3 groups increased the oxidation potentials for the catalysts and enhanced the rate of electrocatalytic water oxidation at low pH. Stopped-flow measurements of cerium(IV)-driven water oxidation at pH 1 revealed two distinct kinetic regimes depending on catalyst concentration. At relatively high catalyst concentration (ca. ≥10 –4more » M), the rate-determining step (RDS) was a proton-coupled oxidation of the catalyst by cerium(IV) with direct kinetic isotope effects (KIE > 1). At low catalyst concentration (ca. ≤10 –6 M), the RDS was a bimolecular step with k H/k D ≈ 0.8. The results support a catalytic mechanism involving coupling of two catalyst molecules. The rate constants for both RDSs were determined for all six catalysts studied. The presence of $-$CF 3 groups had inverse effects on the two steps, with the oxidation step being fastest for the unsubstituted complexes and the bimolecular step being faster for the most electron-deficient complexes. Finally, though the axial ligands studied here did not significantly affect the oxidation potentials of the catalysts, the nature of the ligand was found to be important not only in the bimolecular step but also in facilitating electron transfer from the metal center to the sacrificial oxidant.« less

Esterification free fatty acid in sludge palm oil using ZrO2/SO42- - rice husk ash catalyst

NASA Astrophysics Data System (ADS)

Hidayat, Arif; Sutrisno, Bachrun

2017-05-01

Indonesia, as one of the biggest palm oil producers and exporters in the world, is producing large amounts of low-grade oil such as sludge palm oil (SPO) from palm oil industries. The use of SPO can lower the cost of biodiesel production significantly, which makes SPO a highly potential alternative feedstock for biodiesel production. In this paper, the esterification of free fatty acid on sludge palm oil was studied using rice husk ash as heterogeneous solid catalysts. Heterogeneous solid catalysts offer significant advantages of eliminating separation, corrosion, toxicity and environmental problems. In this paper the esterification of SPO, a by-product from palm oil industry, in the presence of modified rice husk ash catalysts was studied. The rice husk ash catalysts were synthesized by impregnating of Zirconia (Zr) on rice husk ash followed by sulfonation. The rice husk ash catalysts were characterized by using different techniques, such as FT-IR, XRD, and porous analysis. The effects of the mass ratio of catalyst to oil (1 - 10%), the molar ratio of methanol to oil (4:1 - 10:1), and the reaction temperature (40 - 60°C) were studied for the conversion of free fatty acids (FFAs) to optimize the reaction conditions. The results showed that the optimal conditions were an methanol to oil molar ratio of 10:1, the amount of catalyst of 10%w, and reaction temperature of 60°C.

V-doped TiO2 supported Pt as a promising oxygen reduction reaction catalyst: Synthesis, characterization and in-situ evaluation in proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Bharti, Abha; Cheruvally, Gouri

2017-09-01

This study deals with the synthesis and characterization of V-doped, TiO2 supported Pt catalyst (Pt/V-TiO2) for oxygen reduction reaction (ORR) and its in-situ performance investigation in proton exchange membrane (PEM) fuel cell. Pt/V-TiO2 nanocomposite catalyst is prepared via a facile sol-gel and microwave assisted, modified chemical reduction route and its performance is compared with the undoped TiO2 supported catalyst, Pt/TiO2 prepared in an identical way. The prepared Pt/V-TiO2 and Pt/TiO2 catalysts are employed as cathode catalyst in PEM fuel cell and compared with standard Pt/C catalyst. Their comparative studies are conducted with physical and electrochemical techniques. In-situ electrochemical characterization studies show improved ORR catalytic activity of Pt/V-TiO2 compared to Pt/TiO2. Furthermore, both Pt/TiO2 and Pt/V-TiO2 are more stable than Pt/C when subjected to 6000 voltammetric cycles in the range of 0.2-1.2 V vs. standard hydrogen electrode in operating fuel cell conditions, losing only <20% of its electrochemical surface area as compared to 50% loss exhibited by Pt/C. This study thus demonstrates Pt/V-TiO2 nanocomposite material as a potential cathode catalyst for PEM fuel cell with immense scope for further investigation.

H2O2 sensing using HRP modified catalyst-free ZnO nanorods synthesized by RF sputtering

NASA Astrophysics Data System (ADS)

Srivastava, Amit; Kumar, Naresh; Singh, Priti; Singh, Sunil Kumar

2017-06-01

Catalyst-free ( 00 l) oriented ZnO nanorods (NRs) -based biosensor for the H2O2 sensing has been reported. The (002) oriented ZnO NRs as confirmed by X-ray diffraction were successfully grown on indium tin oxide (ITO) coated glass substrate by radio frequency (RF) sputtering technique without using any catalyst. Horseradish peroxidase (HRP) enzyme was immobilized on ZnO NRs by physical adsorption technique to prepare the biosensor. In this HRP/ZnO NR/ITO bioelectrode, nafion solution was added to form a tight membrane on surface. The prepared bioelectrode has been used for biosensing measurements by electrochemical analyzer. The electrochemical studies reveal that the prepared HRP/ZnO NR/ITO biosensor is highly sensitive to the detection of H2O2 over a linear range of 0.250-10 μM. The ZnO NR-based biosensor showed lower value of detection limit (0.125 μM) and higher sensitivity (13.40 µA/µM cm2) towards H2O2. The observed value of higher sensitivity attributed to larger surface area of ZnO nanostructure for effective loading of HRP besides its high electron communication capability. In addition, the biosensor also shows lower value of enzyme's kinetic parameter (Michaelis-Menten constant, K m) of 0.262 μM which indicates enhanced enzyme affinity of HRP to H2O2. The reported biosensor may be useful for various applications in biosensing, clinical, food, and beverage industry.

ZnSe quantum dots modified with a Ni(cyclam) catalyst for efficient visible-light driven CO2 reduction in water.

PubMed

Kuehnel, Moritz F; Sahm, Constantin D; Neri, Gaia; Lee, Jonathan R; Orchard, Katherine L; Cowan, Alexander J; Reisner, Erwin

2018-03-07

A precious metal and Cd-free photocatalyst system for efficient CO 2 reduction in water is reported. The hybrid assembly consists of ligand-free ZnSe quantum dots (QDs) as a visible-light photosensitiser combined with a phosphonic acid-functionalised Ni(cyclam) catalyst, NiCycP. This precious metal-free photocatalyst system shows a high activity for aqueous CO 2 reduction to CO (Ni-based TON CO > 120), whereas an anchor-free catalyst, Ni(cyclam)Cl 2 , produced three times less CO. Additional ZnSe surface modification with 2-(dimethylamino)ethanethiol (MEDA) partially suppresses H 2 generation and enhances the CO production allowing for a Ni-based TON CO of > 280 and more than 33% selectivity for CO 2 reduction over H 2 evolution, after 20 h visible light irradiation ( λ > 400 nm, AM 1.5G, 1 sun). The external quantum efficiency of 3.4 ± 0.3% at 400 nm is comparable to state-of-the-art precious metal photocatalysts. Transient absorption spectroscopy showed that band-gap excitation of ZnSe QDs is followed by rapid hole scavenging and very fast electron trapping in ZnSe. The trapped electrons transfer to NiCycP on the ps timescale, explaining the high performance for photocatalytic CO 2 reduction. With this work we introduce ZnSe QDs as an inexpensive and efficient visible light-absorber for solar fuel generation.

Making ultrafine and highly-dispersive multimetallic nanoparticles in three-dimensional graphene with supercritical fluid as excellent electrocatalyst for oxygen reduction reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Yazhou; Yen, Clive H.; Hu, Yun Hang

2016-01-01

Three-dimensional (3D) graphene showed an advanced support for designing porous electrode materials due to its high specific surface area, large pore volume, and excellent electronic property. However, the electrochemical properties of reported porous electrode materials still need to be improved further. The current challenge is how to deposit desirable nanoparticles (NPs) with controllable structure, loading and composition in 3D graphene while maintaining the high dispersion. Herein, we demonstrate a modified supercritical fluid (SCF) technique to address this issue by controlling the SCF system. Using this superior method, a series of Pt-based/3D graphene materials with the ultrafine-sized, highly dispersive and controllablemore » composition multimetallic NPs were successfully synthesized. Specifically, the resultant Pt40Fe60/3D graphene showed a significant enhancement in electrocatalytic performance for the oxygen reduction reaction (ORR), including a factor of 14.2 enhancement in mass activity (1.70 A mgPt 1), a factor of 11.9 enhancement in specific activity (1.55 mA cm 2), and higher durability compared with that of Pt/C catalyst. After careful comparison, the Pt40Fe60/3D graphene catalyst shows the higher ORR activity than most of the reported similar 3D graphene-based catalysts. The successful synthesis of such attractive materials by this method also paves the way to develop 3D graphene in widespread applications.« less

Technology development for cobalt F-T catalysts. Quarterly technical progress report number 10, January 1--March 31, 1995

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singleton, A.H.

1995-06-28

The goal of this project is the development of a commercially-viable, cobalt-based Fischer-Tropsch (F-T) catalyst for use in a slurry bubble column reactor. The major objectives of this work are (1) to develop a cobalt-based F-T catalyst with low (< 5%) methane selectivity, (2) to develop a cobalt-based F-T catalyst with water-gas shift activity, and (3) to combine both these improvements into one catalyst. The project consists of five major tasks: catalyst development; catalyst testing; catalyst reproducibility tests; catalyst aging tests; and preliminary design and cost estimate for a demonstrate scale catalyst production facility. Technical accomplishments during this reporting periodmore » include the following. It appears that the higher activity obtained for the catalysts prepared using an organic solution and reduced directly without prior calcination was the result of higher dispersions obtained under such pretreatment. A Ru-promoted Co catalyst on alumina with 30% Co loading exhibited a 4-fold increase in dispersion and a 2-fold increase in activity in the fixed-bed reactor from that obtained with the non-promoted catalyst. Several reactor runs have again focused on pushing conversion to higher levels. The maximum conversion obtained has been 49.7% with 26g catalyst. Further investigations of the effect of reaction temperature on the performance of Co catalysts during F-T synthesis were started using a low activity catalyst and one of the most active catalysts. The three 1 kg catalyst batches prepared by Calsicat for the reproducibility and aging studies were tested in both the fixed-bed and slurry bubble column reactors under the standard reaction conditions. The effects of adding various promoters to some cobalt catalysts have also been addressed. Results are presented and discussed.« less

DEVELOPMENT OF ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adeyinka A. Adeyiga

2001-09-01

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. The use of iron-based catalysts is attractive not only due to their low cost and ready availability, but also due to their high water-gas shift activity which makes it possible to use these catalysts with low H{sub 2}/CO ratios. However, a serious problem with use ofmore » Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, makes the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. Recently, fundamental understanding of physical attrition is being addressed by incorporating suitable binders into the catalyst recipe. This has resulted in the preparation of a spray dried Fe-based catalyst having aps of 70 mm with high attrition resistance. This Fe-based attrition resistant, active and selective catalyst gave 95% CO conversion through 125 hours of testing in a fixed-bed at 270 C, 1.48 MPa, H{sub 2}/CO=0.67 and 2.0 NL/g-cat/h with C{sub 5}{sup +} selectivity of >78% and methane selectivity of <5%. However, further development of the catalyst is needed to address the chemical attrition due to phase changes that any Fe-catalyst goes through potentially causing internal stresses within the particle and resulting in weakening, spalling or cracking. The objective of this research is to develop robust iron-based Fischer-Tropsch catalysts that have suitable activity, selectivity and stability to be used in the slurry bubble column reactor. Specifically we aim to develop to: (i) improve the performance and preparation procedure of the high activity, high attrition resistant, high alpha iron-based catalysts synthesized at Hampton University, (ii) seek improvements in the catalyst performance through variations in process conditions, pretreatment procedures and/or modifications in catalyst preparation steps and (iii) investigate the performance in a slurry reactor. The effort during the reporting period has been devoted to attrition study of the iron-based catalysts. Precipitated silica appeared to decrease attrition resistance of spray-dried iron FT catalysts. It was found that the catalyst with precipitated silica content at around 12wt% showed the lowest attrition resistance. The results of net change in volume moment and catalyst morphology showed supporting evidences to the attrition results. Catalysts with low attrition resistance generated more fines loss, had higher net change in volume moment and showed more breakage of particles. BET surface area and pore volume of this catalyst series fluctuated; therefore no conclusion can be drawn from the data obtained. However, catalyst with no precipitated silica showed the lowest in BET surface area and pore volume, as expected. Addition of precipitated silica to the catalysts had no effect to the phase changes of iron that could have significant influence to catalyst attrition. The presence of precipitated silica is needed for enhancing catalyst surface area; however, the amount of silica added should be compromising with attrition resistance of catalysts.« less

Tannic acid- and natural organic matter-coated magnetite as green Fenton-like catalysts for the removal of water pollutants

NASA Astrophysics Data System (ADS)

Nadejde, C.; Neamtu, M.; Hodoroaba, V.-D.; Schneider, R. J.; Paul, A.; Ababei, G.; Panne, U.

2015-12-01

The use of magnetic materials as heterogeneous catalysts has attracted increasing attention in the last years since they proved to be promising candidates for water treatment. In the present study, two types of surface-modified magnetite (Fe3O4) nanoparticles, coated with non-hazardous naturally occurring agents—either tannic acid (TA) or dissolved natural organic matter—were evaluated as magnetic heterogeneous catalysts. Chemical synthesis (co-precipitation) was chosen to yield the nanocatalysts due to its well-established simplicity and efficiency. Subsequently, the properties of the final products were fully assessed by various characterization techniques. The catalytic activity in heterogeneous oxidation of aqueous solutions containing a model pollutant, Bisphenol A (BPA), was comparatively studied. The effect of operational parameters (catalyst loading, H2O2 dosage, and UV light irradiation) on the degradation performance of the oxidation process was investigated. The optimum experimental parameters were found to be 1.0 g/L of catalysts and 10 mM H2O2, under UV irradiation. The highest mineralization rates were observed for Fe3O4-TA catalyst. More than 80 % of BPA was removed after 30 min of reaction time under the specified experimental conditions. The obtained results showed that the two catalysts studied here are suitable candidates for the removal of pollutants in wastewaters by means of heterogeneous reaction using a green sustainable treatment method.

Lagrangian Approach to Study Catalytic Fluidized Bed Reactors

NASA Astrophysics Data System (ADS)

Madi, Hossein; Hossein Madi Team; Marcelo Kaufman Rechulski Collaboration; Christian Ludwig Collaboration; Tilman Schildhauer Collaboration

2013-03-01

Lagrangian approach of fluidized bed reactors is a method, which simulates the movement of catalyst particles (caused by the fluidization) by changing the gas composition around them. Application of such an investigation is in the analysis of the state of catalysts and surface reactions under quasi-operando conditions. The hydrodynamics of catalyst particles within a fluidized bed reactor was studied to improve a Lagrangian approach. A fluidized bed methanation employed in the production of Synthetic Natural Gas from wood was chosen as the case study. The Lagrangian perspective was modified and improved to include different particle circulation patterns, which were investigated through this study. Experiments were designed to evaluate the concepts of the model. The results indicate that the setup is able to perform the designed experiments and a good agreement between the simulation and the experimental results were observed. It has been shown that fluidized bed reactors, as opposed to fixed beds, can be used to avoid the deactivation of the methanation catalyst due to carbon deposits. Carbon deposition on the catalysts tested with the Lagrangian approach was investigated by temperature programmed oxidation (TPO) analysis of ex-situ catalyst samples. This investigation was done to identify the effects of particles velocity and their circulation patterns on the amount and type of deposited carbon on the catalyst surface. Ecole Polytechnique Federale de Lausanne(EPFL), Paul Scherrer Institute (PSI)

Investigation of heterogeneous asymmetric dihydroxylation over OsO{sub 4}-(QN){sub 2}PHAL catalysts of functionalized bimodal mesoporous silica with ionic liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qiu, Shenjie; Sun, Jihong, E-mail: jhsun@bjut.edu.cn; Li, Yuzhen

2011-08-15

Highlights: {yields} Functionalized bimodal mesoporous silica with MTMSPIm{sup +}Cl{sup -}. {yields} Mesoporous catalyst immobilized with OsO{sub 4}-(QN){sub 2}PHAL. {yields} Catalysts for asymmetric dihydroxylation reaction with high yield and enatioselectivity. {yields} Recyclable catalysts. -- Abstract: A novel synthesis of the functionalized bimodal mesoporous silica with ionic liquid (FBMMs) was performed. After grafting 1-methyl-3-(trimethoxysilyl)propylimidazolium chloride onto the surface of bimodal mesoporous silicas, 1,4-bis(9-O-quininyl)phthalazine ((QN){sub 2}-PHAL) and K{sub 2}Os(OH){sub 4}.2H{sub 2}O were immobilized onto the modified FBMMs by adsorption or ionic exchange methods, and then, the asymmetric dihydroxylation reaction was carried out by using solid catalysts. Techniques such as X-ray diffraction, Fourier Transformmore » Infrared spectroscopy, N{sub 2} adsorption and desorption were employed to characterize their structure and properties. The results showed that the mesoporous ordering degree of bimodal mesoporous silica decreased after functionalization and immobilization of OsO{sub 4}-(QN){sub 2}PHAL. Being very effective in asymmetric dihydroxylation with high yield and enantioselectivity, the prepared heterogeneous solid catalyst could be recycled for five times with little loss of enantioselectivity, with comparison of those results obtained in homophase system. Moreover, the effect of Osmium catalyst on asymmetric dihydroxylation was investigated.« less

Development of HAN-based Liquid Propellant Thruster

NASA Astrophysics Data System (ADS)

Hisatsune, K.; Izumi, J.; Tsutaya, H.; Furukawa, K.

2004-10-01

Many of propellants that are applied to the conventional spacecraft propulsion system are toxic propellants. Because of its toxicity, considering the environmental pollution or safety on handling, it will be necessary to apply the "green" propellant to the spacecraft propulsion system. The purpose of this study is to apply HAN based liquid propellant (LP1846) to mono propellant thruster. Compared to the hydrazine that is used in conventional mono propellant thruster, HAN based propellant is not only lower toxic but also can obtain higher specific impulse. Moreover, HAN based propellant can be decomposed by the catalyst. It means there are the possibility of applying to the mono propellant thruster that can leads to the high reliability of the propulsion system.[1],[2] However, there are two technical subjects, to apply HAN based propellant to the mono propellant thruster. One is the high combustion temperature. The catalyst will be damaged under high temperature condition. The other is the low catalytic activity. It is the serious problem on application of HAN based propellant to the mono propellant thruster that is used for attitude control of spacecraft. To improve the catalytic activity of HAN based propellant, it is necessary to screen the best catalyst for HAN based propellant. The adsorption analysis is conducted by Monte Carlo Simulation to screen the catalyst metal for HAN and TEAN. The result of analysis shows the Iridium is the best catalyst metal for HAN and TEAN. Iridium is the catalyst metal that is used at conventional mono propellant thruster catalyst Shell405. Then, to confirm the result of analysis, the reaction test about catalyst is conducted. The result of this test is the same as the result of adsorption analysis. That means the adsorption analysis is effective in screening the catalyst metal. At the evaluating test, the various types of carrier of catalyst are also compared to Shell 405 to improve catalytic activity. The test result shows the inorganic porous media is superior to Shell405 in catalytic activity. Next, the catalyst life with HAN based propellant (LP1846) is evaluated. The Shell405 and inorganic porous media catalyst are compared at the life test. The test result shows the inorganic porous media catalyst is superior to Shell405 in catalyst life. In this paper, the detail of the result of adsorption analysis and evaluating test are reported.

Electrochemical behavior of platinum nanoparticles on a carbon xerogel support modified with a [(trifluoromethyl)-benzenesulfonyl]imide electrolyte.

PubMed

Liu, Bing; Mei, Hua; DesMarteau, Darryl; Creager, Stephen E

2014-12-11

A monoprotic [(trifluoromethyl)benzenesulfonyl]imide (SI) superacid electrolyte was used to covalently modify a mesoporous carbon xerogel (CX) support via reaction of the corresponding trifluoromethyl aryl sulfonimide diazonium zwitterion with the carbon surface. Electrolyte attachment was demonstrated by elemental analysis, acid-base titration, and thermogravimetric analysis. The ion-exchange capacity of the fluoroalkyl-aryl-sulfonimide-grafted carbon xerogel (SI-CX) was ∼0.18 mequiv g(-1), as indicated by acid-base titration. Platinum nanoparticles were deposited onto the SI-grafted carbon xerogel samples by the impregnation and reduction method, and these materials were employed to fabricate polyelectrolyte membrane fuel-cell (PEMFC) electrodes by the decal transfer method. The SI-grafted carbon-xerogel-supported platinum (Pt/SI-CX) was characterized by X-ray diffraction and transmission electron microscopy to determine platinum nanoparticle size and distribution, and the findings are compared with CX-supported platinum catalyst without the grafted SI electrolyte (Pt/CX). Platinum nanoparticle sizes are consistently larger on Pt/SI-CX than on Pt/CX. The electrochemically active surface area (ESA) of platinum catalyst on the Pt/SI-CX and Pt/CX samples was measured with ex situ cyclic voltammetry (CV) using both hydrogen adsorption/desorption and carbon monoxide stripping methods and by in situ CV within membrane electrode assemblies (MEAs). The ESA values for Pt/SI-CX are consistently lower than those for Pt/CX. Some possible reasons for the behavior of samples with and without grafted SI layers and implications for the possible use of SI-grafted carbon layers in PEMFC devices are discussed.

Functionalized multi-walled carbon nanotubes in an aldol reaction

NASA Astrophysics Data System (ADS)

Chronopoulos, D. D.; Kokotos, C. G.; Karousis, N.; Kokotos, G.; Tagmatarchis, N.

2015-01-01

The covalent functionalization of multi-walled carbon nanotubes (MWCNTs) with a proline-based derivative is reported. Initially, MWCNTs were oxidized in order to introduce a large number of carboxylic units on their tips followed by N-tert-butoxycarbonyl-2,2'(ethylenedioxy)bis-(ethylamine) conjugation through an amide bond. Then, a proline derivative bearing a carboxylic terminal moiety at the 4-position was coupled furnishing proline-modified MWCNTs. This new hybrid material was fully characterized by spectroscopic and microscopy means and its catalytic activity in the asymmetric aldol reaction between acetone and 4-nitrobenzaldehyde was evaluated for the first time, showing to proceed almost quantitatively in aqueous media. Furthermore, several amino-modified MWCNTs were prepared and examined in the particular aldol reaction. These new hybrid materials exhibited an enhanced catalytic activity in water, contrasting with the pristine MWCNTs as well as the parent organic molecule, which failed to catalyze the reaction efficiently. Furthermore, the modified MWCNTs proved to catalyze the aldol reaction even after three repetitive cycles. Overall, a green approach for the aldol reaction is presented, where water can be employed as the solvent and modified MWCNTs can be used as catalysts, which can be successfully recovered and reused, while their catalytic activity is retained.The covalent functionalization of multi-walled carbon nanotubes (MWCNTs) with a proline-based derivative is reported. Initially, MWCNTs were oxidized in order to introduce a large number of carboxylic units on their tips followed by N-tert-butoxycarbonyl-2,2'(ethylenedioxy)bis-(ethylamine) conjugation through an amide bond. Then, a proline derivative bearing a carboxylic terminal moiety at the 4-position was coupled furnishing proline-modified MWCNTs. This new hybrid material was fully characterized by spectroscopic and microscopy means and its catalytic activity in the asymmetric aldol reaction between acetone and 4-nitrobenzaldehyde was evaluated for the first time, showing to proceed almost quantitatively in aqueous media. Furthermore, several amino-modified MWCNTs were prepared and examined in the particular aldol reaction. These new hybrid materials exhibited an enhanced catalytic activity in water, contrasting with the pristine MWCNTs as well as the parent organic molecule, which failed to catalyze the reaction efficiently. Furthermore, the modified MWCNTs proved to catalyze the aldol reaction even after three repetitive cycles. Overall, a green approach for the aldol reaction is presented, where water can be employed as the solvent and modified MWCNTs can be used as catalysts, which can be successfully recovered and reused, while their catalytic activity is retained. Electronic supplementary information (ESI) available: Experimental details for the synthesis of 5, 8 and 11; 1H & 13C NMR of compounds 8 and 11; ATR-IR spectra, thermographs and TEM imaging of hybrids 10 and 13. See DOI: 10.1039/c4nr06543c

Autothermal and partial oxidation reformer-based fuel processor, method for improving catalyst function in autothermal and partial oxidation reformer-based processors

DOEpatents

Ahmed, Shabbir; Papadias, Dionissios D.; Lee, Sheldon H. D.; Ahluwalia, Rajesh K.

2013-01-08

The invention provides a fuel processor comprising a linear flow structure having an upstream portion and a downstream portion; a first catalyst supported at the upstream portion; and a second catalyst supported at the downstream portion, wherein the first catalyst is in fluid communication with the second catalyst. Also provided is a method for reforming fuel, the method comprising contacting the fuel to an oxidation catalyst so as to partially oxidize the fuel and generate heat; warming incoming fuel with the heat while simultaneously warming a reforming catalyst with the heat; and reacting the partially oxidized fuel with steam using the reforming catalyst.

Si photoanode protected by a metal modified ITO layer with ultrathin NiO(x) for solar water oxidation.

PubMed

Sun, Ke; Shen, Shaohua; Cheung, Justin S; Pang, Xiaolu; Park, Namseok; Zhou, Jigang; Hu, Yongfeng; Sun, Zhelin; Noh, Sun Young; Riley, Conor T; Yu, Paul K L; Jin, Sungho; Wang, Deli

2014-03-14

We report an ultrathin NiOx catalyzed Si np(+) junction photoanode for a stable and efficient solar driven oxygen evolution reaction (OER) in water. A stable semi-transparent ITO/Au/ITO hole conducting oxide layer, sandwiched between the OER catalyst and the Si photoanode, is used to protect the Si from corrosion in an alkaline working environment, enhance the hole transportation, and provide a pre-activation contact to the NiOx catalyst. The NiOx catalyzed Si photoanode generates a photocurrent of 1.98 mA cm(-2) at the equilibrium water oxidation potential (EOER = 0.415 V vs. NHE in 1 M NaOH solution). A thermodynamic solar-to-oxygen conversion efficiency (SOCE) of 0.07% under 0.51-sun illumination is observed. The successful development of a low cost, highly efficient, and stable photoelectrochemical electrode based on earth abundant elements is essential for the realization of a large-scale practical solar fuel conversion.

Operando investigation of Au-MnO x thin films with improved activity for the oxygen evolution reaction

DOE PAGES

Frydendal, Rasmus; Seitz, Linsey C.; Sokaras, Dimosthenis; ...

2017-01-20

The electrochemical splitting of water holds great potential as a method for producing clean fuels by storing electricity from intermittent energy sources. The efficiency of such a process would be greatly facilitated by incorporating more active catalysts based on abundant materials for the oxygen evolution reaction. Manganese oxides are promising as catalysts for this reaction. Recent reports show that their activity can be drastically enhanced when modified with gold. Herein, we investigate highly active mixed Au-MnO x thin films for the oxygen evolution reaction, which exhibit more than five times improvement over pure MnO x. These films are characterized withmore » operando X-ray Absorption Spectroscopy, which reveal that Mn assumes a higher oxidation state under reaction conditions when Au is present. As a result, the magnitude of the enhancement is correlated to the size of the Au domains, where larger domains are the more beneficial.« less

Catalytic total hydrodeoxygenation of biomass-derived polyfunctionalized substrates to alkanes.

PubMed

Nakagawa, Yoshinao; Liu, Sibao; Tamura, Masazumi; Tomishige, Keiichi

2015-04-13

The total hydrodeoxygenation of carbohydrate-derived molecules to alkanes, a key reaction in the production of biofuel, was reviewed from the aspect of catalysis. Noble metals (or Ni) and acid are the main components of the catalysts, and group 6 or 7 metals such as Re are sometimes added as modifiers of the noble metal. The main reaction route is acid-catalyzed dehydration plus metal-catalyzed hydrogenation, and in some systems metal-catalyzed direct CO dissociation is involved. The appropriate active metal, acid strength, and reaction conditions depend strongly on the reactivity of the substrate. Reactions that use Pt or Pd catalysts supported on Nb-based acids or relatively weak acids are suitable for furanic substrates. Carbohydrates themselves and sugar alcohols undergo CC dissociation easily. The systems that use metal-catalyzed direct CO dissociations can give a higher yield of the corresponding alkane from carbohydrates and sugar alcohols. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxygen-aided synthesis of polycrystalline graphene on silicon dioxide substrates.

PubMed

Chen, Jianyi; Wen, Yugeng; Guo, Yunlong; Wu, Bin; Huang, Liping; Xue, Yunzhou; Geng, Dechao; Wang, Dong; Yu, Gui; Liu, Yunqi

2011-11-09

We report the metal-catalyst-free synthesis of high-quality polycrystalline graphene on dielectric substrates [silicon dioxide (SiO(2)) or quartz] using an oxygen-aided chemical vapor deposition (CVD) process. The growth was carried out using a CVD system at atmospheric pressure. After high-temperature activation of the growth substrates in air, high-quality polycrystalline graphene is subsequently grown on SiO(2) by utilizing the oxygen-based nucleation sites. The growth mechanism is analogous to that of growth for single-walled carbon nanotubes. Graphene-modified SiO(2) substrates can be directly used in transparent conducting films and field-effect devices. The carrier mobilities are about 531 cm(2) V(-1) s(-1) in air and 472 cm(2) V(-1) s(-1) in N(2), which are close to that of metal-catalyzed polycrystalline graphene. The method avoids the need for either a metal catalyst or a complicated and skilled postgrowth transfer process and is compatible with current silicon processing techniques.

Transition metal-modified zinc oxides for UV and visible light photocatalysis.

PubMed

Bloh, J Z; Dillert, R; Bahnemann, D W

2012-11-01

In order to use photocatalysis with solar light, finding more active and especially visible light active photocatalysts is a very important challenge. Also, studies of these photocatalysts should employ a standardized test procedure so that their results can be accurately compared and evaluated with one another. A systematic study of transition metal-modified zinc oxide was conducted to determine whether they are suitable as visible light photocatalysts. The photocatalytic activity of ZnO modified with eight different transition metals (Cu, Co, Fe, Mn, Ni, Ru, Ti, Zr) in three different concentrations (0.01, 0.1, and 1 at.%) was investigated under irradiation with UV as well as with visible light. The employed activity test is the gas-phase degradation of acetaldehyde as described by the ISO standard 22197-2. The results suggest that the UV activity can be improved with almost any modification element and that there exists an optimal modification ratio at about 0.1 at.%. Additionally, Mn- and Ru-modified ZnO display visible light activity. Especially the Ru-modified ZnO is highly active and surpasses the visible light activity of all studied titania standards. These findings suggest that modified zinc oxides may be a viable alternative to titanium dioxide-based catalysts for visible light photocatalysis. Eventually, possible underlying mechanisms are proposed and discussed.

Low platinum loading cathode modified with Cs3H2PMo10V2O40 for polymer electrolyte membrane fuel cells

NASA Astrophysics Data System (ADS)

Renzi, M.; D'Angelo, G.; Marassi, R.; Nobili, F.

2016-09-01

The catalytic activity of commercial Pt nanoparticles mixed with mesoporous polyoxometalate Cs3H2PMo10V2O40 towards oxygen reduction reaction is evaluated. The polyoxometalate co-catalyst is prepared by titration of an aqueous solution of phosphovanadomolibdic acid. SEM micrography shows reduction particle size to less than 300 nm, while XRD confirms that the resulting salt maintains the Kegging structure. The composite catalyst is prepared by mixing the POM salt with Pt/C by sonication. RRDE studies show better kinetics for ORR with low Pt loading at the electrode surface. A MEA is assembled by using a Pt/POM-based cathode, in order to assess performance in a working fuel cell. Current vs. potential curves reveals comparable or better performances at 100%, 62% and 17% relative humidity for the POM-modified MEA with respect to a commercial MEA with higher Pt loading at the cathode. Electrochemical impedance spectroscopy (EIS) confirms better kinetics at low relative humidity. Finally, an accelerated stress test (AST) with square wave (SW) between 0.4 V and 0.8 V is performed to evaluate MEA stability for at least 100 h and make predictions about lifetime, showing that after initial losses the catalytic system can retain stable performance and good morphological stability.

Oxidation of limonene using activated carbon modified in dielectric barrier discharge plasma

NASA Astrophysics Data System (ADS)

Glonek, Karolina; Wróblewska, Agnieszka; Makuch, Edyta; Ulejczyk, Bogdan; Krawczyk, Krzysztof; Wróbel, Rafał. J.; Koren, Zvi C.; Michalkiewicz, Beata

2017-10-01

The waste from industrial fruits processing is utilized for the extraction of limonene, a renewable terpene biomass compound obtained from orange peels. This was followed by limonene oxidation, which produces highly useful oxygenated derivatives (carveol, and perillyl alcohol, 1,2-epoxylimonene and its diol). New catalysts were obtained by treating relatively inexpensive commercially available EuroPh and FPV activated carbons with plasma. These catalysts were characterized by the following instrumental methods XRD, sorption of N2 and CO2, SEM, EDS, TEM, XPS, and Raman spectroscopy. The activities of the plasma-treated catalysts were measured in the oxidation of limonene by means of either hydrogen peroxide or t-butyl hydroperoxide as the oxidizing agents. During the oxidation with hydrogen peroxide the new plasma-treated catalysts were more active than their untreated counterparts. This effect was noticeable in the considerable increase in the conversion of limonene. The mechanism explaining this property is proposed, and it takes into account the role of the appropriate functional groups on the surface of the catalysts. This work has shown for the first time that the commercial EuroPh and FPV activated carbons, after having been treated by plasma, are active catalysts for the selective limonene oxidation for the production of value-added industrial products.

Catalytic pyrolysis of model compounds and waste cooking oil for production of light olefins over La/ZSM-5 catalysts

NASA Astrophysics Data System (ADS)

Li, F. W.; Ding, S. L.; Li, L.; Gao, C.; Zhong, Z.; Wang, S. X.; Li, Z. X.

2016-08-01

Waste cooking oil (WCO) and its model compounds (oleic acid and methyl laurate) are catalytically pyrolyzed in a fixed-bed reactor over La modified ZSM-5 catalysts (La/ZSM-5) aiming for production of C2-C4 light olefins. The LaO content in catalysts was set at 0, 2, 6, 10 and 14 wt%. The gas and liquid products are analyzed. The La/ZSM-5 catalyst with 6% LaO showed higher selectivity to light olefins when WCO and methyl laurate were pyrolyzed, and olefin content was 26% for WCO and 21% for methyl laurate. The catalyst with 10% LaO showed high selectivity to light olefins (28.5%) when oleic acid was pyrolyzed. The liquid products from WCO and model compounds mainly contain esters and aromatic hydrocarbons. More esters were observed in liquid products from methyl laurate and WCO pyrolysis, indicating that it is more difficult to pyrolyze esters and WCO than oleic acid. The coked catalysts were analyzed by temperature-programmed oxidation. The result shows that graphite is the main component of coke. The conversion of WCO to light olefins potentially provides an alternative and sustainable route for production of the key petrochemicals.

Ferric hydroxide supported gold subnano clusters or quantum dots: enhanced catalytic performance in chemoselective hydrogenation.

PubMed

Liu, Lequan; Qiao, Botao; Ma, Yubo; Zhang, Juan; Deng, Youquan

2008-05-21

An attempt to prepare ferric hydroxide supported Au subnano clusters via modified co-precipitation without any calcination was made. High resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) have been employed to study the structure and chemical states of these catalysts. No Au species could be observed in the HRTEM image nor from the XRD pattern, suggesting that the sizes of the Au species in and on the ferric hydroxide support were less than or around 1 nm. Chemoselective hydrogenation of aromatic nitro compounds and alpha,beta-unsaturated aldehydes was selected as a probe reaction to examine the catalytic properties of this catalyst. Under the same reaction conditions, such as 100 degrees C and 1 MPa H2 in the hydrogenation of aromatic nitro compounds, a 96-99% conversion (except for 4-nitrobenzonitrile) with 99% selectivity was obtained over the ferric hydroxide supported Au catalyst, and the TOF values were 2-6 times higher than that of the corresponding ferric oxide supported catalyst with 3-5 nm size Au particles. For further evaluation of this Au catalyst in the hydrogenation of citral and cinnamaldehyde, selectivity towards unsaturated alcohols was 2-20 times higher than that of the corresponding ferric oxide Au catalyst.

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

During this time period, at WVU, the authors have obtained models for the kinetics of the HAS (higher alcohol synthesis) reaction over the Co-K-MoS{sub 2}/C catalyst. The Rotoberty reactor was then replaced in the reactor system by a plug-flow tubular reactor. Accordingly, the authors re-started the investigations on sulfide catalysts. The authors encountered and solved the leak problem from the sampling valve for the non-sulfided reactor system. They also modified the system to eliminate the condensation problem. Accordingly, they are continuing their kinetic studies on the reduced Mo-Ni-K/C catalysts. They have set up an apparatus for temperature-programmed reduction (TPR) studies,more » and have obtained some interesting results on TPR characterizations. At UCC, the complete characterization of selected catalysts has been started. The authors sent nine selected types of ZnO, Zn/CrO and Zn/Cr/MnO catalysts and supports for BET surface area, SEM, XRD and ICP. They also sent fresh and spent samples of the Engelhard Zn/CrO catalyst impregnated with 3 wt% potassium for ISS and XPS testing. In Task 2, work on the design and optimization portion of this task, as well as on the fuel testing, is completed. All funds have been expended and there are no personnel working on this project.« less

A high yield reverse micelle synthesis of catalysts and catalyst precursors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Linehan, J.C.; Matson, D.W.; Darab, J.G.

1995-04-01

Reverse micelles or water-in-oil microemulsions have been prepared using a mixed AOT/SDS surfactant to increase the stability of the microemulsion and thereby allow a high loading of particle-forming precursors in the aqueous cores. The Modified Reverse Micelles (MRM), as these new binary surfactant microemulsions are called, have proven useful for the laboratory-scale synthesis of nanoscale metals, metal oxides, metal sulfides, and mixed metal materials. The system allows control over the phase and size of the precipitated crystallites and is ideal for producing nanocrystalline powders and suspensions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tao, Franklin

Two main categories of heterogeneous catalysts are metal and metal oxide which catalyze 80% chemical reactions at solid-gas and solid-liquid interfaces. Metal oxide catalysts are much more complicated than metal catalysts. The reason is that the cations of the metal atoms could exhibit a few different oxidation states on surface of the same catalyst particle such as Co 3O 4 or change of their oxidation states under different reactive environments. For a metal catalyst, there is only one oxidation state typically. In addition, surface of a metal oxide can be terminated with multiple surface functionalities including O atoms with differentmore » binding configurations and OH group. For metal, only metal atoms are exposed typically. Obviously, the complication of surface chemistry and structure of a metal oxide makes studies of surface of an oxide catalyst very challenging. Due to the complication of surface of a meal oxide, the electronic and geometric structures of surface of a metal oxide and the exposed species have received enormous attention since oxide catalysts catalyze at least 1/3 chemical reactions in chemical and energy industries. Understanding of catalytic reactions on early transition metal oxide-based catalysts is fundamentally intriguing and of great practical interest in energy- and environment-related catalysis. Exploration of surface chemistry of oxide-based catalysts at molecular level during catalysis has remained challenging though it is critical in deeply understanding catalysis on oxide-based catalysts and developing oxide-based catalysts with high activity and selectivity. Thus, the overall objective of this project is to explore surface chemistry and structure of early transition metal oxide-based catalysts through in-situ characterization of surface of catalysts, measurements of catalytic performances, and then build an intrinsic correlation of surface chemistry and structure with their catalytic performances in a few important catalytic reactions, and essentially fundamentally understand catalytic mechanism. Furthermore, this correlation will guide the design of catalysts with high activity and selectivity.« less

Synthesis of block copolymers consists on vinylidene chloride and α- Methylstyrene by cationic polymerization using an acid exchanged motmorillonite clay as heterogeneous catalyst (Algerian MMT)

NASA Astrophysics Data System (ADS)

Ayat, Moulkheir; Belbachir, Mohamed; Rahmouni, Abdelkader

2017-07-01

The aim of this study was to develop the efficient and versatile method for the synthesis of block copolymers consists by cationic polymerization vinylidene chloride (VDC) and alpha-methylstyrene (alpha-MS) in the presence of a natural Algerian montmorillonite clay modified by 0.05-0.35 M H2SO4 (Algerian MMT-H+). It was found that H2SO4 concentration allows controlling the chemical composition, the porous structure of the acid-activated clays and their catalytic performance. The maximal yield of polymer is observed in the presence of Algerian MMT modified by 0.25 M H2SO4. Effects of VDC/MS molar ration, catalyst concentration, reaction time, reaction temperature and polarity medium on yield and molecular weight of polymer were revealed in the presence of the most active sample.

Catalytic conversion of syngas to mixed alcohols over Zn-Mn promoted Cu-Fe based catalyst

DOE PAGES

Lu, Yongwu; Yu, Fei; Hu, Jin; ...

2012-04-12

Zn-Mn promoted Cu-Fe based catalyst was synthesized by the co-precipitation method. Mixed alcohols synthesis from syngas was studied in a half-inch tubular reactor system after the catalyst was reduced. Zn-Mn promoted Cu-Fe based catalyst was characterized by SEM-EDS, TEM, XRD, and XPS. The liquid phase products (alcohol phase and hydrocarbon phase) were analyzed by GC-MS and the gas phase products were analyzed by GC. The results showed that Zn-Mn promoted Cu-Fe based catalyst had high catalytic activity and high alcohol selectivity. The maximal CO conversion rate was 72%, and the yield of alcohol and hydrocarbons were also very high. Cumore » (111) was the active site for mixed alcohols synthesis, Fe 2C (101) was the active site for olefin and paraffin synthesis. The reaction mechanism of mixed alcohols synthesis from syngas over Zn-Mn promoted Cu-Fe based catalyst was proposed. Here, Zn-Mn promoted Cu-Fe based catalyst can be regarded as a potential candidate for catalytic conversion of biomass-derived syngas to mixed alcohols.« less

Mechanism of H adatoms improving the O2 reduction reaction on the Zn-modified anatase TiO2 (101) surface studied by first principles calculation.

PubMed

Liu, Liangliang; Li, Chongyang; Jiang, Man; Li, Xiaodong; Huang, Xiaowei; Wang, Zhu; Jia, Yu

2018-06-05

First principles calculations were performed to cast insight into the mechanism of the improvement of O2 reduction reaction (ORR) activity by Zn and H interstitials on the anatase TiO2 (101) surface. For the Zn-modified anatase TiO2 (101) surface, both surface and subsurface Zn interstitials could contribute to O2 adsorption and dissociation, but the dissociation barriers of O2 molecules are still too high, which limits the ORR activity. After a H adatom is introduced onto the Zn-modified anatase TiO2 (101) surface, the highest energy barriers are greatly reduced compared with those of the Zn-modified surface. Meanwhile, it is observed that the dissociation barriers decrease almost linearly with the increase of the charge difference of adsorption O2 between initial and transition state configurations. Specifically, subsurface Zn and surface H interstitials facilitate O2 dissociation and subsequent oxidation reactions, and further frequency analysis shows that these dissociation processes are frequent even at the room temperature of 300 K. In a word, this work provides a theoretical support to design a high ORR activity catalyst of the TiO2 nanocrystal comparable to precious Pt catalysts.

Electrocatalysts for carbon dioxide conversion

DOEpatents

Masel, Richard I; Salehi-Khojin, Amin

2015-04-21

Electrocatalysts for carbon dioxide conversion include at least one catalytically active element with a particle size above 0.6 nm. The electrocatalysts can also include a Helper Catalyst. The catalysts can be used to increase the rate, modify the selectivity or lower the overpotential of electrochemical conversion of CO.sub.2. Chemical processes and devices using the catalysts also include processes to produce CO, HCO.sup.-, H.sub.2CO, (HCO.sub.2).sup.-, H.sub.2CO.sub.2, CH.sub.3OH, CH.sub.4, C.sub.2H.sub.4, CH.sub.3CH.sub.2OH, CH.sub.3COO.sup.-, CH.sub.3COOH, C.sub.2H.sub.6, (COOH).sub.2, or (COO.sup.-).sub.2, and a specific device, namely, a CO.sub.2 sensor.

Production of monosaccharides and bio-active compounds derived from marine polysaccharides using subcritical water hydrolysis.

PubMed

Meillisa, Aviannie; Woo, Hee-Chul; Chun, Byung-Soo

2015-03-15

Polysaccharides are the major components of brown seaweed, accounting for approximately 40-65% of the total mass. The majority of the brown seaweed polysaccharides consists of alginate (40% of dry matter), a linear hetero-polysaccharides commonly developed in fields. However, depolymerisation of alginate is required to recover high-value compounds. In this report, depolymerisation was performed using subcritical water hydrolysis (SWH) at 180-260°C, with a ratio of material to water of 1:25 (w/v) and 1% formic acid as a catalyst. Sugar recovery was higher at low temperatures in the presence of catalyst. The antioxidant properties of Saccharina japonica showed the best activity at 180°C in the presence of a catalyst. The mass spectra produced using MALDI-TOF showed that polysaccharides and oligosaccharides were produced during hydrothermal treatment. Hydrolysis treatment at 180°C in the presence of a catalyst may be useful for modifying the structure of S. japonica and purified alginate. Copyright © 2014 Elsevier Ltd. All rights reserved.

Preparation of Fe3O4/SiO2-guanidine organobase catalyst for 1,5-diphenylpenta-2,4-dien-1-one synthesis

NASA Astrophysics Data System (ADS)

Cahyana, A. H.; Fitria, D.; Ardiansah, B.; Rahayu, D. U. C.

2017-04-01

A novel heterogeneous organobase catalyst of Fe3O4/SiO2-guanidine was prepared in three stages. First, Fe3O4 nanoparticle was obtained by co-precipitation method using seaweed Sargassum Sp. as natural reductant. Fe3O4 was then coated by SiO2 using TEOS as silica source, resulting Fe3O4/SiO2. Finally, Fe3O4/SiO2-Guanidine was obtained by modifying Fe3O4/SiO2 with guanidine in the suitable reaction condition. This organobase catalyst was characterized by Scanning Electron Microscope (SEM), Energy Dispersive X-ray Spectroscopy (EDS), and Particle Size Analyzer (PSA). The material was then used as a highly active catalyst in aldol condensation reaction between acetophenone and cinnamaldehyde to produce 1,5-diphenylpenta-2,4-dien-1-one. The structure elucidation of the organic product was confirmed by UV-Vis, FTIR, and LC-MS.

Hexagonal mesoporous silica modified with copper phthalocyanine as a photocatalyst for pesticide 2,4-dichlorophenoxiacetic acid degradation.

PubMed

DeOliveira, Edimar; Neri, Cláudio R; Ribeiro, Anderson O; Garcia, Vinícius S; Costa, Leonardo L; Moura, Aline O; Prado, Alexandre G S; Serra, Osvaldo A; Iamamoto, Yassuko

2008-07-01

A new mesoporous catalyst was prepared by the reaction between 3-aminopropyltrimethoxisylane and Cu(II)-hexadecafluorophthalocyanine, followed by co-condensation of tetraethylorthosilicate around a micelle formed by n-dodecylamine. The surfactant was removed from the pores by continuous extraction with ethanol, giving the Si-CuF16Pc catalyst. This catalyst was characterized by SEM, FTIR, TGA, 29Si NMR, N2 adsorption and X-ray diffraction. SEM images confirmed that the catalyst material is formed by nanoaggregates with a diameter of 100 nm. N2 adsorption isotherms showed that Si-CuF16Pc has a surface area of approximately 200 m2 g(-1) and a porous diameter of 7.7 nm, characterizing the mesoporosity of this product. This novel material shows an excellent photocatalytic activity, degrading almost 90% of 2,4-dichlorophenoxyacetic acid (2,4-D) up to 30 min, while only approximately 40% of photodegradation was obtained in its absence.

Stability of High-Performance Pt-Based Catalysts for Oxygen Reduction Reactions.

PubMed

Lin, Rui; Cai, Xin; Zeng, Hao; Yu, Zhuoping

2018-04-01

Due to their environmental sustainability and high efficiency, proton-exchange-membrane fuel cells (PEMFCs) are expected to be an essential type of energy source for electric vehicles, energy generation, and the space industry in the coming decades. Here, the recent developments regarding shape-controlled nanostructure catalysts are reviewed, with a focus on the stability of high-performance Pt-based catalysts and related mechanisms. The catalysts, which possess great activity, are still far from meeting the requirements of their applications, due to stability issues, especially in membrane electrode assemblies (MEAs). Thus, solutions toward the comprehensive performance of Pt-based catalysts are discussed here. The research trends and related theories that can promote the application of Pt-based catalysts are also provided. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design, Synthesis and Mechanistic Evaluation of Iron-Based Catalysis for Synthesis Gas Conversion to Fuels and Chemicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Akio Ishikawa; Manuel Ojeda; Nan Yao

2007-03-31

This project extends previously discovered Fe-based catalysts to hydrogen-poor synthesis gas streams derived from coal and biomass sources. These catalysts have shown unprecedented Fischer-Tropsch synthesis rates and selectivities for synthesis gas derived from methane. During the first reporting period, we certified a microreactor, installed required analytical equipment, and reproduced synthetic protocols and catalytic results previously reported. During the second reporting period, we prepared several Fe-based compositions for Fischer-Tropsch Synthesis and tested the effects of product recycle under both subcritical and supercritical conditions. During the third and fourth reporting periods, we improved the catalysts preparation method, which led to Fe-based materialsmore » with the highest FTS reaction rates and selectivities so far reported, a finding that allowed their operation at lower temperatures and pressures with high selectivity to desired products (C{sub 5+}, olefins). During the fifth and sixth reporting period, we studied the effects of different promoters on catalytic performance, specifically how their sequence of addition dramatically influenced the performance of these materials in the Fischer-Tropsch synthesis. We also continued our studies of the kinetic behavior of these materials during the sixth reporting period. Specifically, the effects of H{sub 2}, CO, and CO{sub 2} on the rates and selectivities of Fischer-Tropsch Synthesis reactions led us to propose a new sequence of elementary steps on Fe and Co Fischer-Tropsch catalysts. Finally, we also started a study of the use of colloidal precipitation methods for the synthesis small Co clusters using recently developed methods to explore possible further improvements in FTS rates and selectivities. We found that colloidal synthesis makes possible the preparation of small cobalt particles, although large amount of cobalt silicate species, which are difficult to reduce, were formed. During this seventh reporting period, we have explored several methods to modify the silanol groups on SiO{sub 2} by using either a homogeneous deposition-precipitation method or surface titration of Si-OH on SiO{sub 2} with zirconium (IV) ethoxide to prevent the formation of unreducible and unreactive CoO{sub x} species during synthesis and FTS catalysis. We have synthesized monometallic Co/ZrO{sub 2}/SiO{sub 2} catalysts with different Co loadings (11-20 wt%) by incipient wetness impregnation methods and characterized the prepared Co supported catalysts by H{sub 2} temperature-programmed reduction (H{sub 2}-TPR) and H{sub 2}-chemisorption. We have measured the catalytic performance in FTS reactions and shown that although the hydroxyl groups on the SiO{sub 2} surface are difficult to be fully titrated by ZrO{sub 2}, modification of ZrO{sub 2} on SiO{sub 2} surface can improve the Co clusters dispersion and lead to a larger number of exposed Co surface atoms after reduction and during FTS reactions. During this seventh reporting period, we have also advanced our development of the reaction mechanism proposed in the previous reporting period. Specifically, we have shown that our novel proposal for the pathways involved in CO activation on Fe and Co catalysts is consistent with state-of-the-art theoretical calculations carried out in collaboration with Prof. Manos Mavrikakis (University of Wisconsin-Madison). Finally, we have also worked on the preparation of several manuscripts describing our findings about the preparation, activation and mechanism of the FTS with Fe-based catalysts and we have started redacting the final report for this project.« less

Visible light assisted photodecolorization of eosin-Y in aqueous solution using hesperidin modified TiO2 nanoparticles

NASA Astrophysics Data System (ADS)

Vignesh, K.; Suganthi, A.; Rajarajan, M.; Sakthivadivel, R.

2012-03-01

Hesperidin a flavanoid, modified TiO2 nanoparticles (Hes-TiO2) was synthesized to improve the visible light driven photocatalytic performance of TiO2. The synthesized nanoparticles were characterized by UV-visible diffuse reflectance spectroscopy (UV-vis-DRS), FT-IR, powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). The photocatalytic activity of Hes-TiO2 was investigated based on the decolorization of eosin-Y under visible light irradiation. Hes-TiO2 showed high efficiency for the decolorization of eosin-Y. The influences of various reaction parameters like effect of pH, catalyst dosage and initial dye concentration on the photocatalytic efficiency were investigated. The adsorption of eosin-Y on Hes-TiO2 was found favorable by the Langmuir approach. The removal percentage of chemical oxygen demand (COD) was determined to evaluate the mineralization of eosin-Y during photodecolorization. Based on the intermediates obtained in the GC-MS spectroscopic technique, a probable degradation mechanism has been proposed.

Extrusion-mixing compared with hand-mixing of polyether impression materials?

PubMed

McMahon, Caroline; Kinsella, Daniel; Fleming, Garry J P

2010-12-01

The hypotheses tested were two-fold (a) whether altering the base:catalyst ratio influences working time, elastic recovery and strain in compression properties of a hand-mixed polyether impression material and (b) whether an extrusion-mixed polyether impression material would have a significant advantage over a hand-mixed polyether impression material mixed to the optimum base:catalyst ratio. The polyether was hand-mixed at the optimum (manufacturers recommended) base:catalyst ratios (7:1) and further groups were made by increasing or decreasing the catalyst length by 25%. Additionally specimens were also made from an extrusion-mixed polyether impression material and compared with the optimum hand-mixed base:catalyst ratio. A penetrometer assembly was used to measure the working time (n=5). Five cylindrical specimens for each hand-mixed and extrusion mixed group investigated were employed for elastic recovery and strain in compression testing. Hand-mixing polyether impression materials with 25% more catalyst than that recommended significantly decreased the working time while hand-mixing with 25% less catalyst than that recommended significantly increased the strain in compression. The extrusion-mixed polyether impression material provided similar working time, elastic recovery and strain in compression to the hand-mixed polyether mixed at the optimum base:catalyst ratio.

Reformer Fuel Injector

NASA Technical Reports Server (NTRS)

Suder, Jennifer L.

2004-01-01

Today's form of jet engine power comes from what is called a gas turbine engine. This engine is on average 14% efficient and emits great quantities of green house gas carbon dioxide and air pollutants, Le. nitrogen oxides and sulfur oxides. The alternate method being researched involves a reformer and a solid oxide fuel cell (SOFC). Reformers are becoming a popular area of research within the industry scale. NASA Glenn Research Center's approach is based on modifying the large aspects of industry reforming processes into a smaller jet fuel reformer. This process must not only be scaled down in size, but also decrease in weight and increase in efficiency. In comparison to today's method, the Jet A fuel reformer will be more efficient as well as reduce the amount of air pollutants discharged. The intent is to develop a 10kW process that can be used to satisfy the needs of commercial jet engines. Presently, commercial jets use Jet-A fuel, which is a kerosene based hydrocarbon fuel. Hydrocarbon fuels cannot be directly fed into a SOFC for the reason that the high temperature causes it to decompose into solid carbon and Hz. A reforming process converts fuel into hydrogen and supplies it to a fuel cell for power, as well as eliminating sulfur compounds. The SOFC produces electricity by converting H2 and CO2. The reformer contains a catalyst which is used to speed up the reaction rate and overall conversion. An outside company will perform a catalyst screening with our baseline Jet-A fuel to determine the most durable catalyst for this application. Our project team is focusing on the overall research of the reforming process. Eventually we will do a component evaluation on the different reformer designs and catalysts. The current status of the project is the completion of buildup in the test rig and check outs on all equipment and electronic signals to our data system. The objective is to test various reformer designs and catalysts in our test rig to determine the most efficient configuration to incorporate into the specific compact jet he1 reformer test rig. Additional information is included in the original extended abstract.

Influence of reaction condition on viscosity of polyurethane modified epoxy based on glycerol monooleate

NASA Astrophysics Data System (ADS)

Triwulandari, Evi; Ramadhan, Mohammad Kemilau; Ghozali, Muhammad

2017-01-01

Polyurethane modified epoxy based on glycerol monooleate (PME-GMO) was synthesized. GMO as polyol for synthesis of PME-GMO was synthesized via Fisher Esterification between oleic acid from palm oil and glycerol by using sulfuric acid as catalyst with time variation i.e. 3, 4, 5 and 6 hours at 160°C. Characterizations of GMO were carried out by analysis of acid number, hydroxyl value and FTIR. The data show that the conversion of oleic acid to ester compound is directly proportional with the increasing of reaction time but the enhancement is not significant after 3 hours. Furthermore, GMO product was used as polyol for modification of epoxy with polyurethane. Modification of epoxy with polyurethane was performed by reacted epoxy, tolonate and GMO simultaneously in one step. In this research, the reaction condition was varied i.e. time reaction (0.5; 1; 1.5; 2; 2.5 hours), composition of polyurethane used (10%, 20% toward epoxy) and rasio of tolonate and GMO (NCO/OH ratio) as component of polyurethane (1.5 and 2.5). Characterization of polyurethane modified epoxy based on glycerol (PME-GMO) was conducted by viscosity and FTIR analysis. The viscosity of PME-GMO increased with increasing of reaction time, polyurethane composition and NCO/OH ratio.

Non-platinum metal-organic framework based electro-catalyst for promoting oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Das, Dipanwita; Raut, Vrushali; Kireeti, Kota V. M. K.; Jha, Neetu

2018-04-01

We developed two non-precious Metal Organic Framework (MOF) based electrocatalysts, MOF-5 and MOF-i using solvothermal and refluxing methods. The MOFs prepared has been characterized by powder X-ray diffractometer (XRD), Fourier Transform Infra-Red Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM) for structural and morphological insights. SEM images reveal cubic shape for solvothermally synthesized MOF-5, whereas refluxing method leads to platelet morphology of MOF-i. The synthesized MOFs has been investigated for Oxygen Reduction Reaction (ORR) studies using Cyclic Voltammetry (CV) and Linear Sweep Voltammetry (LSV), with MOF modified Glassy Carbon (GC) as working electrode. The electrochemical data suggests higher activity of MOF-5 towards ORR compared to MOF-i.

Catalyst and process development for synthesis gas conversion to isobutylene. Final report, September 1, 1990--January 31, 1994

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anthony, R.G.; Akgerman, A.

1994-05-06

Previous work on isosynthesis (conversion of synthesis gas to isobutane and isobutylene) was performed at very low conversions or extreme process conditions. The objectives of this research were (1) determine the optimum process conditions for isosynthesis; (2) determine the optimum catalyst preparation method and catalyst composition/properties for isosynthesis; (3) determine the kinetics for the best catalyst; (4) develop reactor models for trickle bed, slurry, and fixed bed reactors; and (5) simulate the performance of fixed bed trickle flow reactors, slurry flow reactors, and fixed bed gas phase reactors for isosynthesis. More improvement in catalyst activity and selectivity is needed beforemore » isosynthesis can become a commercially feasible (stand-alone) process. Catalysts prepared by the precipitation method show the most promise for future development as compared with those prepared hydrothermally, by calcining zirconyl nitrate, or by a modified sol-gel method. For current catalysts the high temperatures (>673 K) required for activity also cause the production of methane (because of thermodynamics). A catalyst with higher activity at lower temperatures would magnify the unique selectivity of zirconia for isobutylene. Perhaps with a more active catalyst and acidification, oxygenate production could be limited at lower temperatures. Pressures above 50 atm cause an undesirable shift in product distribution toward heavier hydrocarbons. A model was developed that can predict carbon monoxide conversion an product distribution. The rate equation for carbon monoxide conversion contains only a rate constant and an adsorption equilibrium constant. The product distribution was predicted using a simple ratio of the rate of CO conversion. This report is divided into Introduction, Experimental, and Results and Discussion sections.« less

Kinetic study on the catalytic performance of Rh/TiO/sub 2/ reduced at different temperatures in the CO-H/sub 2/ reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fujitsu, H.; Ikeyama, N.; Mochida, I.

1986-08-01

Catalytic CO-H/sub 2/ reaction on Rh/TiO/sub 2/ reduced at 200, 400, and 500/sup 0/C (Cat-200, -400, -500) for 2 h was kinetically studied at 250/sup 0/C using a circulating reactor and Fourier transform-infrared (FT-IR) spectroscopy to determine how Cat-400 exhibited the highest activity. The rate equation distinguished the best catalyst with zero and first orders in CO and H/sub 2/, respectively, from other catalysts with negative order in CO. The adsorption ability of the catalyst at 200/sup 0/C was comparable to that of Cat-200, and two to three times larger than that of Cat-500, although the ability of Cat-200 wasmore » much larger at room temperature. Carbon monoxide adsorbed on the catalysts reversibly as well as irreversibly. IR spectroscopy revealed that the major form of irreversibly adsorbed CO was linear on Cat-200, whereas similar amounts of linear and bridge forms were observed on Cat-400 and Cat-500. These latter forms were highly reactive against hydrogen molecules when no carbon monoxide was present in the gas phase. Based on these results, the highest activity of Cat-400 is ascribed to rhodium metal modified by properly reduced TiO/sub 2/ to show the appropriate adsorption ability of carbon monoxide which least retards the activation of hydrogen according to first-order kinetics. Typical strong metal-support interaction decreases the catalytic activity by decreasing the active sites and strengthening the CO adsorption too much.« less

Improvement of thermal and mechanical properties of composite based on polylactic acid and microfibrillated cellulose through chemical modification

NASA Astrophysics Data System (ADS)

Suryanegara, L.; Nugraha, R. A.; Achmadi, S. S.

2017-07-01

Polylactic acid (PLA) is the most representative sustainable and bio-based polymer environmentally friendly that has a great potential to replace petroleum-based plastics. However, brittleness, low heat resistance, and slow crystallization limit the wide application of PLA. One of strategies to improve PLA properties is by reinforcing with microfibrillated cellulose (MFC). Unfortunately, the hydrophilic properties of MFC make it difficult to attain good dispersion in a hydrophobic PLA matrix. Therefore, modification of MFC was needed to increase its compatibility with PLA in the composite formation. In this experiment, MFC was modified with partial acetylation (degree of substitution: 1) and further grafted with lactide monomers through ring-opening polymerization using Sn(Oct)2 catalyst. The result of acetylation and grafting were verified by infrared spectra. Composites were prepared by mixing PLA (molecular weight of 200,000) and the modified MFC at 9:1 ratio through organic solvent method. Followed by 8 min-kneading and hot pressing at 180°C, the resulted composites were evaluated for their mechanical and thermal properties. Thermal characterization carried out using differential scanning calorimetry measurements showed that the presence of modified MFC increased the temperature of glass transition and accelerated the crystallization of PLA. Mechanical properties measurement showed that the presence of modified MFC enhanced the elongation at break (1.1 to 1.8%), tensile strength (14.9 to 25.7 MPa), and modulus of elasticity (1.7 to 2.1 GPa). These results demonstrated that the modified MFC could extend the application of PLA in industry.

Modification of molybdenum disulfide in methanol solvent for hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Niyitanga, Theophile; Jeong, Hae Kyung

2018-05-01

Molybdenum disulfide is a promising catalyst to replace the expensive platinum as an electrocatalyst but needs to be modified to present excellent electrocatalytic properties. Herein, we successfully modify molybdenum disulfide in methanol solvent for hydrogen evolution reaction by using a simple hydrothermal method. Overpotential reduced to -0.6 V from -1.5 V, and energy band gap decreased from 1.73 eV to 1.58 eV after the modification. The modified molybdenum disulfide also demonstrated lower resistance (42 Ω) at high frequency (1000 kHz) compared with that (240 Ω) of the precursor, showing that conductivity of the modified molybdenum disulfide has improved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yung, Matthew M.; Stanton, Alexander R.; Iisa, Kristiina

Metal-impregnated (Ni or Ga) ZSM-5 catalysts were studied for biomass pyrolysis vapor upgrading to produce hydrocarbons using three reactors constituting a 100 000x change in the amount of catalyst used in experiments. Catalysts were screened for pyrolysis vapor phase upgrading activity in two small-scale reactors: (i) a Pyroprobe with a 10 mg catalyst in a fixed bed and (ii) a fixed-bed reactor with 500 mg of catalyst. The best performing catalysts were then validated with a larger scale fluidized-bed reactor (using ~1 kg of catalyst) that produced measurable quantities of bio-oil for analysis and evaluation of mass balances. Despite somemore » inherent differences across the reactor systems (such as residence time, reactor type, analytical techniques, mode of catalyst and biomass feed) there was good agreement of reaction results for production of aromatic hydrocarbons, light gases, and coke deposition. Relative to ZSM-5, Ni or Ga addition to ZSM-5 increased production of fully deoxygenated aromatic hydrocarbons and light gases. In the fluidized bed reactor, Ga/ZSM-5 slightly enhanced carbon efficiency to condensed oil, which includes oxygenates in addition to aromatic hydrocarbons, and reduced oil oxygen content compared to ZSM-5. Ni/ZSM-5, while giving the highest yield of fully deoxygenated aromatic hydrocarbons, gave lower overall carbon efficiency to oil but with the lowest oxygen content. Reaction product analysis coupled with fresh and spent catalyst characterization indicated that the improved performance of Ni/ZSM-5 is related to decreasing deactivation by coking, which keeps the active acid sites accessible for the deoxygenation and aromatization reactions that produce fully deoxygenated aromatic hydrocarbons. The addition of Ga enhances the dehydrogenation activity of the catalyst, which leads to enhanced olefin formation and higher fully deoxygenated aromatic hydrocarbon yields compared to unmodified ZSM-5. Catalyst characterization by ammonia temperature programmed desorption, surface area measurements, and postreaction temperature-programmed oxidation (TPO) also showed that the metal-modified zeolites retained a greater percentage of their initial acidity and surface area, which was consistent between the reactor scales. These results demonstrate that the trends observed with smaller (milligram to gram) catalyst reactors are applicable to larger, more industrially relevant (kg) scales to help guide catalyst research toward application.« less

Functionalized MIL-101 with imidazolium-based ionic liquids for the cycloaddition of CO2 and epoxides under mild condition

NASA Astrophysics Data System (ADS)

Liu, Dan; Li, Gang; Liu, Haiou

2018-01-01

A kind of multi-functional sites metal-organic framework (MOF) composite (MIL-101-IMBr) was successfully prepared by post-synthesis modification of MIL-101 with imidazolium-based ionic liquids. The ionic liquids not only functionalize as basic sites but also provide halide anions, which serve as a nucleophile in cycloaddition reaction. The prepared functional MOF materials were characterized by X-ray diffraction, fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, N2 adsorption-desorption and CO2 temperature programmed desorption. The results of fourier transform infrared spectroscopy and energy dispersive spectroscopy show that the MIL-101-IMBr composite was successfully synthesized. The N2 adsorption-desorption results clearly demonstrated that the modified composites still preserve high BET surface area and total pore volume. The composite exhibits high catalytic activity for the cycloaddition of CO2 with epoxides under mild and co-catalyst free conditions. The conversion of propylene oxide was 95.8% and the selectivity of cyclic carbonate was 97.6% under 0.8 MPa at 80 °C for 4 h. Moreover, the catalyst can be used for at least five times.

Active site formation mechanism of carbon-based oxygen reduction catalysts derived from a hyperbranched iron phthalocyanine polymer.

PubMed

Hiraike, Yusuke; Saito, Makoto; Niwa, Hideharu; Kobayashi, Masaki; Harada, Yoshihisa; Oshima, Masaharu; Kim, Jaehong; Nabae, Yuta; Kakimoto, Masa-Aki

2015-01-01

Carbon-based cathode catalysts derived from a hyperbranched iron phthalocyanine polymer (HB-FePc) were characterized, and their active-site formation mechanism was studied by synchrotron-based spectroscopy. The properties of the HB-FePc catalyst are compared with those of a catalyst with high oxygen reduction reaction (ORR) activity synthesized from a mixture of iron phthalocyanine and phenolic resin (FePc/PhRs). Electrochemical measurements demonstrate that the HB-FePc catalyst does not lose its ORR activity up to 900°C, whereas that of the FePc/PhRs catalyst decreases above 700°C. Hard X-ray photoemission spectra reveal that the HB-FePc catalysts retain more nitrogen components than the FePc/PhRs catalysts between pyrolysis temperatures of 600°C and 800°C. This is because the linked structure of the HB-FePc precursor has high thermostability against nitrogen desorption. Consequently, effective doping of active nitrogen species into the sp (2) carbon network of the HB-FePc catalysts may occur up to 900°C.

Hierarchical Mesoporous NiO/MnO2@PANI Core-Shell Microspheres, Highly Efficient and Stable Bifunctional Electrocatalysts for Oxygen Evolution and Reduction Reactions.

PubMed

He, Junkai; Wang, Mingchao; Wang, Wenbo; Miao, Ran; Zhong, Wei; Chen, Sheng-Yu; Poges, Shannon; Jafari, Tahereh; Song, Wenqiao; Liu, Jiachen; Suib, Steven L

2017-12-13

We report on the new facile synthesis of mesoporous NiO/MnO 2 in one step by modifying inverse micelle templated UCT (University of Connecticut) methods. The catalyst shows excellent electrocatalytic activity and stability for both the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR) in alkaline media after further coating with polyaniline (PANI). For electrochemical performance, the optimized catalyst exhibits a potential gap, ΔE, of 0.75 V to achieve a current of 10 mA cm -2 for the OER and -3 mA cm -2 for the ORR in 0.1 M KOH solution. Extensive characterization methods were applied to investigate the structure-property of the catalyst for correlations with activity (e.g., XRD, BET, SEM, HRTEM, FIB-TEM, XPS, TGA, and Raman). The high electrocatalytic activity of the catalyst closely relates to the good electrical conductivity of PANI, accessible mesoporous structure, high surface area, as well as the synergistic effect of the specific core-shell structure. This work opens a new avenue for the rational design of core-shell structure catalysts for energy conversion and storage applications.

Modified Ni-Cu catalysts for ethanol steam reforming

NASA Astrophysics Data System (ADS)

Dan, M.; Mihet, M.; Almasan, V.; Borodi, G.; Katona, G.; Muresan, L.; Lazar, M. D.

2013-11-01

Three Ni-Cu catalysts, having different Cu content, supported on γ-alumina were synthesized by wet co-impregnation method, characterized and tested in the ethanol steam reforming (ESR) reaction. The catalysts were characterized for determination of: total surface area and porosity (N2 adsorption - desorption using BET and Dollimer Heal methods), Ni surface area (hydrogen chemisorption), crystallinity and Ni crystallites size (X-Ray Diffraction), type of catalytic active centers (Hydrogen Temperature Programmed Reduction). Total surface area and Ni crystallites size are not significantly influenced by the addition of Cu, while Ni surface area is drastically diminished by increasing of Cu concentration. Steam reforming experiments were performed at atmospheric pressure, temperature range 150-350°C, and ethanol - water molar ration of 1 at 30, using Ar as carrier gas. Ethanol conversion and hydrogen production increase by the addition of Cu. At 350°C there is a direct connection between hydrogen production and Cu concentration. Catalysts deactivation in 24h time on stream was studied by Transmission Electron Microscopy (TEM) and temperature-programmed reduction (TPR) on used catalysts. Coke deposition was observed at all studied temperatures; at 150°C amorphous carbon was evidenced, while at 350°C crystalline, filamentous carbon is formed.

Methane Upgrading of Acetic Acid as a Model Compound for a Biomass-Derived Liquid over a Modified Zeolite Catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Aiguo; Austin, Danielle; Karmakar, Abhoy

The technical feasibility of coaromatization of acetic acid derived from biomass and methane was investigated under mild reaction conditions (400 °C and 30 bar) over silver-, zinc-, and/or gallium-modified zeolite catalysts. On the basis of GC-MS, Micro-GC, and TGA analysis, more light aromatic hydrocarbons, less phenol formation, lower coke production, and higher methane conversion are observed over 5%Zn-1%Ga/ZSM-5 catalyst in comparison with catalytic performance over the other catalysts. Direct evidence of methane incorporation into aromatics over 5%Zn-1%Ga/ZSM-5 catalyst is witnessed in 1H, 2H, and 13C NMR spectra, revealing that the carbon from methane prefers to occupy the phenyl carbon sitesmore » and the benzylic carbon sites, and the hydrogen of methane favors the aromatic and benzylic substitutions of product molecules. In combination with the 13C NMR results for isotopically labeled acetic acid ( 13CH 3COOH and CH 3 13COOH), it can be seen that the methyl and carbonyl carbons of acetic acid are equally involved in the formation of ortho, meta and para carbons of the aromatics, whereas the phenyl carbons directly bonded with alkyl substituent groups and benzylic carbons are derived mainly from the carboxyl carbon of acetic acid. After various catalyst characterizations by using TEM, XRD, DRIFT, NH 3-TPD, and XPS, the excellent catalytic performance might be closely related to the highly dispersed zinc and gallium species on the zeolite support, moderate surface acidity, and an appropriate ratio of weak acidic sites to strong acidic sites as well as the fairly stable oxidation state during acetic acid conversion under a methane environment. Two mechanisms of the coaromatization of acetic acid and methane have also been proposed after consulting all the collected data in this study. In conclusion, the results reported in this paper could potentially lead to more cost-effective utilization of abundant natural gas and biomass.« less

Methane Upgrading of Acetic Acid as a Model Compound for a Biomass-Derived Liquid over a Modified Zeolite Catalyst

DOE PAGES

Wang, Aiguo; Austin, Danielle; Karmakar, Abhoy; ...

2017-04-19

The technical feasibility of coaromatization of acetic acid derived from biomass and methane was investigated under mild reaction conditions (400 °C and 30 bar) over silver-, zinc-, and/or gallium-modified zeolite catalysts. On the basis of GC-MS, Micro-GC, and TGA analysis, more light aromatic hydrocarbons, less phenol formation, lower coke production, and higher methane conversion are observed over 5%Zn-1%Ga/ZSM-5 catalyst in comparison with catalytic performance over the other catalysts. Direct evidence of methane incorporation into aromatics over 5%Zn-1%Ga/ZSM-5 catalyst is witnessed in 1H, 2H, and 13C NMR spectra, revealing that the carbon from methane prefers to occupy the phenyl carbon sitesmore » and the benzylic carbon sites, and the hydrogen of methane favors the aromatic and benzylic substitutions of product molecules. In combination with the 13C NMR results for isotopically labeled acetic acid ( 13CH 3COOH and CH 3 13COOH), it can be seen that the methyl and carbonyl carbons of acetic acid are equally involved in the formation of ortho, meta and para carbons of the aromatics, whereas the phenyl carbons directly bonded with alkyl substituent groups and benzylic carbons are derived mainly from the carboxyl carbon of acetic acid. After various catalyst characterizations by using TEM, XRD, DRIFT, NH 3-TPD, and XPS, the excellent catalytic performance might be closely related to the highly dispersed zinc and gallium species on the zeolite support, moderate surface acidity, and an appropriate ratio of weak acidic sites to strong acidic sites as well as the fairly stable oxidation state during acetic acid conversion under a methane environment. Two mechanisms of the coaromatization of acetic acid and methane have also been proposed after consulting all the collected data in this study. In conclusion, the results reported in this paper could potentially lead to more cost-effective utilization of abundant natural gas and biomass.« less

The novel synthesis of magnetically chitosan/carbon nanotube composites and their catalytic applications.

PubMed

Zarnegar, Zohre; Safari, Javad

2015-04-01

Chitosan-modified magnetic carbon nanotubes (CS-MCNTs) were synthesized and were investigated by FT-IR, EDX, FE-SEM, elemental analysis, XRD, VSM and TGA. In order to synthesize the CS-MCNTs composites, Fe3O4 decorated carbon nanotubes (CNTs-Fe3O4) were modified with a silica layer by the ammonia-catalysed hydrolysis of tetraethyl orthosilicate (CNTs-Fe3O4@SiO2). Then, CS-MCNTs were successfully grafted on the surface of CNTs-Fe3O4@SiO2via a suspension cross-linking method. The CS-MCNT was found to be an excellent heterogeneous catalyst for the synthesis of 1,4-dihydropyridines (DHPs). The attractive advantages of the present process include short reaction times, milder and cleaner conditions, higher purity and yields, easy isolation of products, easier work-up procedure and lower generation of waste or pollutions. This catalyst was easily separated by an external magnet and the recovered catalyst was reused several times without any significant loss of activity. A combination of the advantages of CNTs, chitosan and magnetic nanoparticles provides an important methodology for carrying out catalytic transformations. Therefore, this method provides a green and much improved protocol over the existing methods. Copyright © 2015 Elsevier B.V. All rights reserved.

Are Diatoms "Green" Aluminosilicate Synthesis Microreactors for Future Catalyst Production?

PubMed

Köhler, Lydia; Machill, Susanne; Werner, Anja; Selzer, Carolin; Kaskel, Stefan; Brunner, Eike

2017-12-16

Diatom biosilica may offer an interesting perspective in the search for sustainable solutions meeting the high demand for heterogeneous catalysts. Diatomaceous earth (diatomite), i.e., fossilized diatoms, is already used as adsorbent and carrier material. While diatomite is abundant and inexpensive, freshly harvested and cleaned diatom cell walls have other advantages, with respect to purity and uniformity. The present paper demonstrates an approach to modify diatoms both in vivo and in vitro to produce a porous aluminosilicate that is serving as a potential source for sustainable catalyst production. The obtained material was characterized at various processing stages with respect to morphology, elemental composition, surface area, and acidity. The cell walls appeared normal without morphological changes, while their aluminum content was raised from the molar ratio n (Al): n (Si) 1:600 up to 1:50. A specific surface area of 55 m²/g was measured. The acidity of the material increased from 149 to 320 µmol NH₃/g by ion exchange, as determined by NH₃ TPD. Finally, the biosilica was examined by an acid catalyzed test reaction, the alkylation of benzene. While the cleaned cell walls did not catalyze the reaction at all, and the ion exchanged material was catalytically active. This demonstrates that modified biosilica does indeed has potential as a basis for future catalytically active materials.

Characterization and activity of Pd-modified TiO2 catalysts for photocatalytic oxidation of NO in gas phase.

PubMed

Wu, Zhongbiao; Sheng, Zhongyi; Liu, Yue; Wang, Haiqiang; Tang, Nian; Wang, Jie

2009-05-30

Pd-modified TiO(2) prepared by thermal impregnation method was used in this study for photocatalytic oxidation of NO in gas phase. The physico-chemical properties of Pd/TiO(2) catalysts were characterized by X-ray diffraction analysis (XRD), Brunauer-Emmett-Teller measurements (BET), X-ray photoelectron spectrum analysis (XPS), transmission electron microscopy (TEM), high resolution-transmission electron microscopy (HR-TEM), UV-vis diffuse reflectance spectra (UV-vis DRS) and photoluminescence spectra (PL). It was found that Pd dopant existed as PdO particles in as-prepared photocatalysts. The results of PL spectra indicated that the photogenerated electrons and holes were efficiently separated after Pd doping. During in situ XPS study, it was found that the content of hydroxyl groups on the surface of Pd/TiO(2) increased when the catalyst was irradiated by UV light, which could result in the improvement of photocatalytic activity. The activity test showed that the optimum Pd dopant content was 0.05 wt.%. And the maximum conversion of NO was about 72% higher than that of P25 when the initial concentration of NO was 200 ppm, which showed that Pd/TiO(2) photocatalysts could be potentially applied to oxidize higher concentration of NO.

Performance evaluation of platinum-molybdenum carbide nanocatalysts with ultralow platinum loading on anode and cathode catalyst layers of proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Saha, Shibely; Cabrera Rodas, José Andrés; Tan, Shuai; Li, Dongmei

2018-02-01

An alternative catalyst platform, consisting of a phase-pure transition carbide (TMC) support and Pt nanoparticles (NPs) in the range of subnanometer to < 2.7 nm, is established that can be used in both anode and cathode catalyst layers. While some TMCs with low Pt loadings have demonstrated similar activity as commercial Pt catalyst in idealized disk electrode screening tests, few to none have been applied in a realistic fuel cell membrane electrode assembly (MEA). We recently reported that β-Mo2C hollow nanotubes modified with Pt NPs via atomic layer deposition (ALD) possess better activity and durability than 20% Pt/C. This paper presents systematic evaluation of the Pt/Mo2C catalysts in a MEA, investigating effects of different MEA preparation techniques, gas diffusion layers (GDL) and various Pt loadings in the ultralow range (<0.04 mg/cm2) on MEA performance. Most importantly, we demonstrate, for the first time, that Pt/Mo2C catalyst on both anode and cathode, with a loading of 0.02 mg (Pt) cm-2, generated peak power density of 414 mW cm-2 that corresponds to 10.35 kWgPt-1 using hydrogen (H2) and oxygen (O2). Accelerated degradation tests (ADT) on Pt/Mo2C catalysts show 111% higher power density than commercial 20% Pt/C after the vigorous ADT.

Late-Transition-Metal-Modified β-Mo 2C Catalysts for Enhanced Hydrogenation during Guaiacol Deoxygenation

DOE PAGES

Baddour, Frederick G.; Witte, Vanessa A.; Nash, Connor P.; ...

2017-10-26

Molybdenum carbide has been identified as a promising bifunctional catalyst in the deoxygenation of a variety of pyrolysis vapor model compounds. Although high deoxygenation activity has been demonstrated, complementary hydrogenation activity has been limited, especially for lignin-derived, aromatic model compounds. The ability to control the relative site densities of acidic and hydrogenation functionalities represents a catalyst design challenge for these materials with the goal to improve hydrogenation activity under ex situ catalytic fast pyrolysis (CFP) conditions. Here in this paper, we demonstrate that the addition of Pt and Ni to Mo 2C resulted in an increase in the H*-site densitymore » with only a minor decrease in the acid-site density. In contrast, the addition of Pd did not significantly alter the H* or acid site densities. High conversions (>94%) and high selectivities to 0-oxygen products (>80%) were observed in guaiacol deoxygenation under ex situ CFP conditions (350 °C and 0.44 MPa H 2) for all catalysts. Pt addition resulted in the greatest deoxygenation, and site-time yields to hydrogenated products over the Pt/Mo 2C catalyst were increased to 0.048 s -1 compared to 0.015-0.019 s -1 for all other catalysts. The Pt/Mo 2C catalyst demonstrated the highest hydrogenation performance, but modification with Ni also significantly enhanced hydrogenation performance, representing a promising lower-cost alternative.« less

Late-Transition-Metal-Modified β-Mo 2C Catalysts for Enhanced Hydrogenation during Guaiacol Deoxygenation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baddour, Frederick G.; Witte, Vanessa A.; Nash, Connor P.

Molybdenum carbide has been identified as a promising bifunctional catalyst in the deoxygenation of a variety of pyrolysis vapor model compounds. Although high deoxygenation activity has been demonstrated, complementary hydrogenation activity has been limited, especially for lignin-derived, aromatic model compounds. The ability to control the relative site densities of acidic and hydrogenation functionalities represents a catalyst design challenge for these materials with the goal to improve hydrogenation activity under ex situ catalytic fast pyrolysis (CFP) conditions. Here in this paper, we demonstrate that the addition of Pt and Ni to Mo 2C resulted in an increase in the H*-site densitymore » with only a minor decrease in the acid-site density. In contrast, the addition of Pd did not significantly alter the H* or acid site densities. High conversions (>94%) and high selectivities to 0-oxygen products (>80%) were observed in guaiacol deoxygenation under ex situ CFP conditions (350 °C and 0.44 MPa H 2) for all catalysts. Pt addition resulted in the greatest deoxygenation, and site-time yields to hydrogenated products over the Pt/Mo 2C catalyst were increased to 0.048 s -1 compared to 0.015-0.019 s -1 for all other catalysts. The Pt/Mo 2C catalyst demonstrated the highest hydrogenation performance, but modification with Ni also significantly enhanced hydrogenation performance, representing a promising lower-cost alternative.« less

Study on the mechanism of a manganese-based catalyst for catalytic NOX flue gas denitration

NASA Astrophysics Data System (ADS)

Zhang, Lei; Wen, Xin; Lei, Zhang; Gao, Long; Sha, Xiangling; Ma, Zhenhua; He, Huibin; Wang, Yusu; Jia, Yang; Li, Yonghui

2018-04-01

Manganese-based bimetallic catalysts were prepared with self-made pyrolysis coke as carrier and its denitration performance of low-temperature SCR (selective catalyst reduction) was studied. The effects of different metal species, calcination temperature, calcination time and the metal load quantity on the denitration performance of the catalyst were studied by orthogonal test. The denitration mechanism of the catalyst was analyzed by XRD (X-ray diffraction), SEM (scanning electron microscope), BET test and transient test. The experiments show that: * The denitration efficiency of Mn-based bimetallic catalysts mainly relates to the metal type, the metal load quantity and the catalyst adjuvant type. * The optimal catalyst preparation conditions are as follows: the load quantity of monometallic MnO2 is 10%, calcined at 300°C for 4h, and then loaded with 8% CeO2, calcined at 350°Cfor 3h. * The denitration mechanism of manganese-based bimetallic oxide catalysts is stated as: NH3 is firstly adsorbed by B acid center Mn-OH which nears Mn4+==O to form NH4+, NH4+ was then attacked by the gas phase NO to form N2, H2O and Mn3+-OH. Finally, Mn3+-OH was oxidized by O2 to regenerate Mn4+.

TiO2 Nanotube-Carbon (TNT-C) as Support for Pt-based Catalyst for High Methanol Oxidation Reaction in Direct Methanol Fuel Cell.

PubMed

Abdullah, M; Kamarudin, S K; Shyuan, L K

2016-12-01

In this study, TiO 2 nanotubes (TNTs) were synthesized via a hydrothermal method using highly concentrated NaOH solutions varying from 6 to 12 M at 180 °C for 48 h. The effects of the NaOH concentration and the TNT crystal structure on the performance for methanol oxidation were investigated to determine the best catalyst support for Pt-based catalysts. The results showed that TNTs produced with 10 M NaOH exhibited a length and a diameter of 550 and 70 nm, respectively; these TNTs showed the best nanotube structure and were further used as catalyst supports for a Pt-based catalyst in a direct methanol fuel cell. The synthesized TNT and Pt-based catalysts were analysed by FESEM, TEM, BET, EDX, XRD and FTIR. The electrochemical performance of the catalysts was investigated using cyclic voltammetry (CV) and chronoamperometric (CA) analysis to further understand the methanol oxidation in the direct methanol fuel cell (DMFC). Finally, the result proves that Pt-Ru/TNT-C catalyst shows high performance in methanol oxidation as the highest current density achieved at 3.3 mA/cm 2 (normalised by electrochemically active surface area) and high catalyst tolerance towards poisoning species was established.

Calcium and lanthanum solid base catalysts for transesterification

DOEpatents

Ng, K. Y. Simon; Yan, Shuli; Salley, Steven O.

2015-07-28

In one aspect, a heterogeneous catalyst comprises calcium hydroxide and lanthanum hydroxide, wherein the catalyst has a specific surface area of more than about 10 m.sup.2/g. In another aspect, a heterogeneous catalyst comprises a calcium compound and a lanthanum compound, wherein the catalyst has a specific surface area of more than about 10 m.sup.2/g, and a total basicity of about 13.6 mmol/g. In further another aspect, a heterogeneous catalyst comprises calcium oxide and lanthanum oxide, wherein the catalyst has a specific surface area of more than about 10 m.sup.2/g. In still another aspect, a process for preparing a catalyst comprises introducing a base precipitant, a neutral precipitant, and an acid precipitant to a solution comprising a first metal ion and a second metal ion to form a precipitate. The process further comprises calcining the precipitate to provide the catalyst.

Catalysts as sensors--a promising novel approach in automotive exhaust gas aftertreatment.

PubMed

Moos, Ralf

2010-01-01

Sensors that detect directly and in situ the status of automotive exhaust gas catalysts by monitoring the electrical properties of the catalyst coating itself are overviewed. Examples included in this review are the in-situ determination of the electrical impedance of three-way catalysts based on ceria-zirconia solutions and of lean NO(x) traps of earth-alkaline based coatings, as well as approaches to determine the ammonia loading in Fe-SCR-zeolites with electrical ac measurements. Even more sophisticated approaches based on interactions with electromagnetic waves are also reviewed. For that purpose, metallic stick-like antennas are inserted into the exhaust pipe. The catalyst properties are measured in a contactless manner, directly indicating the catalyst status. The radio frequency probes gauge the oxygen loading degree of three-way catalysts, the NO(x)-loading of lean NO(x) traps, and the soot loading of Diesel particulate filters.

Catalysts as Sensors—A Promising Novel Approach in Automotive Exhaust Gas Aftertreatment

PubMed Central

Moos, Ralf

2010-01-01

Sensors that detect directly and in situ the status of automotive exhaust gas catalysts by monitoring the electrical properties of the catalyst coating itself are overviewed. Examples included in this review are the in-situ determination of the electrical impedance of three-way catalysts based on ceria-zirconia solutions and of lean NOx traps of earth-alkaline based coatings, as well as approaches to determine the ammonia loading in Fe-SCR-zeolites with electrical ac measurements. Even more sophisticated approaches based on interactions with electromagnetic waves are also reviewed. For that purpose, metallic stick-like antennas are inserted into the exhaust pipe. The catalyst properties are measured in a contactless manner, directly indicating the catalyst status. The radio frequency probes gauge the oxygen loading degree of three-way catalysts, the NOx-loading of lean NOx traps, and the soot loading of Diesel particulate filters. PMID:22163575

Catalyst patterning for nanowire devices

NASA Technical Reports Server (NTRS)

Li, Jun (Inventor); Cassell, Alan M. (Inventor); Han, Jie (Inventor)

2004-01-01

Nanowire devices may be provided that are based on carbon nanotubes or single-crystal semiconductor nanowires. The nanowire devices may be formed on a substrate. Catalyst sites may be formed on the substrate. The catalyst sites may be formed using lithography, thin metal layers that form individual catalyst sites when heated, collapsible porous catalyst-filled microscopic spheres, microscopic spheres that serve as masks for catalyst deposition, electrochemical deposition techniques, and catalyst inks. Nanowires may be grown from the catalyst sites.

Bio-oil hydrodeoxygenation catalysts produced using strong electrostatic adsorption

USDA-ARS?s Scientific Manuscript database

We synthesized hydrothermally stable metal catalysts with controlled particle size and distribution, with the goal of determining which catalyst(s) can selectively catalyze the production of aromatics from bio-oil (from pyrolysis of biomass). Both precious and base transition metal catalysts (Ru, Pt...

Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts

PubMed Central

Varnell, Jason A.; Tse, Edmund C. M.; Schulz, Charles E.; Fister, Tim T.; Haasch, Richard T.; Timoshenko, Janis; Frenkel, Anatoly I.; Gewirth, Andrew A.

2016-01-01

The widespread use of fuel cells is currently limited by the lack of efficient and cost-effective catalysts for the oxygen reduction reaction. Iron-based non-precious metal catalysts exhibit promising activity and stability, as an alternative to state-of-the-art platinum catalysts. However, the identity of the active species in non-precious metal catalysts remains elusive, impeding the development of new catalysts. Here we demonstrate the reversible deactivation and reactivation of an iron-based non-precious metal oxygen reduction catalyst achieved using high-temperature gas-phase chlorine and hydrogen treatments. In addition, we observe a decrease in catalyst heterogeneity following treatment with chlorine and hydrogen, using Mössbauer and X-ray absorption spectroscopy. Our study reveals that protected sites adjacent to iron nanoparticles are responsible for the observed activity and stability of the catalyst. These findings may allow for the design and synthesis of enhanced non-precious metal oxygen reduction catalysts with a higher density of active sites. PMID:27538720

Solar H2 evolution in water with modified diketopyrrolopyrrole dyes immobilised on molecular Co and Ni catalyst-TiO2 hybrids.

PubMed

Warnan, Julien; Willkomm, Janina; Ng, Jamues N; Godin, Robert; Prantl, Sebastian; Durrant, James R; Reisner, Erwin

2017-04-01

A series of diketopyrrolopyrrole (DPP) dyes with a terminal phosphonic acid group for attachment to metal oxide surfaces were synthesised and the effect of side chain modification on their properties investigated. The organic photosensitisers feature strong visible light absorption ( λ = 400 to 575 nm) and electrochemical and fluorescence studies revealed that the excited state of all dyes provides sufficient driving force for electron injection into the TiO 2 conduction band. The performance of the DPP chromophores attached to TiO 2 nanoparticles for photocatalytic H 2 evolution with co-immobilised molecular Co and Ni catalysts was subsequently studied, resulting in solar fuel generation with a dye-sensitised semiconductor nanoparticle system suspended in water without precious metal components. The performance of the DPP dyes in photocatalysis did not only depend on electronic parameters, but also on properties of the side chain such as polarity, steric hinderance and hydrophobicity as well as the specific experimental conditions and the nature of the sacrificial electron donor. In an aqueous pH 4.5 ascorbic acid solution with a phosphonated DuBois-type Ni catalyst, a DPP-based turnover number (TON DPP ) of up to 205 was obtained during UV-free simulated solar light irradiation (100 mW cm -2 , AM 1.5G, λ > 420 nm) after 1 day. DPP-sensitised TiO 2 nanoparticles were also successfully used in combination with a hydrogenase or platinum instead of the synthetic H 2 evolution catalysts and the platinum-based system achieved a TON DPP of up to 2660, which significantly outperforms an analogous system using a phosphonated Ru tris(bipyridine) dye (TON Ru = 431). Finally, transient absorption spectroscopy was performed to study interfacial recombination and dye regeneration kinetics revealing that the different performances of the DPP dyes are most likely dictated by the different regeneration efficiencies of the oxidised chromophores.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Weigang; Yuan, Daqiang; Yakovenko, Andrey A

A super-paddlewheel (comprised of two paddlewheels) metal–organic polyhedron (MOP) containing surface hydroxyl groups was synthesized and characterized. Condensation reactions with linear alkyl anhydrides lead to new MOPs with enhanced solubility. As a result, the surface-modified MOP 4 was demonstrated as a homogeneous Lewis-acid catalyst.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Weigang; Yuan, Daqiang; Yakovenko, Andrey

A super-paddlewheel (comprised of two paddlewheels) metal-organic polyhedron (MOP) containing surface hydroxyl groups was synthesized and characterized. Condensation reactions with linear alkyl anhydrides lead to new MOPs with enhanced solubility. As a result, the surface-modified MOP 4 was demonstrated as a homogeneous Lewis-acid catalyst.

Evolution of a Fourth Generation Catalyst for the Amination and Thioetherification of Aryl Halides

PubMed Central

Hartwig, John F.

2010-01-01

Conspectus Synthetic methods to form the carbon-nitrogen bonds in aromatic amines are fundamental enough to be considered part of introductory organic courses. Arylamines are important because they are common precursors to or substructures within active pharmaceutical ingredients and herbicides produced on ton scales, as well as conducting polymers and layers of organic light-emitting diodes produced on small scale. For many years, this class of compound was prepared from classical methods, such as nitration, reduction and reductive alkylation, copper-mediated chemistry at high temperatures, addition to benzyne intermediates, or direct nucleophilic substitution on particularly electron-poor aromatic or heteroaromatic halides. During the past decade, these methods to form aromatic amines have been largely supplanted by palladium-catalyzed coupling reactions of amines with aryl halides. The scope and efficiency of the palladium-catalyzed processes has gradually improved with successive generations of catalysts to the point of being useful for the synthesis of both milligrams and kilograms of product. This Account describes the conceptual basis and utility of our latest, “fourth-generation” catalyst for the coupling of amines and related reagents with aryl halides. The introductory sections of this account describe the progression of catalyst development from the first-generation to current systems and the motivation for selection of the components of the fourth-generation catalyst. This progression began with catalysts containing palladium and sterically hindered monodentate aromatic phosphines used initially for coupling of tin amides with haloarenes in the first work on C-N coupling. A second generation of catalysts was then developed based on the combination of palladium and aromatic bisphosphines. These systems were then followed by third-generation systems catalysts on the combination of palladium and a sterically hindered alkylmonophosphine or N-heterocyclic carbene. During the past five years, we have studied a fourth-generation catalyst for these reactions containing ligands that combine the chelating properties of the second-generation systems with the steric hindrance and strong electron donation of the third-generation systems. This combination has created a catalyst that couples aryl chlorides, bromides and iodides with primary amines, N-H imines, and hydrazones in high yield, with broad scope, high functional group tolerance, nearly perfect selectivity for monoarylation, and the lowest levels of palladium that have been used for C-N coupling. This catalyst is based on palladium and a sterically hindered version of the Josiphos family of ligands that possesses a ferrocenyl-1-ethylbackbone, a hindered di-tert-butylphosphino group, and a hindered dicyclohexylphosphino group. This latest generation of catalyst not only improves the coupling of primary amines and related nucleophiles, but it has dramatically improved the coupling of thiols with haloarenes to form C-S bonds. This catalyst system couples both aliphatic and aromatic thiols with chloroarenes with much greater scope, functional group tolerance, and turnover numbers than had been observed previously. The effects of structural features of the Josiphos ligand on catalyst activity have been revealed by examining the reactivity of catalysts generated from ligands lacking one or more of the structural elements of the most active catalyst. These modified ligands lack the relative stereochemistry of the ferrocenyl-1-ethyl backbone, the strong electron donation of the dialkylphosphino groups, the steric demands of the alkylphosphine groups, or the stability of the ferrocenyl unit. This set of studies showed that each one of these structural features contributed to the high reactivity and selectivity of the catalyst containing the hindered, bidentate Josiphos ligand. Finally, a series of studies on the effect of electronic properties on the rates of reductive elimination have recently distinguished between the effect of the properties of the M-N σ-bond and the nitrogen electron pair on the rate of reductive elimination. These studies have shown that the effect of substituents attached to the metal-bound nitrogen or carbon atoms on the rate of reductive elimination are similar. Because the amido ligands contain an electron pair, while the alkyl ligands do not, we have concluded that the major electronic effect is transmitted through the σ-bond. In other words, we have concluded that the electronic effect on the metal-nitrogen σ bond dominates an electronic effect on the nitrogen electron pair. PMID:18681463

A Novel Slurry-Based Biomass Reforming Process Final Technical Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Emerson, Sean C.; Davis, Timothy D.; Peles, A.

2011-09-30

This project was focused on developing a catalytic means of producing H2 from raw, ground biomass, such as fast growing poplar trees, willow trees, or switch grass. The use of a renewable, biomass feedstock with minimal processing can enable a carbon neutral means of producing H2 in that the carbon dioxide produced from the process can be used in the environment to produce additional biomass. For economically viable production of H2, the biomass is hydrolyzed and then reformed without any additional purification steps. Any unreacted biomass and other byproduct streams are burned to provide process energy. Thus, the development ofmore » a catalyst that can operate in the demanding corrosive environment and presence of potential poisons is vital to this approach. The concept for this project is shown in Figure 1. The initial feed is assumed to be a >5 wt% slurry of ground wood in dilute base, such as potassium carbonate (K2CO3). Base hydrolysis and reforming of the wood is carried out at high but sub-critical pressures and temperatures in the presence of a solid catalyst. A Pd alloy membrane allows the continuous removal of pure , while the retentate, including methane is used as fuel in the plant. The project showed that it is possible to economically produce H2 from woody biomass in a carbon neutral manner. Technoeconomic analyses using HYSYS and the DOE's H2A tool [1] were used to design a 2000 ton day-1 (dry basis) biomass to hydrogen plant with an efficiency of 46% to 56%, depending on the mode of operation and economic assumptions, exceeding the DOE 2012 target of 43%. The cost of producing the hydrogen from such a plant would be in the range of $1/kg H2 to $2/kg H2. By using raw biomass as a feedstock, the cost of producing hydrogen at large biomass consumption rates is more cost effective than steam reforming of hydrocarbons or biomass gasification and can achieve the overall cost goals of the DOE Fuel Cell Technologies Program. The complete conversion of wood to hydrogen, methane, and carbon dioxide was repeatedly demonstrated in batch reactors varying in size from 50 mL to 7.6 L. The different wood sources (e.g., swamp maple, poplar, and commercial wood flour) were converted in the presence of a heterogeneous catalyst and base at relatively low temperatures (e.g., 310°C) at sub-critical pressures sufficient to maintain the liquid phase. Both precious metal and base metal catalysts were found to be active for the liquid phase hydrolysis and reforming of wood. Pt-based catalysts, particularly Pt-Re, were shown to be more selective toward breaking C-C bonds, resulting in a higher selectivity to hydrogen versus methane. Ni-based catalysts were found to prefer breaking C-O bonds, favoring the production of methane. The project showed that increasing the concentration of base (base to wood ratio) in the presence of Raney Ni catalysts resulted in greater selectivity toward hydrogen but at the expense of increasing the production of undesirable organic acids from the wood, lowering the amount of wood converted to gas. It was shown that by modifying Ni-based catalysts with dopants, it was possible to reduce the base concentration while maintaining the selectivity toward hydrogen and increasing wood conversion to gas versus organic acids. The final stage of the project was the construction and testing of a demonstration unit for H2 production. This continuous flow demonstration unit consisted of wood slurry and potassium carbonate feed pump systems, two reactors for hydrolysis and reforming, and a gas-liquid separation system. The technical challenges associated with unreacted wood fines and Raney Ni catalyst retention limited the demonstration unit to using a fixed bed Raney Ni catalyst form. The lower activity of the larger particle Raney Ni in turn limited the residence time and thus the wood mass flow feed rate to 50 g min-1 for a 1 wt% wood slurry. The project demonstrated continuous H2 yields with unmodified, fixed bed Raney Ni, from 63% to 100% with corresponding H2 selectivities of 6% to 21%, for periods of several hours. The fixed bed form of the Raney Ni exhibited signs of deactivation which requires further study.« less

Catalyst for Decomposition of Nitrogen Oxides

NASA Technical Reports Server (NTRS)

Schryer, David R. (Inventor); Akyurtlu, Ates (Inventor); Jordan, Jeffrey D. (Inventor); Akyurtlu, Jale (Inventor)

2015-01-01

This invention relates generally to a platinized tin oxide-based catalyst. It relates particularly to an improved platinized tin oxide-based catalyst able to decompose nitric oxide to nitrogen and oxygen without the necessity of a reducing gas.

New Catalyst Reduces Wasted Carbon in Biofuel Process, Lowers Cost

DOE Office of Scientific and Technical Information (OSTI.GOV)

Researchers at NREL recently developed a catalyst formulation that incorporates more hydrogen into the DME-to-high-octane gasoline process, resulting in a higher yield to gasoline-range products. Further, the researchers developed a secondary process that efficiently couples a portion of the gasoline-range product to yield jet/diesel fuels. The modified catalyst doubles the conversion rate of DME, which can be produced from biomass, to the high-octane gasoline product and significantly decreases the formation of wasted byproducts. For the distillate-range product, 80% of the mixture is in line with ASTM standards for use as a jet fuel blendstock. The increased productivity of high-octane gasolinemore » and the development of a value-added distillate blendstock process further improve the economic viability toward commercially implementing this renewable fuels process.« less

Low oxygen biomass-derived pyrolysis oils and methods for producing the same

DOEpatents

Marinangeli, Richard; Brandvold, Timothy A; Kocal, Joseph A

2013-08-27

Low oxygen biomass-derived pyrolysis oils and methods for producing them from carbonaceous biomass feedstock are provided. The carbonaceous biomass feedstock is pyrolyzed in the presence of a catalyst comprising base metal-based catalysts, noble metal-based catalysts, treated zeolitic catalysts, or combinations thereof to produce pyrolysis gases. During pyrolysis, the catalyst catalyzes a deoxygenation reaction whereby at least a portion of the oxygenated hydrocarbons in the pyrolysis gases are converted into hydrocarbons. The oxygen is removed as carbon oxides and water. A condensable portion (the vapors) of the pyrolysis gases is condensed to low oxygen biomass-derived pyrolysis oil.

CO2 methanation on the catalyst of Ni/MCM-41 promoted with CeO2.

PubMed

Wang, Xiaoliu; Zhu, Lingjun; Liu, Yincong; Wang, Shurong

2018-06-01

CO 2 as a raw feed combined with renewable hydrogen for the production of useful chemicals and alternative energy products is one of the solutions to environmental and energy problems. In this study, a series of Ni-xCeO 2 /MCM-41 catalysts with a nickel content of 20wt% were prepared through deposition precipitation method for CO 2 methanation. Different characterization methods, including BET, XRD, TEM, SEM, H 2 -TPR and H 2 -TPD were applied to help explore the influence mechanism of CeO 2 on Ni/MCM-41 in CO 2 methanation. It was found that all CeO 2 -promoted catalysts exhibited enhanced catalytic activity when compared to Ni/MCM-41. The catalyst modified with 20wt% CeO 2 showed the best catalytic performance, with CO 2 conversion and CH 4 selectivity of 85.6% and 99.8%, respectively, at the temperature of 380°C under atmospheric pressure. The synergetic effects among Ni 0 active sites, the promoter and the support, including nickel dispersion improvement and increased CO 2 adsorption sites due to the addition of CeO 2 , were considered as important factors for high reactivity of the promoted catalysts. The stability test showed that the promoted catalyst maintained its high reactivity after 30h. Copyright © 2017 Elsevier B.V. All rights reserved.

Low Concentration Fe-Doped Alumina Catalysts Using Sol-Gel and Impregnation Methods: The Synthesis, Characterization and Catalytic Performance during the Combustion of Trichloroethylene.

PubMed

Maldonado, Carolina Solis; De la Rosa, Javier Rivera; Lucio-Ortiz, Carlos J; Hernández-Ramírez, Aracely; Barraza, Felipe F Castillón; Valente, Jaime S

2014-03-12

The role of iron in two modes of integration into alumina catalysts was studied at 0.39 wt% Fe and tested in trichloroethylene combustion. One modified alumina was synthesized using the sol-gel method with Fe added in situ during hydrolysis; another modification was performed using calcined alumina, prepared using the sol-gel method and impregnated with Fe. Several characterization techniques were used to study the level of Fe modification in the γ-Al₂O₃ phase formed and to correlate the catalytic properties during trichloroethylene (TCE) combustion. The introduction of Fe in situ during the sol-gel process influenced the crystallite size, and three iron species were generated, namely, magnetite, maghemite and hematite. The impregnated Fe-alumina formed hematite and maghemite, which were highly dispersed on the γ-Al₂O 3 surface. The X-ray photoelectron spectra (XPS), FT-IR and Mössbauer spectroscopy analyses revealed how Fe interacted with the γ-Al₂O₃ lattice in both catalysts. The impregnated Fe-catalyst showed the best catalytic performance compared to the catalyst that was Fe-doped in situ by the sol-gel method; both had better catalytic activity than pure alumina. This difference in activity was correlated with the accessibility of the reactants to the hematite iron species on the surface. The chlorine poisoning for all three catalysts was less than 1.8%.

Catalyst free growth of CNTs by CVD on nanoscale rough surfaces of silicon substrates

NASA Astrophysics Data System (ADS)

Damodar, D.; Sahoo, R. K.; Jacob, C.

2013-06-01

Catalyst free growth of carbon nanotubes (CNT) has been achieved using atmospheric pressure chemical vapor deposition (APCVD) on surface modified Si(111) substrates. The effect of the substrate surface has been observed by partially etching with KOH (potassium hydroxide) solution which is an anisotropic etchant. Scanning electron microscopy (SEM) confirmed the formation of CNTs over most of the area of the substrate where substrates were anisotropically etched. Transmission electron microscopy (TEM) was used to observe the internal structure of the CNTs. Raman spectroscopy further confirmed the formation of the carbon nanostructures and also their graphitic crystallinity.

Characterization and Performance of Melamine Enhanced Urea Formaldehyde Resin for Bonding Southern Pine Particleboard

Treesearch

Qi-Ning Sun; Chung-Yun Hse; Todd F. Shupe

2011-01-01

Urea-formaldehyde resins modified by melamine were synthesized by four catalysts (H2SO4, HCl, H3PO4, and NaOH/NH4OH) with a F/U/M molar ratio of 1.38/1/0.074. Resin structure and thermal behavior were studied by 13C-NMR and DSC techniques. For H2SO4, HCl, and H3PO4 catalysts, resins were prepared by two stage pH adjustment: the first pH stage was set at 1.25 (H3PO4 pH...

Photoelectrochemical electrodes

NASA Technical Reports Server (NTRS)

Williams, R. M.; Rembaum, A. (Inventor)

1983-01-01

The surface of a moderate band gap semiconductor such as p-type molybdenum sulfide is modified to contain an adherent film of charge mediating ionene polymer containing an electroactive unit such as bipyridimium. Electron transport between the electrode and the mediator film is favorable and photocorrosion and recombination processes are suppressed. Incorporation of particles of catalyst such as platinum within the film provides a reduction in overvoltage. The polymer film is readily deposited on the electrode surface and can be rendered stable by ionic or addition crosslinking. Catalyst can be predispersed in the polymer film or a salt can be impregnated into the film and reduced therein.

Effect of Oxide Coating on Performance of Copper-Zinc Oxide-Based Catalyst for Methanol Synthesis via Hydrogenation of Carbon Dioxide.

PubMed

Umegaki, Tetsuo; Kojima, Yoshiyuki; Omata, Kohji

2015-11-16

The effect of oxide coating on the activity of a copper-zinc oxide-based catalyst for methanol synthesis via the hydrogenation of carbon dioxide was investigated. A commercial catalyst was coated with various oxides by a sol-gel method. The influence of the types of promoters used in the sol-gel reaction was investigated. Temperature-programmed reduction-thermogravimetric analysis revealed that the reduction peak assigned to the copper species in the oxide-coated catalysts prepared using ammonia shifts to lower temperatures than that of the pristine catalyst; in contrast, the reduction peak shifts to higher temperatures for the catalysts prepared using L(+)-arginine. These observations indicated that the copper species were weakly bonded with the oxide and were easily reduced by using ammonia. The catalysts prepared using ammonia show higher CO₂ conversion than the catalysts prepared using L(+)-arginine. Among the catalysts prepared using ammonia, the silica-coated catalyst displayed a high activity at high temperatures, while the zirconia-coated catalyst and titania-coated catalyst had high activity at low temperatures. At high temperature the conversion over the silica-coated catalyst does not significantly change with reaction temperature, while the conversion over the zirconia-coated catalyst and titania-coated catalyst decreases with reaction time. From the results of FTIR, the durability depends on hydrophilicity of the oxides.

Effect of Oxide Coating on Performance of Copper-Zinc Oxide-Based Catalyst for Methanol Synthesis via Hydrogenation of Carbon Dioxide

PubMed Central

Umegaki, Tetsuo; Kojima, Yoshiyuki; Omata, Kohji

2015-01-01

The effect of oxide coating on the activity of a copper-zinc oxide–based catalyst for methanol synthesis via the hydrogenation of carbon dioxide was investigated. A commercial catalyst was coated with various oxides by a sol-gel method. The influence of the types of promoters used in the sol-gel reaction was investigated. Temperature-programmed reduction-thermogravimetric analysis revealed that the reduction peak assigned to the copper species in the oxide-coated catalysts prepared using ammonia shifts to lower temperatures than that of the pristine catalyst; in contrast, the reduction peak shifts to higher temperatures for the catalysts prepared using L(+)-arginine. These observations indicated that the copper species were weakly bonded with the oxide and were easily reduced by using ammonia. The catalysts prepared using ammonia show higher CO2 conversion than the catalysts prepared using L(+)-arginine. Among the catalysts prepared using ammonia, the silica-coated catalyst displayed a high activity at high temperatures, while the zirconia-coated catalyst and titania-coated catalyst had high activity at low temperatures. At high temperature the conversion over the silica-coated catalyst does not significantly change with reaction temperature, while the conversion over the zirconia-coated catalyst and titania-coated catalyst decreases with reaction time. From the results of FTIR, the durability depends on hydrophilicity of the oxides. PMID:28793674

Spectroscopic insights into the nature of active sites in iron–nitrogen–carbon electrocatalysts for oxygen reduction in acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jia, Qingying; Ramaswamy, Nagappan; Tylus, Urszula

Developing efficient and inexpensive catalysts for the sluggish oxygen reduction reaction (ORR) constitutes one of the grand challenges in the fabrication of commercially viable fuel cell devices and metal–air batteries for future energy applications. Despite recent achievements in designing advanced Pt-based and Pt-free catalysts, current progress primarily involves an empirical approach of trial-and-error combination of precursors and synthesis conditions, which limits further progress. Rational design of catalyst materials requires proper understanding of the mechanistic origin of the ORR and the underlying surface properties under operating conditions that govern catalytic activity. Herein, several different groups of iron-based catalysts synthesized via differentmore » methods and/or precursors were systematically studied by combining multiple spectroscopic techniques under ex situ and in situ conditions in an effort to obtain a comprehensive understanding of the synthesis-products correlations, nature of active sites, and the reaction mechanisms. These catalysts include original macrocycles, macrocycle-pyrolyzed catalysts, and Fe-N–C catalysts synthesized from individual Fe, N, and C precursors including polymer-based catalysts, metal organic framework (MOF)-based catalysts, and sacrificial support method (SSM)-based catalysts. The latter group of catalysts is most promising as not only they exhibit exceptional ORR activity and/or durability, but also the final products are controllable. We show that the high activity observed for most pyrolyzed Fe-based catalysts can mainly be attributed to a single active site: non-planar Fe–N 4 moiety embedded in distorted carbon matrix characterized by a high potential for the Fe 2+/3+ redox transition in acidic electrolyte/environment. The high intrinsic ORR activity, or turnover frequency (TOF), of this site is shown to be accounted for by redox catalysis mechanism that highlights the dominant role of the site-blocking effect. Moreover, a highly active MOF-based catalyst without Fe–N moieties was developed, and the active sites were identified as nitrogen-doped carbon fibers with embedded iron particles that are not directly involved in the oxygen reduction pathway. The high ORR activity and durability of catalysts involving this second site, as demonstrated in fuel cell, are attributed to the high density of active sites and the elimination or reduction of Fenton-type processes. The latter are initiated by hydrogen peroxide but are known to be accelerated by iron ions exposed to the surface, resulting in the formation of damaging free-radicals.« less

Development of biomimetic catalytic oxidation methods and non-salt methods using transition metal-based acid and base ambiphilic catalysts

PubMed Central

MURAHASHI, Shun-Ichi

2011-01-01

This review focuses on the development of ruthenium and flavin catalysts for environmentally benign oxidation reactions based on mimicking the functions of cytochrome P-450 and flavoenzymes, and low valent transition-metal catalysts that replace conventional acids and bases. Several new concepts and new types of catalytic reactions based on these concepts are described. PMID:21558760

Antifungal Activity of Denture Soft Lining Material Modified by Silver Nanoparticles—A Pilot Study

PubMed Central

Chladek, Grzegorz; Mertas, Anna; Barszczewska-Rybarek, Izabela; Nalewajek, Teresa; Żmudzki, Jarosław; Król, Wojciech; Łukaszczyk, Jan

2011-01-01

Soft liner materials in oral cavity environments are easily colonized both by fungi and dental plaque. These factors are the cause of mucosal infections. The microorganism that most frequently colonizes soft liner materials is Candida albicans. Colonization occurs on the surface of materials and within materials. A solution to this problem might involve modification of soft liner materials with silver nanoparticles (AgNPs). In this article, we present results showing the antifungal efficacy of silicone soft lining materials modified with AgNPs. The modification process was conducted by dissolving both material components (base and catalyst) in a colloidal solution of AgNPs and evaporating the solvent. Composites with various AgNP concentrations (10, 20, 40, 80, 120 and 200 ppm) were examined. The in vitro antifungal efficacy (AFE) of composite samples was 16.3% to 52.5%. PMID:21845108

Magnetic solid base catalyst CaO/CoFe2O4 for biodiesel production: Influence of basicity and wettability of the catalyst in catalytic performance

NASA Astrophysics Data System (ADS)

Zhang, Pingbo; Han, Qiuju; Fan, Mingming; Jiang, Pingping

2014-10-01

A novel magnetic solid base catalyst CaO/CoFe2O4 was successfully prepared with CoFe2O4 synthesized by hydrothermal method as the magnetic core and applied to the transesterification of soybean oil for the production of biodiesel. The magnetic solid base catalysts were characterized by a series of techniques including CO2-TPD, powder XRD, TGA, TEM and the contact angle measurement of the water droplet. It was demonstrated that CaO/CoFe2O4 has stronger magnetic strength indicating perfect utility for repeated use and better basic strength. Compared with CaO/ZnFe2O4 and CaO/MnFe2O4, solid base catalyst CaO/CoFe2O4 has better catalytic performance, weaker hydroscopicity and stronger wettability, demonstrating that catalytic performance was relative to both basicity of catalyst and the full contact between the catalyst and the reactants, but the latter was a main factor in the catalytic system.

Multifunctional Au-Fe3O4@MOF core-shell nanocomposite catalysts with controllable reactivity and magnetic recyclability

NASA Astrophysics Data System (ADS)

Ke, Fei; Wang, Luhuan; Zhu, Junfa

2014-12-01

The recovery and reuse of expensive catalysts are important in both heterogeneous and homogeneous catalysis due to economic and environmental reasons. This work reports a novel multifunctional magnetic core-shell gold catalyst which can be easily prepared and shows remarkable catalytic properties in the reduction of 4-nitrophenol. The novel Au-Fe3O4@metal-organic framework (MOF) catalyst consists of a superparamagnetic Au-Fe3O4 core and a porous MOF shell with controllable thickness. Small Au nanoparticles (NPs) of 3-5 nm are mainly sandwiched between the Fe3O4 core and the porous MOF shell. Catalytic studies show that the core-shell structured Au-Fe3O4@MOF catalyst has a much higher catalytic activity than other reported Au-based catalysts toward the reduction of 4-nitrophenol. Moreover, this catalyst can be easily recycled due to the presence of the superparamagnetic core. Therefore, compared to conventional catalysts used in the reduction of 4-nitrophenol, this porous MOF-based magnetic catalyst is green, cheap and promising for industrial applications.The recovery and reuse of expensive catalysts are important in both heterogeneous and homogeneous catalysis due to economic and environmental reasons. This work reports a novel multifunctional magnetic core-shell gold catalyst which can be easily prepared and shows remarkable catalytic properties in the reduction of 4-nitrophenol. The novel Au-Fe3O4@metal-organic framework (MOF) catalyst consists of a superparamagnetic Au-Fe3O4 core and a porous MOF shell with controllable thickness. Small Au nanoparticles (NPs) of 3-5 nm are mainly sandwiched between the Fe3O4 core and the porous MOF shell. Catalytic studies show that the core-shell structured Au-Fe3O4@MOF catalyst has a much higher catalytic activity than other reported Au-based catalysts toward the reduction of 4-nitrophenol. Moreover, this catalyst can be easily recycled due to the presence of the superparamagnetic core. Therefore, compared to conventional catalysts used in the reduction of 4-nitrophenol, this porous MOF-based magnetic catalyst is green, cheap and promising for industrial applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr05421k

The Concept about the Regeneration of Spent Borohydrides and Used Catalysts from Green Electricity

PubMed Central

Liu, Cheng-Hong; Chen, Bing-Hung

2015-01-01

Currently, the Brown-Schlesinger process is still regarded as the most common and mature method for the commercial production of sodium borohydride (NaBH4). However, the metallic sodium, currently produced from the electrolysis of molten NaCl that is mass-produced by evaporation of seawater or brine, is probably the most costly raw material. Recently, several reports have demonstrated the feasibility of utilizing green electricity such as offshore wind power to produce metallic sodium through electrolysis of seawater. Based on this concept, we have made improvements and modified our previously proposed life cycle of sodium borohydride (NaBH4) and ammonia borane (NH3BH3), in order to further reduce costs in the conventional Brown-Schlesinger process. In summary, the revision in the concept combining the regeneration of the spent borohydrides and the used catalysts with the green electricity is reflected in (1) that metallic sodium could be produced from NaCl of high purity obtained from the conversion of the byproduct in the synthesis of NH3BH3 to devoid the complicated purification procedures if produced from seawater; and (2) that the recycling and the regeneration processes of the spent NaBH4 and NH3BH3 as well as the used catalysts could be simultaneously carried out and combined with the proposed life cycle of borohydrides.

Carbon-Based Oxamate Cobalt(III) Complexes as Bioenzyme Mimics for Contaminant Elimination in High Backgrounds of Complicated Constituents.

PubMed

Li, Nan; Zheng, Yun; Jiang, Xuemei; Zhang, Ran; Pei, Kemei; Chen, Wenxing

2017-10-12

Complex wastewater with massive components is now a serious environmental issue facing humanity. Selective removal of low-concentration contaminants in mixed constituents holds great promise for increasing water supplies. Bioenzymes like horseradish peroxidase exhibit oxidizing power and selectivity. Here, we manufactured its mimic through immobilizing non-heme oxamate anionic cobalt(III) complex ([Co III (opba)] - , opba = o-phenylenebis(oxamate)) onto pyridine (Py) modified multiwalled carbon nanotubes ([Co III (opba)] - -Py-MWCNTs, MWCNTs = multiwalled carbon nanotubes), where MWCNTs captured substrates and Py functioned as the fifth ligand. We chose typical azo dye (C.I. Acid Red 1) and antibiotic (ciprofloxacin) as model substrates. Without •OH, this catalyst could detoxify target micropollutants efficiently at pH from 8 to 11. It also remained efficient in repetitive tests, and the final products were non-poisonous OH-containing acids. Combined with radical scavenger tests and electron paramagnetic resonance result, we speculated that high-valent cobalt-oxo active species and oxygen atom transfer reaction dominated in the reaction pathway. According to density functional theory calculations, the electron spin density distribution order showed that electron-withdrawing ligand was beneficial for inward pulling the excess electron and lowering the corresponding energy levels, achieving an electrophilic-attack enhancement of the catalyst. With target removal property and recyclability, this catalyst is prospective in water detoxication.

Coupled Metal/Oxide Catalysts with Tunable Product Selectivity for Electrocatalytic CO2 Reduction.

PubMed

Huo, Shengjuan; Weng, Zhe; Wu, Zishan; Zhong, Yiren; Wu, Yueshen; Fang, Jianhui; Wang, Hailiang

2017-08-30

One major challenge to the electrochemical conversion of CO 2 to useful fuels and chemical products is the lack of efficient catalysts that can selectively direct the reaction to one desirable product and avoid the other possible side products. Making use of strong metal/oxide interactions has recently been demonstrated to be effective in enhancing electrocatalysis in the liquid phase. Here, we report one of the first systematic studies on composition-dependent influences of metal/oxide interactions on electrocatalytic CO 2 reduction, utilizing Cu/SnO x heterostructured nanoparticles supported on carbon nanotubes (CNTs) as a model catalyst system. By adjusting the Cu/Sn ratio in the catalyst material structure, we can tune the products of the CO 2 electrocatalytic reduction reaction from hydrocarbon-favorable to CO-selective to formic acid-dominant. In the Cu-rich regime, SnO x dramatically alters the catalytic behavior of Cu. The Cu/SnO x -CNT catalyst containing 6.2% of SnO x converts CO 2 to CO with a high faradaic efficiency (FE) of 89% and a j CO of 11.3 mA·cm -2 at -0.99 V versus reversible hydrogen electrode, in stark contrast to the Cu-CNT catalyst on which ethylene and methane are the main products for CO 2 reduction. In the Sn-rich regime, Cu modifies the catalytic properties of SnO x . The Cu/SnO x -CNT catalyst containing 30.2% of SnO x reduces CO 2 to formic acid with an FE of 77% and a j HCOOH of 4.0 mA·cm -2 at -0.99 V, outperforming the SnO x -CNT catalyst which only converts CO 2 to formic acid in an FE of 48%.

Graphene-derived Fe/Co-N-C catalyst in direct methanol fuel cells: Effects of the methanol concentration and ionomer content on cell performance

NASA Astrophysics Data System (ADS)

Park, Jong Cheol; Choi, Chang Hyuck

2017-08-01

Non-precious metal catalysts (typically Fe(Co)-N-C catalysts) have been widely investigated for use as cost-effective cathode materials in low temperature fuel cells. Despite the high oxygen reduction activity and methanol-tolerance of graphene-based Fe(Co)-N-C catalysts in an acidic medium, their use in direct methanol fuel cells (DMFCs) has not yet been successfully implemented, and only a few studies have investigated this topic. Herein, we synthesized a nano-sized graphene-derived Fe/Co-N-C catalyst by physical ball-milling and a subsequent chemical modification of the graphene oxide. Twelve membrane-electrode-assemblies are fabricated with various cathode compositions to determine the effects of the methanol concentration, ionomer (i.e. Nafion) content, and catalyst loading on the DMFC performance. The results show that a graphene-based catalyst is capable of tolerating a highly-concentrated methanol feed up to 10.0 M. The optimized electrode composition has an ionomer content and catalyst loading of 66.7 wt% and 5.0 mg cm-2, respectively. The highest maximum power density is ca. 32 mW cm-2 with a relatively low PtRu content (2 mgPtRu cm-2). This study overcomes the drawbacks of conventional graphene-based electrodes using a nano-sized graphene-based catalyst and further shows the feasibility of their potential applications in DMFC systems.

COMBINED SORBENT/CATALYST MEDIA FOR DESTRUCTION OF HALOGENATED VOCS

EPA Science Inventory

Several chromium modified zeolites have been developed and tested for their ability to physisorb chlorinated VOCs (CVOCs) at ambient and then catalytically destroy them at elevated temperatures (ca. 300 degrees C). These dual function materials, which act as both sorbents and cat...

Pt Nanostructures/N-Doped Carbon hybrid, an Efficient Catalyst for Hydrogen Evolution/Oxidation Reactions: Enhancing its Base Media Activity through Bifunctionality of the Catalyst.

PubMed

Barman, Sudip; Kundu, Manas; Bhowmik, Tanmay; Mishra, Ranjit

2018-06-04

Design and synthesis of active catalyst for HER/HOR are important for the development of hydrogen based renewable technologies. We report synthesis of Pt nanostructures-N-doped carbon hybrid (Pt-(PtO2)-NSs/C) for HER/HOR applications. The HER activity of this Pt-(PtOx)-NSs/C catalyst is 4 and 6.5 times better than commercial Pt/C in acid and base. The catalyst exhibits a current density of 10 mA/cm2 at overpotentials of 5 and 51 mV with tafel slopes of 29 and 64mV/dec in in 0.5 M H2SO4 and 0.5 M KOH. This catalyst also showed superior HOR activity at all pH values. The HER/HOR activity of Pt-(PtOx)-NSs/C and PtOx-free Pt-Nanostructures/C (PtNSs/C) catalysts are comparable in acid. The presence of PtOx in Pt-(PtOx)-NSs/C makes this Pt-catalyst more HER/HOR active in base media. The activity of Pt-(PtOx)NSs/C catalyst is 5 fold higher than that of PtNSs/C catalyst in basic medium although their activity is comparable in acid. Hydrogen binding energy and oxophilicity are the two equivalent descriptors for HER/HOR in basic media. We propose a bi-functional mechanism for the enhanced alkaline HER/HOR activity of Pt(PtOx)-NSs/C catalyst. In bi-functional Pt-(PtOx)-NSs/C catalyst, PtOx provide an active site for OH- adsorption to form OHads which reacts with hydrogen intermediate (Hads), present at neighbouring Pt sites to form H2O leading to enhancement of HOR activity in basic medium This work may provide opportunity to develop catalysts for various renewable energy technologies. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A review of carbon-based and non-carbon-based catalyst supports for the selective catalytic reduction of nitric oxide

PubMed Central

Anthonysamy, Shahreen Binti Izwan; Afandi, Syahidah Binti; Khavarian, Mehrnoush

2018-01-01

Various types of carbon-based and non-carbon-based catalyst supports for nitric oxide (NO) removal through selective catalytic reduction (SCR) with ammonia are examined in this review. A number of carbon-based materials, such as carbon nanotubes (CNTs), activated carbon (AC), and graphene (GR) and non-carbon-based materials, such as Zeolite Socony Mobil–5 (ZSM-5), TiO2, and Al2O3 supported materials, were identified as the most up-to-date and recently used catalysts for the removal of NO gas. The main focus of this review is the study of catalyst preparation methods, as this is highly correlated to the behaviour of NO removal. The general mechanisms involved in the system, the Langmuir–Hinshelwood or Eley–Riedeal mechanism, are also discussed. Characterisation analysis affecting the surface and chemical structure of the catalyst is also detailed in this work. Finally, a few major conclusions are drawn and future directions for work on the advancement of the SCR-NH3 catalyst are suggested. PMID:29600136

A review of carbon-based and non-carbon-based catalyst supports for the selective catalytic reduction of nitric oxide.

PubMed

Anthonysamy, Shahreen Binti Izwan; Afandi, Syahidah Binti; Khavarian, Mehrnoush; Mohamed, Abdul Rahman Bin

2018-01-01

Various types of carbon-based and non-carbon-based catalyst supports for nitric oxide (NO) removal through selective catalytic reduction (SCR) with ammonia are examined in this review. A number of carbon-based materials, such as carbon nanotubes (CNTs), activated carbon (AC), and graphene (GR) and non-carbon-based materials, such as Zeolite Socony Mobil-5 (ZSM-5), TiO 2 , and Al 2 O 3 supported materials, were identified as the most up-to-date and recently used catalysts for the removal of NO gas. The main focus of this review is the study of catalyst preparation methods, as this is highly correlated to the behaviour of NO removal. The general mechanisms involved in the system, the Langmuir-Hinshelwood or Eley-Riedeal mechanism, are also discussed. Characterisation analysis affecting the surface and chemical structure of the catalyst is also detailed in this work. Finally, a few major conclusions are drawn and future directions for work on the advancement of the SCR-NH 3 catalyst are suggested.

Foamed-metal-based catalytic afterburners in automotive exhaust systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pestryakov, A.N.; Ametov, V.A.

1994-08-10

Properties of exhaust afterburning catalysts based on porous cellular materials (foamed metals) have been investigated. Catalysts containing oxides of base metals provide a two-to-threefold reduction of CO emission. Platinum-containing foamed catalysts lower the toxicity of exhaust by 85-90%. A favorable effect is demonstrated by the combined use of afterburners and a motor oil additive based on ultradispersed copper.

Highly active, bi-functional and metal-free B4C-nanoparticle-modified graphite felt electrodes for vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Jiang, H. R.; Shyy, W.; Wu, M. C.; Wei, L.; Zhao, T. S.

2017-10-01

The potential of B4C as a metal-free catalyst for vanadium redox reactions is investigated by first-principles calculations. Results show that the central carbon atom of B4C can act as a highly active reaction site for redox reactions, due primarily to the abundant unpaired electrons around it. The catalytic effect is then verified experimentally by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests, both of which demonstrate that B4C nanoparticles can enhance the kinetics for both V2+/V3+ and VO2+/VO2+ redox reactions, indicating a bi-functional effect. The B4C-nanoparticle-modified graphite felt electrodes are finally prepared and tested in vanadium redox flow batteries (VRFBs). It is shown that the batteries with the prepared electrodes exhibit energy efficiencies of 88.9% and 80.0% at the current densities of 80 and 160 mA cm-2, which are 16.6% and 18.8% higher than those with the original graphite felt electrodes. With a further increase in current densities to 240 and 320 mA cm-2, the batteries can still maintain energy efficiencies of 72.0% and 63.8%, respectively. All these results show that the B4C-nanoparticle-modified graphite felt electrode outperforms existing metal-free catalyst modified electrodes, and thus can be promising electrodes for VRFBs.

Attrition resistant catalysts and sorbents based on heavy metal poisoned FCC catalysts

DOEpatents

Gangwal, S.; Jothimurugesan, K.

1999-07-27

A heavy metal poisoned, spent FCC catalyst is treated by chemically impregnating the poisoned catalyst with a new catalytic metal or metal salt to provide an attrition resistant catalyst or sorbent for a different catalytic or absorption process, such as catalysts for Fischer-Tropsh Synthesis, and sorbents for removal of sulfur gases from fuel gases and flue-gases. The heavy metal contaminated FCC catalyst is directly used as a support for preparing catalysts having new catalytic properties and sorbents having new sorbent properties, without removing or passivating the heavy metals on the spent FCC catalyst as an intermediate step.

Attrition resistant catalysts and sorbents based on heavy metal poisoned FCC catalysts

DOEpatents

Gangwal, Santosh; Jothimurugesan, Kandaswamy

1999-01-01

A heavy metal poisoned, spent FCC catalyst is treated by chemically impregnating the poisoned catalyst with a new catalytic metal or metal salt to provide an attrition resistant catalyst or sorbent for a different catalytic or absorption processes, such as catalysts for Fischer-Tropsh Synthesis, and sorbents for removal of sulfur gasses from fuel gases and flue-gases. The heavy metal contaminated FCC catalyst is directly used as a support for preparing catalysts having new catalytic properties and sorbents having new sorbent properties, without removing or "passivating" the heavy metals on the spent FCC catalyst as an intermediate step.

Synthesis Gas Conversion over Rh-Based Catalysts Promoted by Fe and Mn

DOE PAGES

Liu, Yifei; Göeltl, Florian; Ro, Insoo; ...

2017-06-13

Rh/SiO2 catalysts promoted with Fe and Mn are selective for synthesis gas conversion to oxygenates and light hydrocarbons at 523 K and 580 psi. Selective anchoring of Fe and Mn species on Rh nanoparticles was achieved by controlled surface reactions and was evidenced by ultraviolet–visible absorption spectroscopy, scanning transmission electron microscopy, and inductively coupled plasma absorption emission spectroscopy. The interaction between Rh and Fe promotes the selective production of ethanol through hydrogenation of acetaldehyde and enhances the selectivity toward C2 oxygenates, which include ethanol and acetaldehyde. The interaction between Rh and Mn increases the overall reaction rate and the selectivitymore » toward C2+ hydrocarbons. The combination of Fe and Mn on Rh/SiO2 results in trimetallic Rh-Fe-Mn catalysts that surpass the performance of their bimetallic counterparts. The highest selectivities toward ethanol (36.9%) and C2 oxygenates (39.6%) were achieved over the Rh-Fe-Mn ternary system with a molar ratio of 1:0.15:0.10, as opposed to the selectivities obtained over Rh/SiO2, which were 3.5% and 20.4%, respectively. The production of value-added oxygenates and C2+ hydrocarbons over this trimetallic catalyst accounted for 55% of the total products. X-ray photoelectron spectroscopy measurements suggest that significant fractions of the Fe and Mn species exist as metallic iron and manganese oxides on the Rh surface upon reduction. These findings are rationalized by density functional theory (DFT) calculations, which reveal that the exact state of metals on the surfaces is condition-dependent, with Mn present as Mn(I) and Mn(II) oxide on the Rh (211) step edges and Fe present as Fe(I) oxide on the step edge and metallic subsurface iron on both Rh steps and terraces. CO Fourier transform infrared spectroscopy and DFT calculations suggest that the binding of CO to Rh (211) step edges modified by Fe and/or manganese oxide is altered in comparison to CO adsorption on a clean Rh (211) surface. These results suggest that Mn2Ox species and Fe and Fe2O modify bonding at Rh step edges and shift reaction selectivity away from CH4.« less

Catalyseur d'hydrocraquage à base de sulfure de NiMo déposé sur une zéolithe HEMT modifiée

NASA Astrophysics Data System (ADS)

Baalala, M.; Becue, T.; Leglise, J.; Manoli, J. M.; van Gestel, J. N. M.; Lamotte, J.; Bensitel, M.; Goupil, J. M.; Cornet, D.

1999-02-01

Treating a NH4EMT zeolite with a solution of (NH4)2SiF6 at 80 °C affords a solid containing amorphous SiO2 intimately mixed with the zeolite. This acidic support EMT-Si was loaded with NiMo sulfide in order to prepare a bifunctional catalyst, which was tested for the hydrogenation of benzene and the hydrocracking of n-heptane. This NiMo/EMT-Si catalyst was found more active for hydrogenation than the analogous NiMo/HY. This is ascribed to a higher dispersion of the NiMo sulfide, which is almost equally shared between the internal mesopores in the modified EMT solid, and the fissures, which were created throughout the zeolite grains upon inserting the NiMo sulfide. The catalyst with the EMT-Si support was also found more active than the NiMo/HY for the hydrocracking of heptane, with a slightly higher selectivity into heptane isomers. Le traitement d'une zéolithe NH4EMT par une solution de (NH4)2SiF6 fournit un solide comportant une phase SiO2 amorphe intimement mélangée aux parties intactes de la zéolithe. Sur ce support acide EMT-Si, on a greffé un sulfure de NiMo afin de préparer un catalyseur bifonctionnel qui a été testé dans les réactions d'hydrogénation du benzène et d'hydrocraquage du n-heptane. Ce catalyseur NiMo/EMT-Si s'avère plus actif en hydrogénation que son analogue NiMo/HY, en raison d'une meilleure dispersion du sulfure de NiMo. Sur le solide EMT modifié, le sulfure se répartit à peu près également entre les mésopores internes et les fissures crées dans les grains de zéolithe lors de l'insertion du sulfure de NiMo. Au contraire sur le support Y, une partie du sulfure est externe aux grains de zéolithe et inactive en catalyse. Le catalyseur NiMo/EMT-Si est aussi trouvé plus actif que le NiMo/HY en hydrocraquage du n-heptane, et un peu plus sélectif en isomères.

Dual properties of a hydrogen oxidation Ni-catalyst entrapped within a polymer promote self-defense against oxygen.

PubMed

Oughli, Alaa A; Ruff, Adrian; Boralugodage, Nilusha Priyadarshani; Rodríguez-Maciá, Patricia; Plumeré, Nicolas; Lubitz, Wolfgang; Shaw, Wendy J; Schuhmann, Wolfgang; Rüdiger, Olaf

2018-02-28

The Ni(P 2 N 2 ) 2 catalysts are among the most efficient non-noble-metal based molecular catalysts for H 2 cycling. However, these catalysts are O 2 sensitive and lack long term stability under operating conditions. Here, we show that in a redox silent polymer matrix the catalyst is dispersed into two functionally different reaction layers. Close to the electrode surface is the "active" layer where the catalyst oxidizes H 2 and exchanges electrons with the electrode generating a current. At the outer film boundary, insulation of the catalyst from the electrode forms a "protection" layer in which H 2 is used by the catalyst to convert O 2 to H 2 O, thereby providing the "active" layer with a barrier against O 2 . This simple but efficient polymer-based electrode design solves one of the biggest limitations of these otherwise very efficient catalysts enhancing its stability for catalytic H 2 oxidation as well as O 2 tolerance.

Encapsulated heterogeneous base catalysts onto SBA-15 nanoporous material as highly active catalysts in the transesterification of sunflower oil to biodiesel

NASA Astrophysics Data System (ADS)

Albayati, Talib M.; Doyle, Aidan M.

2015-02-01

Alkali metals and their hydroxides, Na, NaOH, Li, and LiOH, were encapsulated onto SBA-15 nanoporous material as highly active catalysts for the production of biodiesel fuel from sunflower oil. The incipient wetness impregnation method was adopted for the prepared catalysts. The characterization properties of the catalysts and unmodified SBA-15 were determined using X-ray diffraction, scanning electron microscopy, EDAX, nitrogen adsorption-desorption porosimetry (Brunauer-Emmett-Teller), Fourier-transform infrared spectroscopy, and transmission electron microscopy. Transesterification was conducted in a batch reactor at atmospheric pressure and 65 °C. The catalysts were highly active with yields of fatty acid methyl ester (FAME) in the range 96-99 %. Na/SBA-15 catalyst was reused for seven consecutive cycles under the same reaction conditions; the yield to FAME on the final cycle was 96 %. This study shows that the alkali metals and their hydroxides supported on SBA-15-based catalyst are excellent catalysts for the biodiesel reaction.

NREL Research Advances Hydrogen Production Efforts | News | NREL

Science.gov Websites

-effective, however. The use of cheaper molecular catalysts instead of precious metals has been proposed, but -based catalysts. Instead, the NREL researchers decided to examine molecular catalysts outside of the the semiconductor and bond the molecular catalyst to the TiO2. Their work showed molecular catalysts

Nano-array based monolithic catalysts: Concept, rational materials design and tunable catalytic performance

DOE PAGES

Ren, Zheng; Guo, Yanbing; Gao, Pu-Xian

2015-03-20

Monolithic catalysts, also known as structured catalysts, represent an important catalyst configuration widely used in automotive, chemical, and energy industries. However, several issues associated with washcoat based monolithic catalyst preparation are ever present, such as compromised materials utilization efficiency due to a less-than-ideal wash coating process, difficulty in precise and optimum microstructure control and lack of structure-property correlation. Here, in this mini-review, we introduce the concept of nano-array catalyst, a new type of monolithic catalyst featuring high catalyst utilization efficiency, good thermal/mechanical robustness, and catalytic performance tunability. A comprehensive overview is presented with detailed discussion of the strategies for nano-arraymore » catalyst preparation and rational catalytic activity adjustment enabled by the well-defined nano-array geometry. Specifically their scalable fabrication processes are reviewed in conjunction with discussion of their various catalytic oxidation reaction performances at low temperature. Finally, we hope this review will serve as a timely and useful research guide for rational design and utilization of the new type of monolithic catalysts.« less

Attrition Resistant Fischer-Tropsch Catalysts Based on FCC Supports

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adeyiga, Adeyinka

2010-02-05

Commercial spent fluid catalytic cracking (FCC) catalysts provided by Engelhard and Albemarle were used as supports for Fe-based catalysts with the goal of improving the attrition resistance of typical F-T catalysts. Catalysts with the Ruhrchemie composition (100 Fe/5 Cu/4.2 K/25 spent FCC on mass basis) were prepared by wet impregnation. XRD and XANES analysis showed the presence of Fe{sub 2}O{sub 3} in calcined catalysts. FeC{sub x} and Fe{sub 3}O{sub 4} were present in the activated catalysts. The metal composition of the catalysts was analyzed by ICP-MS. F-T activity of the catalysts activated in situ in CO at the same conditionsmore » as used prior to the attrition tests was measured using a fixed bed reactor at T = 573 K, P = 1.38 MPa and H{sub 2}:CO ratio of 0.67. Cu and K promoted Fe supported over Engelhard provided spent FCC catalyst shows relatively good attrition resistance (8.2 wt% fines lost), high CO conversion (81%) and C{sub 5}+ hydrocarbons selectivity (18.3%).« less

Metal-free carbon materials-catalyzed sulfate radical-based advanced oxidation processes: A review on heterogeneous catalysts and applications.

PubMed

Zhao, Qingxia; Mao, Qiming; Zhou, Yaoyu; Wei, Jianhong; Liu, Xiaocheng; Yang, Junying; Luo, Lin; Zhang, Jiachao; Chen, Hong; Chen, Hongbo; Tang, Lin

2017-12-01

In recent years, advanced oxidation processes (AOPs), especially sulfate radical based AOPs have been widely used in various fields of wastewater treatment due to their capability and adaptability in decontamination. Recently, metal-free carbon materials catalysts in sulfate radical production has been more and more concerned because these materials have been demonstrated to be promising alternatives to conventional metal-based catalysts, but the review of metal-free catalysts is rare. The present review outlines the current state of knowledge on the generation of sulfate radical using metal-free catalysts including carbon nanotubes, graphene, mesoporous carbon, activated carbon, activated carbon fiber, nanodiamond. The mechanism such as the radical pathway and non-radical pathway, and factors influencing of the activation of sulfate radical was also be revealed. Knowledge gaps and research needs have been identified, which include the perspectives on challenges related to metal-free catalyst, heterogeneous metal-free catalyst/persulfate systems and their potential in practical environmental remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Two-Dimensional N,S-Codoped Carbon/Co 9 S 8 Catalysts Derived from Co(OH) 2 Nanosheets for Oxygen Reduction Reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, Shaofang; Zhu, Chengzhou; Song, Junhua

Investigation of highly active and cost-efficient electrocatalysts for oxygen reduction reaction is of great importance in a wide range of clean energy devices, including fuel cells and metal-air batteries. Herein, the simultaneous formation of Co9S8 and N,S-codoped carbon was achieved in a dual templates system. First, Co(OH)2 nanosheets and tetraethyl orthosilicate were utilized to direct the formation of two-dimensional carbon precursors, which were then dispersed into thiourea solution. After subsequent pyrolysis and templates removal, N/S-codoped porous carbon sheets confined Co9S8 catalysts (Co9S8/NSC) were obtained. Owing to the morphological and compositional advantages as well as the synergistic effects, the resultant Co9S8/NSCmore » catalysts with modified doping level and pyrolysis degree exhibit superior ORR catalytic activity and long-term stability compared with the state-of-the-art Pt/C catalyst in alkaline media. Remarkably, the as-prepared carbon composites also reveal exceptional tolerance of methanol, indicating their potential applications in fuel cells.« less

New insights into proton surface mobility processes in PEMFC catalysts using isotopic exchange methods.

PubMed

Ferreira-Aparicio, Paloma

2009-09-01

The surface chemistry and the adsorption/desorption/exchange behavior of a proton-exchange membrane fuel cell catalyst are analyzed as a case study for the development of tailor-made support materials of enhanced performance and stability. By using H2, D2, and CO as probe molecules, the relevance of some surface functional groups of the catalyst support on several diffusion processes taking place during the adsorption is shown. Sulfonic groups associated with the vulcanized carbon black surface have been detected by means of spectroscopic techniques (X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy) and by analysis of the desorbed products during temperature-programmed desorption tests by mass spectrometry. Such hydrophilic species have been observed to favor proton surface mobility and exchange with Pt-adsorbed deuterium even in the presence of adsorbed CO. This behavior is relevant both for the proper characterization of these kinds of catalysts using adsorption probes and for the design of new surface-modified carbon supports, enabling alternative proton-transfer pathways throughout the catalytic layers toward the membrane.

Insights into the effect of the catalytic functions on selective production of ethylene glycol from lignocellulosic biomass over carbon supported ruthenium and tungsten catalysts.

PubMed

Ribeiro, Lucília Sousa; Órfão, José J Melo; Pereira, Manuel Fernando Ribeiro

2018-05-09

The one-pot conversion of cellulose to ethylene glycol (EG) was investigated using a combination of a ruthenium catalyst supported on carbon nanotubes modified with nitric acid (Ru/CNT 1 ) and a tungsten catalyst supported on commercial non-treated carbon nanotubes (W/CNT 0 ). This physical mixture allowed to obtain an EG yield of 41% in just 5 h at 205 °C and 50 bar of H 2 , which overcame the result obtained using a Ru-W bimetallic catalyst supported on commercial carbon nanotubes (35%) under the same conditions. Tissue paper, a potential waste cellulosic material, and eucalyptus were also tested under the same conditions and EG yields of 34 and 36%, respectively, were attained over the aforementioned catalytic physical mixture. To the best of our knowledge, this work presents for the first time the catalytic conversion of lignocellulosic materials, namely tissue paper and eucalyptus, directly into EG by an environmentally friendly process. Copyright © 2018 Elsevier Ltd. All rights reserved.

Hybrid Mo-CT nanowires as highly efficient catalysts for direct dehydrogenation of isobutane.

PubMed

Mu, Jiali; Shi, Junjun; France, Liam John; Wu, Yongshan; Zeng, Qiang; Liu, Baoan; Jiang, Lilong; Long, Jinxing; Li, Xuehui

2018-06-20

Direct dehydrogenation of isobutane to isobutene has drawn extensive attention for synthesizing various chemicals. The Mo-based catalysts hold promise as an alternative to the toxic CrOx- and scarce Pt-based catalysts. However, the low activity and rapid deactivation of the Mo-based catalysts greatly hinder their practical applications. Herein, we demonstrate a feasible approach towards the development of efficient and non-noble metal dehydrogenation catalysts basing on Mo-CT hybrid nanowires calcined at different temperatures. In particular, the optimal Mo-C700 catalyst exhibits isobutane consumption rate of 3.9 mmol g-1 h-1, and isobutene selectivity of 73% with production rate of 2.8 mmol g-1 h-1. The catalyst maintained 90% of its initial activity after 50 h of reaction. Extensive characterizations reveal that such prominent performance is well-correlated with the adsorption abilities of isobutane and isobutene, and the formation of η-MoC species. By contrast, the generation of β-Mo2C crystalline phase during long-term reaction causes minor decline in activity. Compared to MoO2 and β-Mo2C, η-MoC plays a role more likely in suppressing the cracking reaction. This work demonstrates a feasible approach towards the development of efficient and non-noble metal dehydrogenation catalysts.

Design and application of sporopollenin microcapsule supported palladium catalyst: Remarkably high turnover frequency and reusability in catalysis of biaryls.

PubMed

Baran, Talat; Sargin, Idris; Kaya, Murat; Menteş, Ayfer; Ceter, Talip

2017-01-15

Bio-based catalyst support materials with high thermal and structural stability are desired for catalysts systems requiring harsh conditions. In this study, a thermally stable palladium catalyst (up to 440°C) was designed from sporopollenin, which occurs naturally in the outer exine layer of pollens and is widely acknowledged as chemically very stable and inert biological material. Catalyst design procedure included (1) extraction of sporopollenin microcapsules from Betula pendula pollens (∼25μm), (2) amino-functionalisation of the microcapsules, (3) Schiff base modification and (4) preparation of Pd(II) catalyst. The catalytic activity of the sporopollenin microcapsule supported palladium catalyst was tested in catalysis of biaryls by following a fast, simple and green microwave-assisted method. We recorded outstanding turnover number (TON: 40,000) and frequency (TOF: 400,000) for the catalyst in Suzuki coupling reactions. The catalyst proved to be reusable at least in eight cycles. The catalyst can be suggested for different catalyst systems due to its thermal and structural durability, reusability, inertness to air and its eco-friendly nature. Copyright © 2016 Elsevier Inc. All rights reserved.

Development and Progress in Enabling the Photocatalyst Ti02 Visible-Light-Active

NASA Technical Reports Server (NTRS)

Levine, Lanfang H.; Coutts, Janelle L.; Clausen, Christian A.

2011-01-01

Photocatalytic oxidation (PCO) of organic contaminants is a promising air and water quality management approach which offers energy and cost savings compared to thermal catalytic oxidation (TCO). The most widely used photocatalyst, anatase TiO2, has a wide band gap (3.2 eV) and is activated by UV photons. Since solar radiation consists of less than 4% UV, but contains 45% visible light, catalysts capable of utilizing these visible photons need to be developed to make peo approaches more efficient, economical, and safe. Researchers have attempted various approaches to enable TiO2 to be visible-light-active with varied degrees of success'. Strategies attempted thus far fall into three categories based on their electrochemical' mechanisms: 1) narrowing the band gap of TiO2 by implantation of transition metal elements or nonmetal elements such as N, S, and C, 2) modifying electron-transfer processes during PCO by adsorbing sensitizing dyes, and 3) employing light-induced interfacial electron transfer in the heteronanojunction systems consisting of narrow band gap semiconductors represented by metal sulfides and TiO2. There are diverse technical approaches to implement each of these strategies. This paper presents a review of these approaches and results of the photocatalytic activity and photonic efficiency of the end .products under visible light. Although resulting visible-light-active (VLA) photocatalysts show promise, there is often no comparison with unmodified TiO2 under UV. In a limited number of studies where such comparison was provided, the UV-induced catalytic activity of bare TiO2 is much greater than the visible-light-induced catalytic activity of the VLA catalyst. Furthermore, VLA-catalysts have much lower quantum efficiency compared to the approx.50% quantum efficiency of UV-catalysts. This stresses the need for continuing research in this area.

On two alternative mechanisms of ethane activation over ZSM-5 zeolite modified by Zn2+ and Ga1+ cations.

PubMed

Kazansky, V B; Subbotina, I R; Rane, N; van Santen, R A; Hensen, E J M

2005-08-21

The activation of ethane over zinc- and gallium-modified HZSM-5 dehydrogenation catalysts was studied by diffuse reflectance infrared spectroscopy. Hydrocarbon activation on HZSM-5 modified by bivalent Zn and univalent Ga cations proceeds via two distinctly different mechanisms. The stronger molecular adsorption of ethane by the acid-base pairs formed by distantly separated cationic Zn2+ and basic oxygen sites results already at room temperature in strong polarizability of adsorbed ethane and subsequent heterolytic dissociative adsorption at moderate temperatures. In contrast, molecular adsorption of ethane on Ga+ cations is weak. At high temperatures dissociative hydrocarbon adsorption takes place, resulting in the formation of ethyl and hydride fragments coordinating to the cationic gallium species. Whereas in the zinc case a Brønsted acid proton is formed upon ethane dissociation, decomposition of the ethyl fragment on gallium results in gallium dihydride species and does not lead to Brønsted acid protons. This difference in alkane activation has direct consequences for hydrocarbon conversions involving dehydrogenation.

Immobilization of nanobeads on a surface to control the size, shape and distribution of pores in electrochemically generated sol-gel films.

PubMed

Ciabocco, Michela; Berrettoni, Mario; Zamponi, Silvia; Cox, James A

2015-07-01

Electrochemically assisted deposition of an ormosil film at a potential where hydrogen ion is generated as the catalyst yields insulating films on electrodes. When the base electrode is modified with 20-nm poly(styrene sulfonate), PSS, beads bound to the surface with 3-aminopropyltriethoxysilane (APTES) and using (CH 3 ) 3 SiOCH 3 as the precursor, the resulting film of organically modified silica (ormosil) has cylindrical channels that reflect both the diameter of the PSS and the distribution of the APTES-PSS on the electrode. At an electrode modified by a 20-min immersion in 0.5 mmol dm -3 APTES followed by a 30-s immersion in PSS, a 20-min electrolysis at 1.5 V in acidified (CH 3 ) 3 SiOCH 3 resulted in an ormosil film with 20-nm pores separated by 100 nm. Cyclic voltammetry of Ru(CN) 6 4- at scan rates above 5 mVs -1 yielded currents controlled primarily by linear diffusion. Below 5 mVs -1 , convection rather than the expected factor, radial diffusion, apparently limited the current.

A delafossite-based copper catalyst for sustainable Cl2 production by HCl oxidation.

PubMed

Mondelli, Cecilia; Amrute, Amol P; Schmidt, Timm; Pérez-Ramírez, Javier

2011-07-07

A copper catalyst based on a delafossite precursor (CuAlO(2)) displays high activity and extraordinary lifetime in the gas-phase oxidation of HCl to Cl(2), representing a cost-effective alternative to RuO(2)-based catalysts for chlorine recycling. This journal is © The Royal Society of Chemistry 2011

Enhanced activity of Pt/CNTs anode catalyst for direct methanol fuel cells using Ni2P as co-catalyst

NASA Astrophysics Data System (ADS)

Li, Xiang; Luo, Lanping; Peng, Feng; Wang, Hongjuan; Yu, Hao

2018-03-01

The direct methanol fuel cell is a promising energy conversion device because of the utilization of the state-of-the-art platinum (Pt) anode catalyst. In this work, novel Pt/Ni2P/CNTs catalysts were prepared by the H2 reduction method. It was found that the activity and stability of Pt for methanol oxidation reaction (MOR) could be significantly enhanced while using nickel phosphide (Ni2P) nanoparticles as co-catalyst. X-ray photoelectron spectroscopy revealed that the existence of Ni2P affected the particle size and electronic distribution of Pt obviously. Pt/CNTs catalyst, Pt/Ni2P/CNTs catalysts with different Ni2P amount were synthesized, among which Pt/6%Ni2P/CNTs catalyst exhibited the best MOR activity of 1400 mAmg-1Pt, which was almost 2.5 times of the commercial Pt/C-JM catalyst. Moreover, compared to other Pt-based catalysts, this novel Pt/Ni2P/CNTs catalyst also exhibited higher onset current density and better steady current density. The result of this work may provide positive guidance to the research on high efficiency and stability of Pt-based catalyst for direct methanol fuel cells.

Designing supported palladium-on-gold bimetallic nano-catalysts for controlled hydrogenation of acetylene in large excess of ethylene

NASA Astrophysics Data System (ADS)

Malla, Pavani

Ethylene is used as a starting point for many chemical intermediates in the petrochemical industry. It is predominantly produced through steam cracking of higher hydrocarbons (ethane, propane, butane, naphtha, and gas oil). During the cracking process, a small amount of acetylene is produced as a side product. However, acetylene must be removed since it acts as a poison for ethylene polymerization catalysts at even ppm concentrations (>5 ppm). Thus, the selective hydrogenation of acetylene to ethylene is an important process for the purification of ethylene. Conventional, low weight loading Pd catalysts are used for this selective reaction in high concentration ethylene streams. Gold was initially considered to be catalytically inactive for a long time. This changed when gold was seen in the context of the nanometric scale, which has indeed shown it to have excellent catalytic activity as a homogeneous or a heterogeneous catalyst. Gold is proved to have high selectivity to ethylene but poor at conversion. Bimetallic Au and Pd catalysts have exhibited superior activity as compared to Pd particles in semi-hydrogenation. Hydrogenation of acetylene was tested using this bimetallic combination. The Pd-on-Au bimetallic catalyst structure provides a new synthesis approach in improving the catalytic properties of monometallic Pd materials. TiO 2 as a support material and 0.05%Pd loading on 1%Au on titania support and used different treatment methods like washing plasma and reduction between the two metal loadings and was observed under 2:1 ratio. In my study there were two set of catalysts which were prepared by a modified incipient wetness impregnation technique. Out of all the reaction condition the catalyst which was reduced after impregnating gold and then impregnating palladium which was further treated in non-thermal hydrogen plasma and then pretreated in hydrogen till 250°C for 1 hour produced the best activity of 76% yield at 225°C. Stability tests were conducted on the catalysts which were followed by TGA analysis to analyze the coke formation on the catalyst in a period of time at a particular temperature. The catalysts were characterized by the hydrogen chemisorption and atomic absorption spectroscopy.

Evaluation of the Effect of Water Vapor On the Performance of NASA's NMRO Catalysts for Carbon Monoxide Oxidation

NASA Technical Reports Server (NTRS)

Akyurtlu, Ates; Akyurtlu, Jale F.; Ammons, Vaughnery; Battle, Taikelia; Gay, Amy; Bray, Kyle; Washington, Boe; Schryer, David (Technical Monitor); Jordan, Jeff (Technical Monitor)

2002-01-01

The Noble Metal Reducible Oxide (NMRO) catalysts for the low temperature oxidation of carbon monoxide were developed by NASA for the reoxidation of carbon monoxide which forms by the dissociation of carbon dioxide during the operation of sealed carbon dioxide lasers. The NMRO catalyst, which consists of a noble metal in conjunction with a reducible metal oxide, was evaluated under conditions that will be encountered in a CO2 laser operation, namely temperatures in the range 298 to 373 K and no significant reaction gas components other than CO, CO2 and O2. The NMRO catalysts may have significant potential for spin-off applications such as the prevention of carbon monoxide build-up in closed spaces as in space vehicle cabins or submarines, and the elimination of the cold start-up problem of automobile exhaust catalysts. The most significant difference in the conditions of these possible future applications is the high moisture content of the gases to be processed. Lack of understanding of the effects of water vapor and high temperature on catalyst activity and operation for extended periods are currently the main stumbling blocks for the transfer of this NASA technology to be used for commercial purposes. In the original proposal the following objectives were stated: To obtain experimental data on the adsorption, desorption and reaction characteristics of CO and CO2 the catalysts under high moisture conditions; to collect evidence on the presence of carbonate and hydroxyl surface species and their involvement in the CO oxidation mechanism; and to model the reaction system using a Monte-Carlo simulation to gain insight on the various steps involved. After the work has commenced the NASA technical monitor Mr. David Scheyer informed us that there was increased interest in the possible use of the NMRO catalysts as automobile exhaust catalysts and therefore NASA wanted to know whether the catalysts can operate at high temperatures as well as with high moisture gases. At that meeting it was decided that investigation of the high temperature performance of the NMRO catalysts should be given priority and replace the Monte-Carlo simulation objective. As a result, the modified objectives of the investigation were taken as the investigation of the high-temperature activity of the NMRO catalysts, and the effect of water vapor on the performance of these catalysts.

Electronic modification of Pt via Ti and Se as tolerant cathodes in air-breathing methanol microfluidic fuel cells.

PubMed

Ma, Jiwei; Habrioux, Aurélien; Morais, Cláudia; Alonso-Vante, Nicolas

2014-07-21

We reported herein on the use of tolerant cathode catalysts such as carbon supported Pt(x)Ti(y) and/or Pt(x)Se(y) nanomaterials in an air-breathing methanol microfluidic fuel cell. In order to show the improvement of mixed-reactant fuel cell (MRFC) performances obtained with the developed tolerant catalysts, a classical Pt/C nanomaterial was used for comparison. Using 5 M methanol concentration in a situation where the fuel crossover is 100% (MRFC-mixed reactant fuel cell application), the maximum power density of the fuel cell with a Pt/C cathodic catalyst decreased by 80% in comparison with what is observed in the laminar flow fuel cell (LFFC) configuration. With Pt(x)Ti(y)/C and Pt(x)Se(y)/C cathode nanomaterials, the performance loss was only 55% and 20%, respectively. The evaluation of the tolerant cathode catalysts in an air-breathing microfluidic fuel cell suggests the development of a novel nanometric system that will not be size restricted. These interesting results are the consequence of the high methanol tolerance of these advanced electrocatalysts via surface electronic modification of Pt. Herein we used X-ray photoelectron and in situ FTIR spectroscopies to investigate the origin of the high methanol tolerance on modified Pt catalysts.

A novel iron (Ⅱ) polyphthalocyanine catalyst assembled on graphene with significantly enhanced performance for oxygen reduction reaction in alkaline medium

NASA Astrophysics Data System (ADS)

Lin, Lin; Li, Meng; Jiang, Liqing; Li, Yongfeng; Liu, Dajun; He, Xingquan; Cui, Lili

2014-12-01

To realize the large-scale commercial application of direct methanol fuel cells (DMFCs), the catalysts for oxygen reduction reaction (ORR) are the crucial obstacle. Here, an efficient non-noble-metal catalyst for ORR, denoted FePPc/PSS-Gr, has been obtained by anchoring p-phenyl-bis(3,4-dicyanophenyl) ether iron(Ⅱ) polyphthalocyanine (FePPc) on poly(sodium-p-styrenesulfonate) (PSS) modified graphene (PSS-Gr) through a solvothermally assisted π-π assembling approach. The Ultraviolet-visible (UV-vis) spectroscopy, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) results reveal the π-π interaction between FePPc and PSS-Gr. The rotating disk electrode (RDE) and rotating ring disk electrode (RRDE) measurements show that the proposed catalyst possesses an excellent catalytic performance towards ORR comparable with the commercial Pt/C catalyst in alkaline medium, such as high onset potential (-0.08 V vs. SCE), half-wave potential (-0.19 V vs. SCE), better tolerance to methanol crossover, excellent stability (81.1%, retention after 10,000 s) and an efficient four-electron pathway. The enhanced electrocatalytic performance could be chiefly attributed to its large electrochemically accessible surface area, fast electron transfer rate of PSS-Gr, in particular, the synergistic effect between the FePPc moieties and the PSS-Gr sheets.

Effect of different promoter precursors in a model Ru-Cs/graphite system on the catalytic selectivity for Fischer-Tropsch reaction

NASA Astrophysics Data System (ADS)

Eslava, José L.; Iglesias-Juez, Ana; Fernández-García, Marcos; Guerrero-Ruiz, Antonio; Rodríguez-Ramos, Inmaculada

2018-07-01

The effect of using two different promoter precursors on the Fischer-Tropsch synthesis was studied over cesium promoted ruthenium catalysts supported on a high surface area graphite support. In this work we reveal significant modifications in the selectivity values for Fischer-Tropsch reaction depending on the Cs promoter precursor (CsCl vs CsNO3). Specifically the bimetallic catalyst (4Ru-4Cs), prepared from nitrates both for metal and promoter precursors, showed a high selectivity to CO2 during reaction. By modifying the cesium precursor, it was possible to inhibit the water gas shift reaction, decreasing significantly the selectivity to CO2. In order to understand the chemical origin of these modifications a careful characterization of the materials was performed including: X-ray absorption near edge spectroscopy, transmission electron microscopy measurements, temperature programmed reduction studies, determination of the CO uptakes on the catalysts and the evolution of the CO adsorption heats as a function of surface coverages. It was found that upon reduction and under reaction atmosphere the promoter in the ex-nitrate catalyst appears as Cs2O which is considered responsible of the CO2 production, while in the catalysts prepared with Cs chloride the promoter remains as CsCl suffering a slight partial reduction.

Influence of various carbon nano-forms as supports for Pt catalyst on proton exchange membrane fuel cell performance

NASA Astrophysics Data System (ADS)

Bharti, Abha; Cheruvally, Gouri

2017-08-01

In this study, we discuss the influence of various carbon supports for Pt on proton exchange membrane (PEM) fuel cell performance. Here, Pt supported on various carbon nano-forms [Pt/carbon black (Pt/CB), Pt/single-walled carbon nanotubes (Pt/SWCNT), Pt/multi-walled carbon nanotubes (Pt/MWCNT) and Pt/graphene (Pt/G)] are synthesized by a facile, single step, microwave-assisted, modified chemical reduction route. Their physical, chemical and electrochemical characteristics pertaining to oxygen reduction reaction (ORR) catalytic activity and stability in PEM fuel cell are studied in detail by various techniques and compared. The study shows that the different carbon supports does not significantly affect the Pt particle size during synthesis, but leads to different amount of defective sites in the carbon framework which influence both the availability of active metal nano-catalysts and metal-support interaction. In-situ electrochemical investigations reveal that the different carbon supports influence both ORR catalytic activity and stability of the catalyst. This is further corroborated by the demonstration of varying polarization characteristics on PEM fuel cell performance by different carbon supported Pt catalysts. This study reveals MWCNT as the most suitable carbon support for Pt catalyst, exhibiting high activity and stability for ORR in PEM fuel cell.

Cerium and lanthanum-modified, magnetically separable nano-catalysts for water treatment

EPA Science Inventory

Currently, people are exposed to many chemicals in the environment by a variety of chemicals used and produced for anthropogenic activities. Many studies reportadverse effects of chemicals in the environment on the health of humans and animals; such as endocrine disruption, femin...

A new chitosan Schiff base supported Pd(II) complex for microwave-assisted synthesis of biaryls compounds

NASA Astrophysics Data System (ADS)

Baran, Talat

2017-08-01

In this study, a new heterogeneous palladium (II) catalyst that contains O-carboxymethyl chitosan Schiff base has been designed for Suzuki coupling reactions. The chemical structures of the synthesized catalyst were characterized with the FTIR, TG/DTG, ICP-OES, SEM/EDAX, 1H NMR, 13C NMR, GC/MS, XRD, and magnetic moment techniques. The reusability and catalytic behavior of heterogeneous catalyst was tested towards Suzuki reactions. As a result of the tests, excellent selectivity was obtained, and by-products of homo coupling were not seen in the spectra. The biaryls products were identified on a GC/MS. In addition, it was determined in the reusability tests that the catalysts could be used several times (seven runs). More importantly, with very low catalyst loading (6 × 10-3 mol %) in very short reaction time (5 min), chitosan Schiff base supported Pd(II) complex gave high TON and TOF values. These findings showed that Schiff base supported Pd(II) catalyst is suitable for Suzuki cross coupling reactions.

Nanocrystalline Iron-Ore-Based Catalysts for Fischer-Tropsch Synthesis.

PubMed

Yong, Seok; Park, Ji Chan; Lee, Ho-Tae; Yang, Jung-Il; Hong, SungJun; Jung, Heon; Chun, Dong Hyun

2016-02-01

Nanocrystalline iron ore particles were fabricated by a wet-milling process using an Ultra Apex Mill, after which they were used as raw materials of iron-based catalysts for low-temperature Fischer-Tropsch synthesis (FTS) below 280 degrees C, which usually requires catalysts with a high surface area, a large pore volume, and a small crystallite size. The wet-milling process using the Ultra Apex Mill effectively destroyed the initial crystallite structure of the natural iron ores of several tens to hundreds of nanometers in size, resulting in the generation of nanocrystalline iron ore particles with a high surface area and a large pore volume. The iron-ore-based catalysts prepared from the nanocrystalline iron ore particles effectively catalyzed the low-temperature FTS, displaying a high CO conversion (about 90%) and good C5+ hydrocarbon productivity (about 0.22 g/g(cat)(-h)). This demonstrates the feasibility of using the iron-ore-based catalysts as inexpensive and disposable catalysts for the low-temperature FTS.

Effect of betaine in the successful synthesis of CoFe2O4 containing octahedron nanoparticles for electrocatalytic water oxidation

NASA Astrophysics Data System (ADS)

Valdez, R.; Olivas, A.; Grotjahn, D. B.; Barrios, E.; Arjona, N.; Antaño, R.; Oropeza-Guzman, M. T.

2017-12-01

The development of robust catalysts that oxidize water is necessary for their application in artificial photosynthesis cells. Here we report the synthesis and characterization of octahedral CoFe2O4 nanoparticles obtained through a novel aqueous method that employs betaine, (CH3)3+NCH2COO-, as the stabilizer agent. The synthetic conditions are modified changing the betaine content and the metal precursor ratios. These conditions modify the shape of CoFe2O4 finding both, octahedral and semi-spherical nanoparticles. Linear voltammetry measurements show the octahedral CoFe2O4 lead to an overpotential of ∼390 mV at the onset potential for water oxidation at alkaline conditions. Among the as-synthesized cobalt-ferrite nanomaterials, the CoFe(1:2)-C in the form of tiny nanoparticles performed a superior electrocatalytic water oxidation in alkaline conditions, showing an overpotential of ∼335 mV, which is lower than other similar catalysts in literature.

Single-catalyst high-weight% hydrogen storage in an N-heterocycle synthesized from lignin hydrogenolysis products and ammonia

PubMed Central

Forberg, Daniel; Schwob, Tobias; Zaheer, Muhammad; Friedrich, Martin; Miyajima, Nobuyoshi; Kempe, Rhett

2016-01-01

Large-scale energy storage and the utilization of biomass as a sustainable carbon source are global challenges of this century. The reversible storage of hydrogen covalently bound in chemical compounds is a particularly promising energy storage technology. For this, compounds that can be sustainably synthesized and that permit high-weight% hydrogen storage would be highly desirable. Herein, we report that catalytically modified lignin, an indigestible, abundantly available and hitherto barely used biomass, can be harnessed to reversibly store hydrogen. A novel reusable bimetallic catalyst has been developed, which is able to hydrogenate and dehydrogenate N-heterocycles most efficiently. Furthermore, a particular N-heterocycle has been identified that can be synthesized catalytically in one step from the main lignin hydrogenolysis product and ammonia, and in which the new bimetallic catalyst allows multiple cycles of high-weight% hydrogen storage. PMID:27762267

Single-catalyst high-weight% hydrogen storage in an N-heterocycle synthesized from lignin hydrogenolysis products and ammonia.

PubMed

Forberg, Daniel; Schwob, Tobias; Zaheer, Muhammad; Friedrich, Martin; Miyajima, Nobuyoshi; Kempe, Rhett

2016-10-20

Large-scale energy storage and the utilization of biomass as a sustainable carbon source are global challenges of this century. The reversible storage of hydrogen covalently bound in chemical compounds is a particularly promising energy storage technology. For this, compounds that can be sustainably synthesized and that permit high-weight% hydrogen storage would be highly desirable. Herein, we report that catalytically modified lignin, an indigestible, abundantly available and hitherto barely used biomass, can be harnessed to reversibly store hydrogen. A novel reusable bimetallic catalyst has been developed, which is able to hydrogenate and dehydrogenate N-heterocycles most efficiently. Furthermore, a particular N-heterocycle has been identified that can be synthesized catalytically in one step from the main lignin hydrogenolysis product and ammonia, and in which the new bimetallic catalyst allows multiple cycles of high-weight% hydrogen storage.

Catalyst recognition of cis-1,2-diols enables site-selective functionalization of complex molecules

NASA Astrophysics Data System (ADS)

Sun, Xixi; Lee, Hyelee; Lee, Sunggi; Tan, Kian L.

2013-09-01

Carbohydrates and natural products serve essential roles in nature, and also provide core scaffolds for pharmaceutical agents and vaccines. However, the inherent complexity of these molecules imposes significant synthetic hurdles for their selective functionalization and derivatization. Nature has, in part, addressed these issues by employing enzymes that are able to orient and activate substrates within a chiral pocket, which increases dramatically both the rate and selectivity of organic transformations. In this article we show that similar proximity effects can be utilized in the context of synthetic catalysts to achieve general and predictable site-selective functionalization of complex molecules. Unlike enzymes, our catalysts apply a single reversible covalent bond to recognize and bind to specific functional group displays within substrates. By combining this unique binding selectivity and asymmetric catalysis, we are able to modify the less reactive axial positions within monosaccharides and natural products.

RGO modified Ni doped FeOOH for enhanced electrochemical and photoelectrochemical water oxidation

NASA Astrophysics Data System (ADS)

Zhang, Xiaofan; Zhang, Bingyan; Liu, Shuangshuang; Kang, Hongwei; Kong, Weiqian; Zhang, Shouren; Shen, Yan; Yang, Baocheng

2018-04-01

Ni,Fe-based (oxy)hydroxides have been one of the most active catalysts for the oxygen evolution reaction. In this article, reduced graphene oxide supported Ni doped FeOOH (RGO/Ni:FeOOH) was prepared for electrochemical and photoelectrochemical (PEC) water oxidation. The RGO/Ni:FeOOH exhibited a lower over-potential (260 mV at 10 mA cm-2) and smaller Tafel slope (32.3 mV dec-1) than that of the FeOOH and Ni:FeOOH. Such significant enhancement is attributed to Ni doping and RGO, which reduce the over-potential, improve the conductivity and enlarge surface areas. Besides, RGO/Ni:FeOOH decorated the TiO2 nanorods (NRs) was also fabricated for photoelectrochemical (PEC) water oxidation, which exhibited a higher photocurrent density and lower onset potential than that of TiO2 NRs the bare under illumination due to the synergistic effect of RGO and Ni:FeOOH. These results demonstrate the RGO/Ni:FeOOH has great promising as a co-catalyst to improve the PEC performance.

TiO2-PANI/Cork composite: A new floating photocatalyst for the treatment of organic pollutants under sunlight irradiation.

PubMed

Sboui, Mouheb; Nsib, Mohamed Faouzi; Rayes, Ali; Swaminathan, Meenakshisundaram; Houas, Ammar

2017-10-01

A novel photocatalyst based on TiO 2 -PANI composite supported on small pieces of cork has been reported. It was prepared by simple impregnation method of the polyaniline (PANI)-modified TiO 2 on cork. The TiO 2 -PANI/Cork catalyst shows the unique feature of floating on the water surface. The as-synthesized catalyst was characterized by X-ray diffraction (XRD), scanning electron micrograph (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), UV-vis diffuse reflectance spectra (UV-vis DRS) and the Brunauer-Emmett-Teller (BET) surface area analysis. Characterization suggested the formation of anatase highly dispersed on the cork surface. The prepared floating photocatalyst showed high efficiency for the degradation of methyl orange dye and other organic pollutants under solar irradiation and constrained conditions, i.e., no-stirring and no-oxygenation. The TiO 2 -PANI/Cork floating photocatalyst can be reused for at least four consecutive times without significant decrease of the degradation efficiency. Copyright © 2017. Published by Elsevier B.V.

High mass resolution time of flight mass spectrometer for measuring products in heterogeneous catalysis in highly sensitive microreactors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andersen, T.; Jensen, R.; Christensen, M. K.

2012-07-15

We demonstrate a combined microreactor and time of flight system for testing and characterization of heterogeneous catalysts with high resolution mass spectrometry and high sensitivity. Catalyst testing is performed in silicon-based microreactors which have high sensitivity and fast thermal response. Gas analysis is performed with a time of flight mass spectrometer with a modified nude Bayard-Alpert ionization gauge as gas ionization source. The mass resolution of the time of flight mass spectrometer using the ion gauge as ionization source is estimated to m/{Delta}m > 2500. The system design is superior to conventional batch and flow reactors with accompanying product detectionmore » by quadrupole mass spectrometry or gas chromatography not only due to the high sensitivity, fast temperature response, high mass resolution, and fast acquisition time of mass spectra but it also allows wide mass range (0-5000 amu in the current configuration). As a demonstration of the system performance we present data from ammonia oxidation on a Pt thin film showing resolved spectra of OH and NH{sub 3}.« less

High mass resolution time of flight mass spectrometer for measuring products in heterogeneous catalysis in highly sensitive microreactors

NASA Astrophysics Data System (ADS)

Andersen, T.; Jensen, R.; Christensen, M. K.; Pedersen, T.; Hansen, O.; Chorkendorff, I.

2012-07-01

We demonstrate a combined microreactor and time of flight system for testing and characterization of heterogeneous catalysts with high resolution mass spectrometry and high sensitivity. Catalyst testing is performed in silicon-based microreactors which have high sensitivity and fast thermal response. Gas analysis is performed with a time of flight mass spectrometer with a modified nude Bayard-Alpert ionization gauge as gas ionization source. The mass resolution of the time of flight mass spectrometer using the ion gauge as ionization source is estimated to m/Δm > 2500. The system design is superior to conventional batch and flow reactors with accompanying product detection by quadrupole mass spectrometry or gas chromatography not only due to the high sensitivity, fast temperature response, high mass resolution, and fast acquisition time of mass spectra but it also allows wide mass range (0-5000 amu in the current configuration). As a demonstration of the system performance we present data from ammonia oxidation on a Pt thin film showing resolved spectra of OH and NH3.

Decorating CoP and Pt Nanoparticles on Graphitic Carbon Nitride Nanosheets to Promote Overall Water Splitting by Conjugated Polymers.

PubMed

Pan, Zhiming; Zheng, Yun; Guo, Fangsong; Niu, Pingping; Wang, Xinchen

2017-01-10

The splitting of water into H 2 and O 2 using solar energy is one of the key steps in artificial photosynthesis for the future production of renewable energy. Here, we show the first use of CoP and Pt nanoparticles as dual co-catalysts to modify graphitic carbon nitride (g-C 3 N 4 ) polymer to achieve overall water splitting under visible light irradiation. Our findings demonstrate that loading dual co-catalysts on delaminated g-C 3 N 4 imparts surface redox sites on the g-C 3 N 4 nanosheets that can not only promote catalytic kinetics but also promote charge separation and migration in the soft interface, thus improving the photocatalytic efficiency for overall water splitting. This robust, abundant, and stable photocatalyst based on covalent organic frameworks is demonstrated to hold great promise by forming heterojunctions with CoP and Pt for catalyzing the direct splitting of water into stoichiometric H 2 and O 2 using energy from photons. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

High performing and stable supported nano-alloys for the catalytic hydrogenation of levulinic acid to γ-valerolactone

PubMed Central

Luo, Wenhao; Sankar, Meenakshisundaram; Beale, Andrew M.; He, Qian; Kiely, Christopher J.; Bruijnincx, Pieter C. A.; Weckhuysen, Bert M.

2015-01-01

The catalytic hydrogenation of levulinic acid, a key platform molecule in many biorefinery schemes, into γ-valerolactone is considered as one of the pivotal reactions to convert lignocellulose-based biomass into renewable fuels and chemicals. Here we report on the development of highly active, selective and stable supported metal catalysts for this reaction and on the beneficial effects of metal nano-alloying. Bimetallic random alloys of gold-palladium and ruthenium-palladium supported on titanium dioxide are prepared with a modified metal impregnation method. Gold-palladium/titanium dioxide shows a marked,~27-fold increase in activity (that is, turnover frequency of 0.1 s−1) compared with its monometallic counterparts. Although ruthenium-palladium/titanium dioxide is not only exceptionally active (that is, turnover frequency of 0.6 s−1), it shows excellent, sustained selectivity to γ-valerolactone (99%). The dilution and isolation of ruthenium by palladium is thought to be responsible for this superior catalytic performance. Alloying, furthermore, greatly improves the stability of both supported nano-alloy catalysts. PMID:25779385

High mass resolution time of flight mass spectrometer for measuring products in heterogeneous catalysis in highly sensitive microreactors.

PubMed

Andersen, T; Jensen, R; Christensen, M K; Pedersen, T; Hansen, O; Chorkendorff, I

2012-07-01

We demonstrate a combined microreactor and time of flight system for testing and characterization of heterogeneous catalysts with high resolution mass spectrometry and high sensitivity. Catalyst testing is performed in silicon-based microreactors which have high sensitivity and fast thermal response. Gas analysis is performed with a time of flight mass spectrometer with a modified nude Bayard-Alpert ionization gauge as gas ionization source. The mass resolution of the time of flight mass spectrometer using the ion gauge as ionization source is estimated to m/Δm > 2500. The system design is superior to conventional batch and flow reactors with accompanying product detection by quadrupole mass spectrometry or gas chromatography not only due to the high sensitivity, fast temperature response, high mass resolution, and fast acquisition time of mass spectra but it also allows wide mass range (0-5000 amu in the current configuration). As a demonstration of the system performance we present data from ammonia oxidation on a Pt thin film showing resolved spectra of OH and NH(3).

Development of biomimetic catalytic oxidation methods and non-salt methods using transition metal-based acid and base ambiphilic catalysts.

PubMed

Murahashi, Shun-Ichi

2011-01-01

This review focuses on the development of ruthenium and flavin catalysts for environmentally benign oxidation reactions based on mimicking the functions of cytochrome P-450 and flavoenzymes, and low valent transition-metal catalysts that replace conventional acids and bases. Several new concepts and new types of catalytic reactions based on these concepts are described. (Communicated by Ryoji Noyori, M.J.A.).

Evolving Maturation of the Series-Bosch System

NASA Technical Reports Server (NTRS)

Stanley, Christine; Abney, Morgan B.; Barnett, Bill

2017-01-01

Human exploration missions to Mars and other destinations beyond low Earth orbit require highly robust, reliable, and maintainable life support systems that maximize recycling of water and oxygen. In order to meet this requirement, NASA has continued the development of a Series-Bosch System, a two stage reactor process that reduces carbon dioxide (CO2) with hydrogen (H2) to produce water and solid carbon. Theoretically, the Bosch process can recover 100% of the oxygen (O2) from CO2 in the form of water, making it an attractive option for long duration missions. The Series Bosch system includes a reverse water gas shift (RWGS) reactor, a carbon formation reactor (CFR), an H2 extraction membrane, and a CO2 extraction membrane. In 2016, the results of integrated testing of the Series Bosch system showed great promise and resulted in design modifications to the CFR to further improve performance. This year, integrated testing was conducted with the modified reactor to evaluate its performance and compare it with the performance of the previous configuration. Additionally, a CFR with the capability to load new catalyst and remove spent catalyst in-situ was built. Flow demonstrations were performed to evaluate both the catalyst loading and removal process and the hardware performance. The results of the integrated testing with the modified CFR as well as the flow demonstrations are discussed in this paper.

A novel alcohol/iron (III) fuel cell

NASA Astrophysics Data System (ADS)

Yi, Qingfeng; Zou, Tao; Zhang, Yuanyuan; Liu, Xiaoping; Xu, Guorong; Nie, Huidong; Zhou, Xiulin

2016-07-01

A novel alcohol fuel cell is constructed by using Fe3+ as the oxidation agent instead of the conventional O2. Various alcohols as the fuels are tested, including methanol, ethanol, n-propanol and iso-propanol. In this fuel cell, the anode catalysts tested are PdSn/β-cd-CNT, PdSn/CNT, Pd/β-cd-CNT, Pd/CNT and Pd/β-cd-C, prepared by using multi-walled carbon nanotube (CNT) and carbon powder (C), as well as β-cyclodexdrin (β-cd) modified CNT (β-cd-CNT) and β-cd modified C (β-cd-C), as the substrates to immobilize PdSn and Pd nanoparticles in glycol solvent. The as-synthesized PdSn/β-cd-CNT catalyst presents significantly higher electroactivity for alcohol oxidation than the conventional Pd/C catalyst. Fe3+ reduction reaction is carried out on the cathode made of carbon powder. The anolyte (alcohols in 1 mol L-1 NaOH) and catholyte (Fe3+ in 0.5 mol L-1 NaCl) are separated with a Nafion 117 membrane. Open circuit voltage (OCV) of the cell with the anode PdSn/β-cd-CNT is 1.14-1.22 V, depending upon the used alcohol. The maximum power densities with methanol, ethanol, n-propanol and iso-propanol fuels are 15.2, 16.1, 19.9 and 12.2 mW cm-2, respectively.

Method for providing a low density high strength polyurethane foam

DOEpatents

Whinnery, Jr., Leroy L.; Goods, Steven H.; Skala, Dawn M.; Henderson, Craig C.; Keifer, Patrick N.

2013-06-18

Disclosed is a method for making a polyurethane closed-cell foam material exhibiting a bulk density below 4 lbs/ft.sup.3 and high strength. The present embodiment uses the reaction product of a modified MDI and a sucrose/glycerine based polyether polyol resin wherein a small measured quantity of the polyol resin is "pre-reacted" with a larger quantity of the isocyanate in a defined ratio such that when the necessary remaining quantity of the polyol resin is added to the "pre-reacted" resin together with a tertiary amine catalyst and water as a blowing agent, the polymerization proceeds slowly enough to provide a stable foam body.

Modification of SiO2 nanowires with metallic nanocrystals from supercritical CO2.

PubMed

Ye, Xiang-Rong; Zhang, Hai-Feng; Lin, Yuehe; Wang, Lai-Sheng; Wai, Chien M

2004-01-01

Through hydrogen reduction of metal precursors in supercritical CO2, Cu, and Pd, nanocrystals were deposited onto SiO2 nanowires to form different types of nanostructured materials, including nanocrystal-nanowire, spherical aggregation-nanowire, shell-nanowire composites, and "mesoporous" metals supported by the framework of nanowires. This supercritical fluid deposition technique is an attractive approach for modifying nanowires because of its generality and simplicity; the modified nanowires could be useful as catalysts and for further fabrication of multifunctional composites.

Sol-gel based oxidation catalyst and coating system using same

NASA Technical Reports Server (NTRS)

Leighty, Bradley D. (Inventor); Watkins, Anthony N. (Inventor); Patry, JoAnne L. (Inventor); Schryer, Jacqueline L. (Inventor); Oglesby, Donald M. (Inventor)

2010-01-01

An oxidation catalyst system is formed by particles of an oxidation catalyst dispersed in a porous sol-gel binder. The oxidation catalyst system can be applied by brush or spray painting while the sol-gel binder is in its sol state.

Radio-Frequency-Based NH3-Selective Catalytic Reduction Catalyst Control: Studies on Temperature Dependency and Humidity Influences

PubMed Central

Dietrich, Markus; Hagen, Gunter; Reitmeier, Willibald; Burger, Katharina; Hien, Markus; Grass, Philippe; Kubinski, David; Visser, Jaco; Moos, Ralf

2017-01-01

The upcoming more stringent automotive emission legislations and current developments have promoted new technologies for more precise and reliable catalyst control. For this purpose, radio-frequency-based (RF) catalyst state determination offers the only approach for directly measuring the NH3 loading on selective catalytic reduction (SCR) catalysts and the state of other catalysts and filter systems. Recently, the ability of this technique to directly control the urea dosing on a current NH3 storing zeolite catalyst has been demonstrated on an engine dynamometer for the first time and this paper continues that work. Therefore, a well-known serial-type and zeolite-based SCR catalyst (Cu-SSZ-13) was investigated under deliberately chosen high space velocities. At first, the full functionality of the RF system with Cu-SSZ-13 as sample was tested successfully. By direct RF-based NH3 storage control, the influence of the storage degree on the catalyst performance, i.e., on NOx conversion and NH3 slip, was investigated in a temperature range between 250 and 400 °C. For each operation point, an ideal and a critical NH3 storage degree was found and analyzed in the whole temperature range. Based on the data of all experimental runs, temperature dependent calibration functions were developed as a basis for upcoming tests under transient conditions. Additionally, the influence of exhaust humidity was observed with special focus on cold start water and its effects to the RF signals. PMID:28704929

Radio-Frequency-Based NH₃-Selective Catalytic Reduction Catalyst Control: Studies on Temperature Dependency and Humidity Influences.

PubMed

Dietrich, Markus; Hagen, Gunter; Reitmeier, Willibald; Burger, Katharina; Hien, Markus; Grass, Philippe; Kubinski, David; Visser, Jaco; Moos, Ralf

2017-07-12

The upcoming more stringent automotive emission legislations and current developments have promoted new technologies for more precise and reliable catalyst control. For this purpose, radio-frequency-based (RF) catalyst state determination offers the only approach for directly measuring the NH₃ loading on selective catalytic reduction (SCR) catalysts and the state of other catalysts and filter systems. Recently, the ability of this technique to directly control the urea dosing on a current NH₃ storing zeolite catalyst has been demonstrated on an engine dynamometer for the first time and this paper continues that work. Therefore, a well-known serial-type and zeolite-based SCR catalyst (Cu-SSZ-13) was investigated under deliberately chosen high space velocities. At first, the full functionality of the RF system with Cu-SSZ-13 as sample was tested successfully. By direct RF-based NH₃ storage control, the influence of the storage degree on the catalyst performance, i.e., on NO x conversion and NH₃ slip, was investigated in a temperature range between 250 and 400 °C. For each operation point, an ideal and a critical NH₃ storage degree was found and analyzed in the whole temperature range. Based on the data of all experimental runs, temperature dependent calibration functions were developed as a basis for upcoming tests under transient conditions. Additionally, the influence of exhaust humidity was observed with special focus on cold start water and its effects to the RF signals.

Atomic-Scale Design of Iron Fischer-Tropsch Catalysts; A Combined Computational Chemistry, Experimental, and Microkinetic Modeling Approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manos Mavrikakis; James Dumesic; Rahul Nabar

2008-09-29

This work focuses on (1) searching/summarizing published Fischer-Tropsch synthesis (FTS) mechanistic and kinetic studies of FTS reactions on iron catalysts; (2) preparation and characterization of unsupported iron catalysts with/without potassium/platinum promoters; (3) measurement of H{sub 2} and CO adsorption/dissociation kinetics on iron catalysts using transient methods; (3) analysis of the transient rate data to calculate kinetic parameters of early elementary steps in FTS; (4) construction of a microkinetic model of FTS on iron, and (5) validation of the model from collection of steady-state rate data for FTS on iron catalysts. Three unsupported iron catalysts and three alumina-supported iron catalysts weremore » prepared by non-aqueous-evaporative deposition (NED) or aqueous impregnation (AI) and characterized by chemisorption, BET, temperature-programmed reduction (TPR), extent-of-reduction, XRD, and TEM methods. These catalysts, covering a wide range of dispersions and metal loadings, are well-reduced and relatively thermally stable up to 500-600 C in H{sub 2} and thus ideal for kinetic and mechanistic studies. Kinetic parameters for CO adsorption, CO dissociation, and surface carbon hydrogenation on these catalysts were determined from temperature-programmed desorption (TPD) of CO and temperature programmed surface hydrogenation (TPSR), temperature-programmed hydrogenation (TPH), and isothermal, transient hydrogenation (ITH). A microkinetic model was constructed for the early steps in FTS on polycrystalline iron from the kinetic parameters of elementary steps determined experimentally in this work and from literature values. Steady-state rate data were collected in a Berty reactor and used for validation of the microkinetic model. These rate data were fitted to 'smart' Langmuir-Hinshelwood rate expressions derived from a sequence of elementary steps and using a combination of fitted steady-state parameters and parameters specified from the transient measurements. The results provide a platform for further development of microkinetic models of FTS on Fe and a basis for more precise modeling of FTS activity of Fe catalysts. Calculations using periodic, self-consistent Density Functional Theory (DFT) methods were performed on various realistic models of industrial, Fe-based FTS catalysts. Close-packed, most stable Fe(110) facet was analyzed and subsequently carbide formation was found to be facile leading to the choice of the FeC(110) model representing a Fe facet with a sub-surface C atom. The Pt adatom (Fe{sup Pt}(110)) was found to be the most stable model for our studies into Pt promotion and finally the role of steps was elucidated by recourse to the defected Fe(211) facet. Binding Energies(BEs), preferred adsorption sites and geometries for all FTS relevant stable species and intermediates were evaluated on each model catalyst facet. A mechanistic model (comprising of 32 elementary steps involving 19 species) was constructed and each elementary step therein was fully characterized with respect to its thermochemistry and kinetics. Kinetic calculations involved evaluation of the Minimum Energy Pathways (MEPs) and activation energies (barriers) for each step. Vibrational frequencies were evaluated for the preferred adsorption configuration of each species with the aim of evaluating entropy-changes, pre exponential factors and serving as a useful connection with experimental surface science techniques. Comparative analysis among these four facets revealed important trends in their relative behavior and roles in FTS catalysis. Overall the First Principles Calculations afforded us a new insight into FTS catalysis on Fe and modified-Fe catalysts.« less

Attrition Resistant Iron-Based Fischer-Tropsch Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jothimurugesan, K.; Goodwin, J.G.; Spivey, J.J.

1997-03-26

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRS) can largely solve this problem. Iron-based (Fe) catalysts are preferred catalysts for F-T when using low CO/H{sub 2} ratio synthesis gases derived from modem coal gasifiers. This is because in addition to reasonable F-T activity, the FT catalysts also possess high water gas shift (WGS) activity. However, a serious problem withmore » the use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, making the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. The objectives of this research are to develop a better understanding of the parameters affecting attrition resistance of Fe F-T catalysts suitable for use in SBCRs and to incorporate this understanding into the design of novel Fe catalysts having superior attrition resistance. Catalyst preparations will be based on the use of spray drying and will be scalable using commercially available equipment. The research will employ among other measurements, attrition testing and F-T synthesis, including long duration slurry reactor runs in order to ascertain the degree of success of the various preparations. The goal is to develop an Fe catalyst which can be used in a SBCR having only an internal filter for separation of the catalyst from the liquid product, without sacrificing F-T activity and selectivity.« less

Attrition Resistant Iron-Based Fischer-Tropsch Catalysts.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jothimurugesan, K.; Goodwin, J.S.; Spivey, J.J.

1997-09-22

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO and H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. Iron-based (Fe) catalysts are preferred catalysts for F-T when using low CO/H{sub 2} ratio synthesis gases derived from modern coal gasifiers. This is because in addition to reasonable F-T activity, the F-T catalysts also possess high water gas shift (WGS) activity. However, a seriousmore » problem with the use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, making the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. The objectives of this research are to develop a better understanding of the parameters affecting attrition resistance of Fe F-T catalysts suitable for use in SBCRs and to incorporate this understanding into the design of novel Fe catalysts having superior attrition resistance. Catalyst preparations will be based on the use of spray drying and will be scalable using commercially available equipment. The research will employ among other measurements, attrition testing and F-T synthesis, including long duration slurry reactor runs in order to ascertain the degree of success of the various preparations. The goal is to develop an Fe catalyst which can be used in a SBCR having only an internal filter for separation of the catalyst from the liquid product, without sacrificing F-T activity and selectivity.« less

Low Concentration Fe-Doped Alumina Catalysts Using Sol-Gel and Impregnation Methods: The Synthesis, Characterization and Catalytic Performance during the Combustion of Trichloroethylene

PubMed Central

Maldonado, Carolina Solis; De la Rosa, Javier Rivera; Lucio-Ortiz, Carlos J.; Hernández-Ramírez, Aracely; Castillón Barraza, Felipe F.; Valente, Jaime S.

2014-01-01

The role of iron in two modes of integration into alumina catalysts was studied at 0.39 wt% Fe and tested in trichloroethylene combustion. One modified alumina was synthesized using the sol-gel method with Fe added in situ during hydrolysis; another modification was performed using calcined alumina, prepared using the sol-gel method and impregnated with Fe. Several characterization techniques were used to study the level of Fe modification in the γ-Al2O3 phase formed and to correlate the catalytic properties during trichloroethylene (TCE) combustion. The introduction of Fe in situ during the sol-gel process influenced the crystallite size, and three iron species were generated, namely, magnetite, maghemite and hematite. The impregnated Fe-alumina formed hematite and maghemite, which were highly dispersed on the γ-Al2O3 surface. The X-ray photoelectron spectra (XPS), FT-IR and Mössbauer spectroscopy analyses revealed how Fe interacted with the γ-Al2O3 lattice in both catalysts. The impregnated Fe-catalyst showed the best catalytic performance compared to the catalyst that was Fe-doped in situ by the sol-gel method; both had better catalytic activity than pure alumina. This difference in activity was correlated with the accessibility of the reactants to the hematite iron species on the surface. The chlorine poisoning for all three catalysts was less than 1.8%. PMID:28788556

Reaction mechanism of WGS and PROX reactions catalyzed by Pt/oxide catalysts revealed by an FeO(111)/Pt(111) inverse model catalyst.

PubMed

Xu, Lingshun; Wu, Zongfang; Jin, Yuekang; Ma, Yunsheng; Huang, Weixin

2013-08-07

We have employed XPS and TDS to study the adsorption and surface reactions of H2O, CO and HCOOH on an FeO(111)/Pt(111) inverse model catalyst. The FeO(111)-Pt(111) interface of the FeO(111)/Pt(111) inverse model catalyst exposes coordination-unsaturated Fe(II) cations (Fe(II)CUS) and the Fe(II)CUS cations are capable of modifying the reactivity of neighbouring Pt sites. Water facilely dissociates on the Fe(II)CUS cations at the FeO(111)-Pt(111) interface to form hydroxyls that react to form both water and H2 upon heating. Hydroxyls on the Fe(II)CUS cations can react with CO(a) on the neighbouring Pt(111) sites to produce CO2 at low temperatures. Hydroxyls act as the co-catalyst in the CO oxidation by hydroxyls to CO2 (PROX reaction), while they act as one of the reactants in the CO oxidation by hydroxyls to CO2 and H2 (WGS reaction), and the recombinative reaction of hydroxyls to produce H2 is the rate-limiting step in the WGS reaction. A comparison of reaction behaviors between the interfacial CO(a) + OH reaction and the formate decomposition reaction suggest that formate is the likely surface intermediate of the CO(a) + OH reaction. These results provide some solid experimental evidence for the associative reaction mechanism of WGS and PROX reactions catalyzed by Pt/oxide catalysts.

Multi-pedal DNA walker biosensors based on catalyzed hairpin assembly and isothermal strand-displacement polymerase reaction for the chemiluminescent detection of proteins.

PubMed

Li, Ningxing; Du, Mingyuan; Liu, Yucheng; Ji, Xinghu; He, Zhike

2018-06-25

Two kinds of sensitive biosensors based on multi-pedal DNA walker along a 3-D DNA functional magnet particles track for the chemiluminescent detection of streptavidin are constructed and compared in this study. In the presence of SA, multi-pedal DNA walker has been constructed by biotin-modified catalyst as a result of the terminal protection for avoiding the digestion by exonuclease I. Then a toehold of CHA-H1 conjugated with magnetic microparticles (MMPs) could interact with a 'leg' of multi-pedal DNA walker to open the hairpin via toehold-mediated strand exchange catalysis. A newly exposed DNA segment in CHA-H1 would be hybridized with a toehold of biotin-labeled H2. Via the strand displacement process, H2 displaces one 'leg' of multi-pedal DNA walker, and the other 'leg' could still hybridize with neighboring H1 to initiate the next cycle. In order to solve the high background caused by the hybridization between CHA-H1 and H2 without CHA-catalyst, the other model has been designed. The principle of the other model (ISDPR DNA walker) is similar to the above one. After the terminal protection of SA, a 'leg' of multi-pedal DNA walker triggers the opening of the hairpin of ISDPR-H1 conjugated with MMPs. Then the biotin-modified primer could hybridize with the open stem, triggering the polymerization reaction in the presence of dNTPs/polymerase. As the extension of the primer, the 'leg' of multi-pedal DNA walker is displaced so that the other 'leg' could trigger proximal H1 to go on the next cycle. Due to its lower background and stronger signal, multi-pedal DNA walker based on ISDPR has a lower limit of detection for SA. The limit of detection (LOD) for SA is 6.5 pM. What's more, these DNA walker methods have been applied in complex samples successfully.

Effect of Nitrogen Post-Doping on a Commercial Platinum-Ruthenium/Carbon Anode Catalyst

DTIC Science & Technology

2014-02-15

polymer electrolyte membrane fuel cells ( PEMFCs ) closer to commercial viability. However, further improvements in fuel cell durability, particularly...have recently led to significant improvements [3e5]. The genesis of interest in modified carbon support materials for PEMFCs and DMFCs originated in

Intermetallic nickel silicide nanocatalyst—A non-noble metal–based general hydrogenation catalyst

PubMed Central

Pohl, Marga-Martina; Agapova, Anastasiya

2018-01-01

Hydrogenation reactions are essential processes in the chemical industry, giving access to a variety of valuable compounds including fine chemicals, agrochemicals, and pharmachemicals. On an industrial scale, hydrogenations are typically performed with precious metal catalysts or with base metal catalysts, such as Raney nickel, which requires special handling due to its pyrophoric nature. We report a stable and highly active intermetallic nickel silicide catalyst that can be used for hydrogenations of a wide range of unsaturated compounds. The catalyst is prepared via a straightforward procedure using SiO2 as the silicon atom source. The process involves thermal reduction of Si–O bonds in the presence of Ni nanoparticles at temperatures below 1000°C. The presence of silicon as a secondary component in the nickel metal lattice plays the key role in its properties and is of crucial importance for improved catalytic activity. This novel catalyst allows for efficient reduction of nitroarenes, carbonyls, nitriles, N-containing heterocycles, and unsaturated carbon–carbon bonds. Moreover, the reported catalyst can be used for oxidation reactions in the presence of molecular oxygen and is capable of promoting acceptorless dehydrogenation of unsaturated N-containing heterocycles, opening avenues for H2 storage in organic compounds. The generality of the nickel silicide catalyst is demonstrated in the hydrogenation of over a hundred of structurally diverse unsaturated compounds. The wide application scope and high catalytic activity of this novel catalyst make it a nice alternative to known general hydrogenation catalysts, such as Raney nickel and noble metal–based catalysts. PMID:29888329

Intermetallic nickel silicide nanocatalyst-A non-noble metal-based general hydrogenation catalyst.

PubMed

Ryabchuk, Pavel; Agostini, Giovanni; Pohl, Marga-Martina; Lund, Henrik; Agapova, Anastasiya; Junge, Henrik; Junge, Kathrin; Beller, Matthias

2018-06-01

Hydrogenation reactions are essential processes in the chemical industry, giving access to a variety of valuable compounds including fine chemicals, agrochemicals, and pharmachemicals. On an industrial scale, hydrogenations are typically performed with precious metal catalysts or with base metal catalysts, such as Raney nickel, which requires special handling due to its pyrophoric nature. We report a stable and highly active intermetallic nickel silicide catalyst that can be used for hydrogenations of a wide range of unsaturated compounds. The catalyst is prepared via a straightforward procedure using SiO 2 as the silicon atom source. The process involves thermal reduction of Si-O bonds in the presence of Ni nanoparticles at temperatures below 1000°C. The presence of silicon as a secondary component in the nickel metal lattice plays the key role in its properties and is of crucial importance for improved catalytic activity. This novel catalyst allows for efficient reduction of nitroarenes, carbonyls, nitriles, N-containing heterocycles, and unsaturated carbon-carbon bonds. Moreover, the reported catalyst can be used for oxidation reactions in the presence of molecular oxygen and is capable of promoting acceptorless dehydrogenation of unsaturated N-containing heterocycles, opening avenues for H 2 storage in organic compounds. The generality of the nickel silicide catalyst is demonstrated in the hydrogenation of over a hundred of structurally diverse unsaturated compounds. The wide application scope and high catalytic activity of this novel catalyst make it a nice alternative to known general hydrogenation catalysts, such as Raney nickel and noble metal-based catalysts.

Preparation, characterization, and catalytic activity of zirconocene bridged on surface of silica gel

NASA Astrophysics Data System (ADS)

El Majdoub, Lotfia; Shi, Yasai; Yuan, Yuan; Zhou, Annan; Abutartour, Abubaker; Xu, Qinghong

2015-10-01

Zirconocene catalyst supported on silica gel was prepared for olefin polymerization by surface modification of calcined silica with SiCl4, and the reaction between the modified silica and cyclopentadienyl sodium and ZrCl4. The catalyst was characterized by using Fourier-transform infrared (FT-IR) spectrometer, thermogravimetric (TG), and differential scanning calorimetric (DSC) analytic spectrometer. It was found that the metallocene structure could be formed and connected on silica surface by chemical bond. Initial catalytic tests showed that the supported metallocene was catalytically active (methylaluminoxane as a cocatalyst), producing polymer with higher molecular weight than the metallocene just immobilized on the surface of silica gel.

Dilute acid/metal salt hydrolysis of lignocellulosics

DOEpatents

Nguyen, Quang A.; Tucker, Melvin P.

2002-01-01

A modified dilute acid method of hydrolyzing the cellulose and hemicellulose in lignocellulosic material under conditions to obtain higher overall fermentable sugar yields than is obtainable using dilute acid alone, comprising: impregnating a lignocellulosic feedstock with a mixture of an amount of aqueous solution of a dilute acid catalyst and a metal salt catalyst sufficient to provide higher overall fermentable sugar yields than is obtainable when hydrolyzing with dilute acid alone; loading the impregnated lignocellulosic feedstock into a reactor and heating for a sufficient period of time to hydrolyze substantially all of the hemicellulose and greater than 45% of the cellulose to water soluble sugars; and recovering the water soluble sugars.

Highly efficient molybdenum-based catalysts for enantioselective alkene metathesis

PubMed Central

Malcolmson, Steven J.; Meek, Simon J.; Sattely, Elizabeth S.; Schrock, Richard R.; Hoveyda, Amir H.

2009-01-01

Discovery of efficient catalysts is one of the most compelling objectives of modern chemistry. Chiral catalysts are in particularly high demand, as they facilitate synthesis of enantiomerically enriched small molecules that are critical to developments in medicine, biology and materials science1. Especially noteworthy are catalysts that promote—with otherwise inaccessible efficiency and selectivity levels—reactions demonstrated to be of great utility in chemical synthesis. Here we report a class of chiral catalysts that initiate alkene metathesis1 with very high efficiency and enantioselectivity. Such attributes arise from structural fluxionality of the chiral catalysts and the central role that enhanced electronic factors have in the catalytic cycle. The new catalysts have a stereogenic metal centre and carry only monodentate ligands; the molybdenum-based complexes are prepared stereoselectively by a ligand exchange process involving an enantiomerically pure aryloxide, a class of ligands scarcely used in enantioselective catalysis2,3. We demonstrate the application of the new catalysts in an enantioselective synthesis of the Aspidosperma alkaloid, quebrachamine, through an alkene metathesis reaction that cannot be promoted by any of the previously reported chiral catalysts. PMID:19011612

Co-Production of Electricity and Hydrogen Using a Novel Iron-based Catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hilaly, Ahmad; Georgas, Adam; Leboreiro, Jose

2011-09-30

The primary objective of this project was to develop a hydrogen production technology for gasification applications based on a circulating fluid-bed reactor and an attrition resistant iron catalyst. The work towards achieving this objective consisted of three key activities: Development of an iron-based catalyst suitable for a circulating fluid-bed reactor; Design, construction, and operation of a bench-scale circulating fluid-bed reactor system for hydrogen production; Techno-economic analysis of the steam-iron and the pressure swing adsorption hydrogen production processes. This report describes the work completed in each of these activities during this project. The catalyst development and testing program prepared and iron-basedmore » catalysts using different support and promoters to identify catalysts that had sufficient activity for cyclic reduction with syngas and steam oxidation and attrition resistance to enable use in a circulating fluid-bed reactor system. The best performing catalyst from this catalyst development program was produced by a commercial catalyst toll manufacturer to support the bench-scale testing activities. The reactor testing systems used during material development evaluated catalysts in a single fluid-bed reactor by cycling between reduction with syngas and oxidation with steam. The prototype SIP reactor system (PSRS) consisted of two circulating fluid-bed reactors with the iron catalyst being transferred between the two reactors. This design enabled demonstration of the technical feasibility of the combination of the circulating fluid-bed reactor system and the iron-based catalyst for commercial hydrogen production. The specific activities associated with this bench-scale circulating fluid-bed reactor systems that were completed in this project included design, construction, commissioning, and operation. The experimental portion of this project focused on technical demonstration of the performance of an iron-based catalyst and a circulating fluid-bed reactor system for hydrogen production. Although a technology can be technically feasible, successful commercial deployment also requires that a technology offer an economic advantage over existing commercial technologies. To effective estimate the economics of this steam-iron process, a techno-economic analysis of this steam iron process and a commercial pressure swing adsorption process were completed. The results from this analysis described in this report show the economic potential of the steam iron process for integration with a gasification plant for coproduction of hydrogen and electricity.« less

Lability and Basicity of Bipyridine-Carboxylate-Phosphonate Ligand Accelerate Single-Site Water Oxidation by Ruthenium-Based Molecular Catalysts

DOE PAGES

Shaffer, David W.; Xie, Yan; Szalda, David J.; ...

2017-09-24

Here, a critical step in creating an artificial photosynthesis system for energy storage is designing catalysts that can thrive in an assembled device. Single-site catalysts have an advantage over bimolecular catalysts because they remain effective when immobilized. Hybrid water oxidation catalysts described here, combining the features of single-site bis-phosphonate catalysts and fast bimolecular bis-carboxylate catalysts, have reached turnover frequencies over 100 s –1, faster than both related catalysts under identical conditions. The new [(bpHc)Ru(L) 2] (bpH 2cH = 2,2'-bipyridine-6-phosphonic acid-6'-carboxylic acid, L = 4-picoline or isoquinoline) catalysts proceed through a single-site water nucleophilic attack pathway. The pendant phosphonate base mediatesmore » O–O bond formation via intramolecular atom-proton transfer with a calculated barrier of only 9.1 kcal/mol. Additionally, the labile carboxylate group allows water to bind early in the catalytic cycle, allowing intramolecular proton-coupled electron transfer to lower the potentials for oxidation steps and catalysis. That a single-site catalyst can be this fast lends credence to the possibility that the oxygen evolving complex adopts a similar mechanism.« less

Lability and Basicity of Bipyridine-Carboxylate-Phosphonate Ligand Accelerate Single-Site Water Oxidation by Ruthenium-Based Molecular Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shaffer, David W.; Xie, Yan; Szalda, David J.

Here, a critical step in creating an artificial photosynthesis system for energy storage is designing catalysts that can thrive in an assembled device. Single-site catalysts have an advantage over bimolecular catalysts because they remain effective when immobilized. Hybrid water oxidation catalysts described here, combining the features of single-site bis-phosphonate catalysts and fast bimolecular bis-carboxylate catalysts, have reached turnover frequencies over 100 s –1, faster than both related catalysts under identical conditions. The new [(bpHc)Ru(L) 2] (bpH 2cH = 2,2'-bipyridine-6-phosphonic acid-6'-carboxylic acid, L = 4-picoline or isoquinoline) catalysts proceed through a single-site water nucleophilic attack pathway. The pendant phosphonate base mediatesmore » O–O bond formation via intramolecular atom-proton transfer with a calculated barrier of only 9.1 kcal/mol. Additionally, the labile carboxylate group allows water to bind early in the catalytic cycle, allowing intramolecular proton-coupled electron transfer to lower the potentials for oxidation steps and catalysis. That a single-site catalyst can be this fast lends credence to the possibility that the oxygen evolving complex adopts a similar mechanism.« less

"Catalysis in a tea bag": synthesis, catalytic performance and recycling of dendrimer-immobilised bis- and trisoxazoline copper catalysts.

PubMed

Gaab, Manuela; Bellemin-Laponnaz, Stéphane; Gade, Lutz H

2009-01-01

Bis- and trisoxazolines (BOX and trisox), containing a linker unit in the ligand backbone that allows their covalent attachment to carbosilane dendrimers, have been employed as polyfunctional ligands for recyclable Cu(II) Lewis acid catalysts that were immobilised in a membrane bag. The oxazolines contained an alkynyl unit attached to their backbone that was deprotonated with LDA or BuLi and then reacted with the chlorosilyl termini of zeroth-, first- and second-generation carbosilane dendrimers in the presence of TlPF(6). The functionalised dendritic systems were subsequently separated from excess ligand by way of dialysis. The general catalytic potential of these systems was assessed by studying two benchmark reactions, the alpha-hydrazination of a beta-keto ester as well as the Henry reaction of 2-nitrobenzaldehyde with nitromethane. For both reactions the bisoxazoline-based catalysts displayed superior selectivity and, in particular, catalyst activity. The latter was interpreted as being due to the hindered decoordination of the third oxazoline unit, the key step in the generation of the active catalyst, in the immobilised trisox-copper complexes. Solutions of the second-generation dendrimer catalysts were placed in membrane bags, fabricated from commercially available dialysis membranes, with the purpose of catalyst recycling based on dialysis. Overall, the supported BOX catalyst gave good and highly reproducible results throughout the study, whereas the performance of the trisox dendrimer system decreased monotonically. The reason for the different behaviour is the markedly lower activity of trisox-based catalysts relative to those based on the BOX ligand. This necessitated an increased reaction time for each cycle of the trisox derivatives, resulting in higher levels of catalyst leaching, which was attributed to a modification of the structure of the membrane by its exposure to the solvent trifluoroethanol at 40 degrees C.

Dual gold catalysis: σ,π-propyne acetylide and hydroxyl-bridged digold complexes as easy-to-prepare and easy-to-handle precatalysts.

PubMed

Hashmi, A Stephen K; Lauterbach, Tobias; Nösel, Pascal; Vilhelmsen, Mie Højer; Rudolph, Matthias; Rominger, Frank

2013-01-14

A series of dinuclear gold σ,π-propyne acetylide complexes were prepared and tested for their catalytic ability in dual gold catalysis that was based on the reaction of an electrophilic π-complex of gold with a gold acetylide. The air-stable and storable catalysts can be isolated as silver-free catalysts in their activated form. These dual catalysts allow a fast initiation phase for the dual catalytic cycles without the need for additional additives for acetylide formation. Because propyne serves as a throw-away ligand, no traces of the precatalyst are generated. Based on the fast initiation process, side products are minimized and reaction rates are higher for these catalysts. A series of test reactions were used to demonstrate the general applicability of these catalysts. Lower catalyst loadings, faster reaction rates, and better selectivity, combined with the practicability of these catalysts, make them ideal catalysts for dual gold catalysis. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

New Ni-based quaternary disk-shaped catalysts for low-temperature CO2 methanation: Fabrication, characterization, and performance.

PubMed

Moon, Dea Hyun; Lee, Sang Moon; Ahn, Jeong Yoon; Nguyen, Dinh Duc; Kim, Sung Su; Chang, Soon Woong

2018-07-15

Ni-based quaternary disk catalysts were manufactured for low-temperature CO 2 methanation reactions, and the reaction activity was examined with respect to the thermal treatment conditions. By applying varying reduction and combustion treatments, the same catalysts were compared, and the Ni oxidation conditions and physical features were confirmed through X-Ray diffraction, scanning electron microscopy, and energy dispersive X-ray analyses. In addition, oxygen adsorption/desorption changes were measured by temperature-programmed reduction after pre-treating with oxygen and hydrogen. The reduction treatment catalyst showed a conversion of 20% at 280 °C, and the 70% calcined catalyst did not form a NiO crystalloid. The activation of the catalyst increased because of NiO movement on the catalyst surface, which enabled easy transformation to metallic Ni. The prepared catalyst is a highly reactive, yet stable, candidate for practical catalytic CO 2 methanation. Copyright © 2018 Elsevier Ltd. All rights reserved.

Overcoming the Instability of Nanoparticle-Based Catalyst Films in Alkaline Electrolyzers by using Self-Assembling and Self-Healing Films.

PubMed

Barwe, Stefan; Masa, Justus; Andronescu, Corina; Mei, Bastian; Schuhmann, Wolfgang; Ventosa, Edgar

2017-07-10

Engineering stable electrodes using highly active catalyst nanopowders for electrochemical water splitting remains a challenge. We report an innovative and general approach for attaining highly stable catalyst films with self-healing capability based on the in situ self-assembly of catalyst particles during electrolysis. The catalyst particles are added to the electrolyte forming a suspension that is pumped through the electrolyzer. Particles with negatively charged surfaces stick onto the anode, while particles with positively charged surfaces stick to the cathode. The self-assembled catalyst films have self-healing properties as long as sufficient catalyst particles are present in the electrolyte. The proof-of-concept was demonstrated in a non-zero gap alkaline electrolyzer using NiFe-LDH and Ni x B catalyst nanopowders for anode and cathode, respectively. Steady cell voltages were maintained for at least three weeks during continuous electrolysis at 50-100 mA cm -2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Heterogeneous electro-Fenton catalyst for 1-butylpyridinium chloride degradation.

PubMed

Meijide, Jessica; Pazos, Marta; Sanromán, Maria Ángeles

2017-10-15

The application of the electro-Fenton process for organic compound mineralisation has been widely reported over the past years. However, operational problems related to the use of soluble iron salt as a homogeneous catalyst involve the development of novel catalysts that are able to operate in a wide pH range. For this purpose, polyvinyl alcohol-alginate beads, containing goethite as iron, were synthesised and evaluated as heterogeneous electro-Fenton catalyst for 1-butylpyridinium chloride mineralisation. The influence of catalyst dosage and pH solution on ionic liquid degradation was analysed, achieving almost total oxidation after 60 min under optimal conditions (2 g/L catalyst concentration and pH 3). The results showed good catalyst stability and reusability, although its effectiveness decreases slightly after three successive cycles. Furthermore, a plausible mineralisation pathway was proposed based on the oxidation byproducts determined by chromatographic techniques. Finally, the Microtox® test revealed notable detoxification after treatment which demonstrates high catalyst ability for pyridinium-based ionic liquid degradation by the electro-Fenton process.

Catalytic wet air oxidation of coke-plant wastewater on ruthenium-based eggshell catalysts in a bubbling bed reactor.

PubMed

Yang, M; Sun, Y; Xu, A H; Lu, X Y; Du, H Z; Sun, C L; Li, C

2007-07-01

Catalytic wet air of coke-plant wastewater was studied in a bubbling bed reactor. Two types of supported Ru-based catalysts, eggshell and uniform catalysts, were employed. Compared with the results in the wet air oxidation of coke-plant wastewater, supported Ru uniform catalysts showed high activity for chemical oxygen demand (COD) and ammonia/ammonium compounds (NH3-N) removal at temperature of 250 degrees C and pressure of 4.8 MPa, and it has been demonstrated that the catalytic activity of uniform catalyst depended strongly on the distribution of active sites of Ru on catalyst. Compared to the corresponding uniform catalysts with the same Ru loading (0.25 wt.% and 0.1 wt.%, respectively), the eggshell catalysts showed higher activities for CODcr removal and much higher activities for NH3-N degradation. The high activity of eggshell catalyst for treatment of coke-plant wastewater can be attributed to the higher density of active Ru sites in the shell layer than that of the corresponding uniform catalyst with the same Ru loading. It has been also evidenced that the active Ru sites in the internal core of uniform catalyst have very little or no contribution to CODcr and NH3-N removal in the total oxidation of coke-plant wastewater.