Silver-palladium catalysts for the direct synthesis of hydrogen peroxide

NASA Astrophysics Data System (ADS)

Khan, Zainab; Dummer, Nicholas F.; Edwards, Jennifer K.

2017-11-01

A series of bimetallic silver-palladium catalysts supported on titania were prepared by wet impregnation and assessed for the direct synthesis of hydrogen peroxide, and its subsequent side reactions. The addition of silver to a palladium catalyst was found to significantly decrease hydrogen peroxide productivity and hydrogenation, but crucially increase the rate of decomposition. The decomposition product, which is predominantly hydroxyl radicals, can be used to decrease bacterial colonies. The interaction between silver and palladium was characterized using scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and temperature programmed reduction (TPR). The results of the TPR and XPS indicated the formation of a silver-palladium alloy. The optimal 1% Ag-4% Pd/TiO2 bimetallic catalyst was able to produce approximately 200 ppm of H2O2 in 30 min. The findings demonstrate that AgPd/TiO2 catalysts are active for the synthesis of hydrogen peroxide and its subsequent decomposition to reactive oxygen species. The catalysts are promising for use in wastewater treatment as they combine the disinfectant properties of silver, hydrogen peroxide production and subsequent decomposition. This article is part of a discussion meeting issue 'Providing sustainable catalytic solutions for a rapidly changing world'.

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.

Photogeneration of active formate decomposition catalysts to produce hydrogen from formate and water

DOEpatents

King, Jr., Allen D.; King, Robert B.; Sailers, III, Earl L.

1983-02-08

A process for producing hydrogen from formate and water by photogenerating an active formate decomposition catalyst from transition metal carbonyl precursor catalysts at relatively low temperatures and otherwise mild conditions is disclosed. Additionally, this process may be expanded to include the generation of formate from carbon monoxide and hydroxide such that the result is the water gas shift reaction.

Synthesis and characterization of nickel and zinc ferrite nanocatalysts for decomposition of CO2 greenhouse effect gas.

PubMed

Lin, Kuen-Song; Adhikari, Abhijit Krishna; Wang, Chi-Yu; Hsu, Pei-Ju; Chan, Ho-Yang

2013-04-01

The decomposition of CO2 over oxygen deficient nickel ferrite nanoparticles (NFNs) and zinc ferrite nanoparticles (ZFNs) at 573 K was studied. The oxidation states with fine structure of Fe/Ni or Fe/Zn species were also measured in NFNs and ZFNs catalysts, respectively. Oxygen deficiency of catalysts was obtained by reduction in hydrogen. Decomposition of CO2 into carbon and oxygen has been carried out within few minutes when it comes into contact with oxygen deficient catalysts through incorporation of oxygen into ferrite nanoparticles. Oxygen and carbon rather than CO were produced in the decomposition process. The complete decomposition of CO2 was possible because of higher degree of oxygen deficiency andsurface-to-volume ratio of the catalysts. The pre-edge XANES spectra of Fe species in both catalysts exhibit an absorbance feature at 7114 eV for the 1s to 3d transition which is forbidden by the selection rule in case of perfect octahedral symmetry. The EXAFS data showed that the NFNs had two central Fe atoms coordinated by primarily Fe-O and Fe-Fe with bond distances of 1.871 and 3.051 angstroms, respectively. In case of ZFNs these values are 1.889 and 3.062 A, respectively. Methane gas was produced during the reactivation of NFNs by flowing hydrogen gas. Decomposition of CO2, moreover, recovery of valuable methane using heat energy of offgas produced from power generation plant or steel industry is an appealing alternative for energy recovery.

Bimolecular Coupling as a Vector for Decomposition of Fast-Initiating Olefin Metathesis Catalysts.

PubMed

Bailey, Gwendolyn A; Foscato, Marco; Higman, Carolyn S; Day, Craig S; Jensen, Vidar R; Fogg, Deryn E

2018-06-06

The correlation between rapid initiation and rapid decomposition in olefin metathesis is probed for a series of fast-initiating, phosphine-free Ru catalysts: the Hoveyda catalyst HII, RuCl 2 (L)(═CHC 6 H 4 - o-O i Pr); the Grela catalyst nG (a derivative of HII with a nitro group para to O i Pr); the Piers catalyst PII, [RuCl 2 (L)(═CHPCy 3 )]OTf; the third-generation Grubbs catalyst GIII, RuCl 2 (L)(py) 2 (═CHPh); and dianiline catalyst DA, RuCl 2 (L)( o-dianiline)(═CHPh), in all of which L = H 2 IMes = N,N'-bis(mesityl)imidazolin-2-ylidene. Prior studies of ethylene metathesis have established that various Ru metathesis catalysts can decompose by β-elimination of propene from the metallacyclobutane intermediate RuCl 2 (H 2 IMes)(κ 2 -C 3 H 6 ), Ru-2. The present work demonstrates that in metathesis of terminal olefins, β-elimination yields only ca. 25-40% propenes for HII, nG, PII, or DA, and none for GIII. The discrepancy is attributed to competing decomposition via bimolecular coupling of methylidene intermediate RuCl 2 (H 2 IMes)(═CH 2 ), Ru-1. Direct evidence for methylidene coupling is presented, via the controlled decomposition of transiently stabilized adducts of Ru-1, RuCl 2 (H 2 IMes)L n (═CH 2 ) (L n = py n' ; n' = 1, 2, or o-dianiline). These adducts were synthesized by treating in situ-generated metallacyclobutane Ru-2 with pyridine or o-dianiline, and were isolated by precipitating at low temperature (-116 or -78 °C, respectively). On warming, both undergo methylidene coupling, liberating ethylene and forming RuCl 2 (H 2 IMes)L n . A mechanism is proposed based on kinetic studies and molecular-level computational analysis. Bimolecular coupling emerges as an important contributor to the instability of Ru-1, and a potentially major pathway for decomposition of fast-initiating, phosphine-free metathesis catalysts.

Nano or micro? A mechanism on thermal decomposition of ammonium perchlorate catalyzed by cobalt oxalate.

PubMed

Zou, Min; Jiang, Xiaohong; Lu, Lude; Wang, Xin

2012-07-30

Micrometer-sized cobalt oxalates with different morphologies have been prepared in the presence of surfactants. The effect of catalysts morphology on the thermal decomposition of ammonium perchlorate (AP) was evaluated by differential thermal analysis (DSC). Remarkably, contrary to the well-accepted concepts, no direct relationship between the morphologies of catalysts and their activities has been observed. Based on the structural and morphological variation of the catalysts during the reaction, a catalytic mechanism on thermal decomposition of ammonium perchlorate catalyzed by cobalt oxalate is proposed. We believe that it is the "self-crushing and self-distributed" occurred within the reaction that really works for the improvement of the overall catalytic activities. In this process, both catalysts and reactants have been crashed and distributed uniformly in an automatic way. This work provides an in-depth insight into the thermal decomposition mechanism of AP as catalyzed by oxalates. Copyright © 2012 Elsevier B.V. All rights reserved.

Catalytic and inhibiting effects of lithium peroxide and hydroxide on sodium chlorate decomposition

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

Cannon, J.C.; Zhang, Y.

1995-09-01

Chemical oxygen generators based on sodium chlorate and lithium perchlorate are used in airplanes, submarines, diving, and mine rescue. Catalytic decomposition of sodium chlorate in the presence of cobalt oxide, lithium peroxide, and lithium hydroxide is studied using thermal gravimetric analysis. Lithium peroxide and hydroxide are both moderately active catalysts for the decomposition of sodium chlorate when used alone, and inhibitors when used with the more active catalyst cobalt oxide.

Innovative PCDD/F-containing gas stream generating system applied in catalytic decomposition of gaseous dioxins over V2O5-WO3/TiO2-based catalysts.

PubMed

Yang, Chia Cheng; Chang, Shu Hao; Hong, Bao Zhen; Chi, Kai Hsien; Chang, Moo Been

2008-10-01

Development of effective PCDD/F (polychlorinated dibenzo-p-dioxin and dibenzofuran) control technologies is essential for environmental engineers and researchers. In this study, a PCDD/F-containing gas stream generating system was developed to investigate the efficiency and effectiveness of innovative PCDD/F control technologies. The system designed and constructed can stably generate the gas stream with the PCDD/F concentration ranging from 1.0 to 100ng TEQ Nm(-3) while reproducibility test indicates that the PCDD/F recovery efficiencies are between 93% and 112%. This new PCDD/F-containing gas stream generating device is first applied in the investigation of the catalytic PCDD/F control technology. The catalytic decomposition of PCDD/Fs was evaluated with two types of commercial V(2)O(5)-WO(3)/TiO(2)-based catalysts (catalyst A and catalyst B) at controlled temperature, water vapor content, and space velocity. 84% and 91% PCDD/F destruction efficiencies are achieved with catalysts A and B, respectively, at 280 degrees C with the space velocity of 5000h(-1). The results also indicate that the presence of water vapor inhibits PCDD/F decomposition due to its competition with PCDD/F molecules for adsorption on the active vanadia sites for both catalysts. In addition, this study combined integral reaction and Mars-Van Krevelen model to calculate the activation energies of OCDD and OCDF decomposition. The activation energies of OCDD and OCDF decomposition via catalysis are calculated as 24.8kJmol(-1) and 25.2kJmol(-1), respectively.

Metal-porphyrin: a potential catalyst for direct decomposition of N(2)O by theoretical reaction mechanism investigation.

PubMed

Maitarad, Phornphimon; Namuangruk, Supawadee; Zhang, Dengsong; Shi, Liyi; Li, Hongrui; Huang, Lei; Boekfa, Bundet; Ehara, Masahiro

2014-06-17

The adsorption of nitrous oxide (N2O) on metal-porphyrins (metal: Ti, Cr, Fe, Co, Ni, Cu, or Zn) has been theoretically investigated using density functional theory with the M06L functional to explore their use as potential catalysts for the direct decomposition of N2O. Among these metal-porphyrins, Ti-porphyrin is the most active for N2O adsorption in the triplet ground state with the strongest adsorption energy (-13.32 kcal/mol). Ti-porphyrin was then assessed for the direct decomposition of N2O. For the overall reaction mechanism of three N2O molecules on Ti-porphyrin, two plausible catalytic cycles are proposed. Cycle 1 involves the consecutive decomposition of the first two N2O molecules, while cycle 2 is the decomposition of the third N2O molecule. For cycle 1, the activation energies of the first and second N2O decompositions are computed to be 3.77 and 49.99 kcal/mol, respectively. The activation energy for the third N2O decomposition in cycle 2 is 47.79 kcal/mol, which is slightly lower than that of the second activation energy of the first cycle. O2 molecules are released in cycles 1 and 2 as the products of the reaction, which requires endothermic energies of 102.96 and 3.63 kcal/mol, respectively. Therefore, the O2 desorption is mainly released in catalytic cycle 2 of a TiO3-porphyrin intermediate catalyst. In conclusion, regarding the O2 desorption step for the direct decomposition of N2O, the findings would be very useful to guide the search for potential N2O decomposition catalysts in new directions.

Modeling of methanol decomposition on Pt/CeO2/ZrO2 catalyst in a packed bed microreactor

NASA Astrophysics Data System (ADS)

Pohar, Andrej; Belavič, Darko; Dolanc, Gregor; Hočevar, Stanko

2014-06-01

Methanol decomposition on Pt/CeO2/ZrO2 catalyst is studied inside a packed bed microreactor in the temperature range of 300-380 °C. The microreactor is fabricated using low-temperature co-fired ceramic (LTCC) technology, which is well suited for the production of relatively complex three-dimensional structures. It is packed with 2 wt% Pt-CeO2 catalyst, which is deposited onto ZrO2 spherical particles. A 1D mathematical model, which incorporates diffusion, convection and mass transfer through the boundary layer to the catalyst particles, as well as a 3D computational fluid dynamics model, are developed to describe the methanol decomposition process inside the packed bed. The microreactor exhibits reliable operation and no catalyst deactivation was observed during three months of experimentation. A comparison between the 1D mathematical model and the 3D model, considering the full 3D geometry of the microreactor is made and the differences between the models are identified and evaluated.

Synthesis of seaweed based carbon acid catalyst by thermal decomposition of ammonium sulfate for biodiesel production

NASA Astrophysics Data System (ADS)

Ee, Tang Zo; Lim, Steven; Ling, Pang Yean; Huei, Wong Kam; Chyuan, Ong Hwai

2017-04-01

Experiment was carried out to study the feasibility of biomass derived solid acid catalyst for the production of biodiesel using Palm Fatty Acid Distillate (PFAD). Malaysia indigenous seaweed was selected as the biomass to be carbonized as the catalyst support. Sulfonation of seaweed based carbon material was carried out by thermal decomposition of ammonium sulfate, (NH4)2SO4. The effects of carbonization temperature at 200 to 600°C on the catalyst physical and chemical properties were studied. The effect of reaction parameters on the fatty acid methyl ester (FAME) yield was studied by varying the concentration of ammonium sulfate (5.0 to 40.0 w/v%) and thermal decomposition time (15 to 90 min). Characterizations of catalyst were carried out to study the catalyst surface morphology with Scanning Electron Microscope (SEM), acid density with back titration and functional group attached with FT-IR. Results showed that when the catalyst sulfonated with 10.0 w/v% ammonium sulfate solution and heated to 235°C for 30 min, the highest FAME yield achieved was 23.7% at the reaction condition of 5.0 wt.% catalyst loading, esterification time of 4 h, methanol to PFAD molar ratio of 20:1 at 100°C reaction temperature.

Nanoparticle-assisted photo-Fenton reaction for photo-decomposition of humic acid

NASA Astrophysics Data System (ADS)

Banik, Jhuma; Basumallick, Srijita

2017-11-01

We report here the synthesis of CuO-doped ZnO composite nanomaterials (NMs) by chemical route and demonstrated for the first time that these NMs are efficient catalysts for H2O2-assisted photo-decomposition (photo-Fenton type catalyst) of humic acid, a natural pollutant of surface water by solar irradiation. This has been explained by faster electron transfer to OH radical at the p-n hetero-junction of this composite catalyst. Application of this composite catalyst in decomposing humus substances of local pond water by solar energy has been demonstrated.

Marine environmental protection: An application of the nanometer photo catalyst method on decomposition of benzene.

PubMed

Lin, Mu-Chien; Kao, Jui-Chung

2016-04-15

Bioremediation is currently extensively employed in the elimination of coastal oil pollution, but it is not very effective as the process takes several months to degrade oil. Among the components of oil, benzene degradation is difficult due to its stable characteristics. This paper describes an experimental study on the decomposition of benzene by titanium dioxide (TiO2) nanometer photocatalysis. The photocatalyst is illuminated with 360-nm ultraviolet light for generation of peroxide ions. This results in complete decomposition of benzene, thus yielding CO2 and H2O. In this study, a nonwoven fabric is coated with the photocatalyst and benzene. Using the Double-Shot Py-GC system on the residual component, complete decomposition of the benzene was verified by 4h of exposure to ultraviolet light. The method proposed in this study can be directly applied to elimination of marine oil pollution. Further studies will be conducted on coastal oil pollution in situ. Copyright © 2016 Elsevier Ltd. All rights reserved.

Catalyst comprising Ir or Ir and Ru for hydrazine decomposition

NASA Technical Reports Server (NTRS)

Armstrong, Warren E. (Inventor); Voge, Hervey H. (Inventor); Ryland, Lloyd B. (Inventor)

1978-01-01

A catalyst for hydrazine decomposition consisting essentially of a carrier having a pore volume of at least 0.1 cubic centimeters per gram and a specific surface area, measured in square meters per gram, equal to 195 (C.sub.p + 0.013 + 0.736 V.sub.p) where C.sub.p is the specific heat capacity of the carrier at about 25.degree. C in calories per gram per degree and V.sub.p is the pore volume of the carrier in cubic centimeters per gram and metal of the group consisting of iridium, and mixtures consisting of iridium and ruthenium deposited on said carrier in an amount between 20% and about 40% by weight of the catalyst and distributed through the pores thereof in discrete particles sufficiently separated from each other so that they do not sinter or fuse together when the catalyst is at hydrazine decomposition temperature.

Decomposition of environmentally persistent perfluorooctanoic acid in water by photochemical approaches.

PubMed

Hori, Hisao; Hayakawa, Etsuko; Einaga, Hisahiro; Kutsuna, Shuzo; Koike, Kazuhide; Ibusuki, Takashi; Kiatagawa, Hiroshi; Arakawa, Ryuichi

2004-11-15

The decomposition of persistent and bioaccumulative perfluorooctanoic acid (PFOA) in water by UV-visible light irradiation, by H202 with UV-visible light irradiation, and by a tungstic heteropolyacid photocatalyst was examined to develop a technique to counteract stationary sources of PFOA. Direct photolysis proceeded slowly to produce CO2, F-, and short-chain perfluorocarboxylic acids. Compared to the direct photolysis, H2O2 was less effective in PFOA decomposition. On the other hand, the heteropolyacid photocatalyst led to efficient PFOA decomposition and the production of F- ions and CO2. The photocatalyst also suppressed the accumulation of short-chain perfluorocarboxylic acids in the reaction solution. PFOA in the concentrations of 0.34-3.35 mM, typical of those in wastewaters after an emulsifying process in fluoropolymer manufacture, was completely decomposed by the catalyst within 24 h of irradiation from a 200-W xenon-mercury lamp, with no accompanying catalyst degradation, permitting the catalyst to be reused in consecutive runs. Gas chromatography/mass spectrometry (GC/MS) measurements showed no trace of environmentally undesirable species such as CF4, which has a very high global-warming potential. When the (initial PFOA)/(initial catalyst) molar ratio was 10: 1, the turnover number for PFOA decomposition reached 4.33 over 24 h of irradiation.

Ozone assisted oxidation of gaseous PCDD/Fs over CNTs-containing composite catalysts at low temperature.

PubMed

Wang, Qiulin; Tang, Minghui; Peng, Yaqi; Du, Cuicui; Lu, Shengyong

2018-05-01

Ozone assisted carbon nanotubes (CNTs) supported vanadium oxide/titanium dioxide (V/Ti-CNTs) or vanadium oxide-manganese oxide/titanium dioxide (V-Mn/Ti-CNTs) catalysts towards gaseous PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans) catalytic oxidations at low temperature (150 °C) were investigated. The removal efficiency (RE) and decomposition efficiency (DE) of PCDD/Fs achieved with V-Mn/Ti-CNTs alone were 95% and 45% at 150 °C under a space velocity (SV) of 14000 h -1 ; yet, these values reached 99% and 91% when catalyst and low concentration (50 ppm) ozone were used in combined. The ozone promotion effect on catalytic activity was further enhanced with the addition of manganese oxide (MnO x ) and CNTs. Adding MnO x and CNTs in V/Ti catalysts facilitated the ozone decomposition (creating more active species on catalyst surface), thus, improved ozone utilization (demanding relatively lower ozone addition concentration). On the other hand, this study threw light upon ozone promotion mechanism based on the comparison of catalyst properties (i.e. components, surface area, surface acidity, redox ability and oxidation state) before and after ozone treatment. The experimental results indicate that a synergistic effect exists between catalyst and ozone: ozone is captured and decomposed on catalyst surface; meanwhile, the catalyst properties are changed by ozone in return. Reactive oxygen species from ozone decomposition and the accompanied catalyst properties optimization are crucial reasons for catalyst activation at low temperature. Copyright © 2018 Elsevier Ltd. All rights reserved.

Highly efficient and stable catalyst for peroxynitrite decomposition

Treesearch

Yurii V. Geletii; Alan J. Bailey; Jennifer J. Cowan; Ira A. Weinstock; Craig L. Hill

2001-01-01

The new cobalt substituted-polyoxometalate K7[CoAlW11O39]•15H2O and the simple CoCl2•6H2O salt are efficient catalysts for peroxynitrite decomposition. These compounds also catalyze the oxidation of ascorbic acid and the nitration of phenol by peroxynitrite.

Removal of ammonia from urine vapor by a dual-catalyst system

NASA Technical Reports Server (NTRS)

Budininkas, P.

1977-01-01

The feasibility of removing ammonia from urine vapor by a low-temperature dual-catalyst system has been demonstrated. The process is based on the catalytic oxidation of ammonia to a mixture of nitrogen, nitrous oxide, and water, followed by a catalytic decomposition of the nitrous oxide into its elements. Potential ammonia oxidation and nitrous oxide decomposition catalysts were first screened with artificial gas mixtures, then tested with the actual urine vapor produced by boiling untreated urine. A suitable dual-catalyst bed arrangement was found that achieved the removal of ammonia and also organic carbon, and recovered water of good quality from urine vapor.

Comparative study of activated carbon, natural zeolite, and green sand supports for CuOX and ZnO sites as ozone decomposition catalyst

NASA Astrophysics Data System (ADS)

Azhariyah, A. S.; Pradyasti, A.; Dianty, A. G.; Bismo, S.

2018-03-01

This research was based on ozone decomposition in industrial environment. Ozone is harmful to human. Therefore, catalysts were made as a mask filter to decompose ozone. Comparison studies of catalyst supports were done using Granular Activated Carbon (GAC), Natural Zeolite (NZ), and Green Sand (GS). GAC showed the highest catalytic activity compared to other supports with conversion of 98%. Meanwhile, the conversion using NZ was only 77% and GS had been just 27%. GAC had the highest catalytic activity because it had the largest pore volume, which is 0.478 cm3/g. So GAC was used as catalyst supports. To have a higher conversion in ozone decomposition, GAC was impregnated with metal oxide as the active site of the catalyst. Active site comparison was made using CuOX and ZnO as the active site. Morphology, composition, and crystal phase were analyzed using SEM-EDX, XRF, and XRD methods. Mask filter, which contained catalysts for ozone decomposition, was tested using a fixed bed reactor at room temperature and atmospheric pressure. The result of conversion was analyzed using iodometric method. CuOX/GAC and ZnO/GAC 2%-w showed the highest catalytic activity and conversion reached 100%. From the durability test, CuOX/GAC 2%-w was better than ZnO/GAC 2%-w because the conversion of ozone to oxygen reached 100% with the lowest conversion was 70% for over eight hours.

Catalytic decomposition of tar derived from wood waste pyrolysis using Indonesian low grade iron ore as catalyst

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

Wicakso, Doni Rahmat; Chemical Engineering Department, Faculty of Engineering, Gadjah Mada University, Jalan Grafika No. 2 Bulaksumur, Yogyakarta, 55281; Sutijan

Low grade iron ore can be used as an alternative catalyst for bio-tar decomposition. Compared to other catalysts, such as Ni, Rd, Ru, Pd and Pt, iron ore is cheaper. The objective of this research was to investigate the effect of using low grade iron ore as catalyst for tar catalytic decomposition in fixed bed reactor. Tar used in this experiment was pyrolysis product of wood waste while the catalyst was Indonesian low grade iron ore. The variables studied were temperatures between 500 – 600 °C and catalyst weight between 0 – 40 gram. The first step, tar was evaporatedmore » at 450 °C to produce tar vapor. Then, tar vapor was flowed to fixed bed reactor filled low grade iron ore. Gas and tar vapor from reactor was cooled, then the liquid and uncondensable gas were analyzed by GC/MS. The catalyst, after experiment, was weighed to calculate total carbon deposited into catalyst pores. The results showed that the tar components that were heavy and light hydrocarbon were decomposed and cracked within the iron ore pores to from gases, light hydrocarbon (bio-oil) and carbon, thus decreasing content tar in bio-oil and increasing the total gas product. In conclusion, the more low grade iron ore used as catalyst, the tar content in the liquid decrease, the H{sup 2} productivity increased and calorimetric value of bio-oil increased.« less

Hydrogen iodide decomposition

DOEpatents

O'Keefe, Dennis R.; Norman, John H.

1983-01-01

Liquid hydrogen iodide is decomposed to form hydrogen and iodine in the presence of water using a soluble catalyst. Decomposition is carried out at a temperature between about 350.degree. K. and about 525.degree. K. and at a corresponding pressure between about 25 and about 300 atmospheres in the presence of an aqueous solution which acts as a carrier for the homogeneous catalyst. Various halides of the platinum group metals, particularly Pd, Rh and Pt, are used, particularly the chlorides and iodides which exhibit good solubility. After separation of the H.sub.2, the stream from the decomposer is countercurrently extracted with nearly dry HI to remove I.sub.2. The wet phase contains most of the catalyst and is recycled directly to the decomposition step. The catalyst in the remaining almost dry HI-I.sub.2 phase is then extracted into a wet phase which is also recycled. The catalyst-free HI-I.sub.2 phase is finally distilled to separate the HI and I.sub.2. The HI is recycled to the reactor; the I.sub.2 is returned to a reactor operating in accordance with the Bunsen equation to create more HI.

Haloporphyrins and their preparation and use as catalysts

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1997-01-01

The invention provides novel catalyst compositions, useful in the oxidation of hydrocarbons with air or oxygen to form hydroxy-group containing compounds and in the decomposition of hydroperoxides to form hydroxy-group containing compounds. The catalysts comprise transition metal complexes of a porphyrin ring having 1 to 12 halogen substituents on the porphyrin ring, at least one of said halogens being in a meso position and/or the catalyst containing no aryl group in a meso position. The compositions are prepared by halogenating a transition metal complex of a porphyrin. In one embodiment, a complex of a porphyrin with a metal whose porphyrin complexes are not active for oxidation of hydrocarbons is halogenated, thereby to obtain a haloporphyrin complex of that metal, the metal is removed from the haloporphyrin complex to obtain the free base form of the haloporphyrin, and a metal such as iron whose porphyrin complexes are active for oxidation of hydrocarbons and for the decomposition of alkyl hydroperoxides is complexed with the free base to obtain an active catalyst for oxidation of hydrocarbons and decomposition of alkyl hydroperoxides.

Haloporphyrins and their preparation and use as catalysts

DOEpatents

Ellis, P.E. Jr.; Lyons, J.E.

1997-09-02

The invention provides novel catalyst compositions, useful in the oxidation of hydrocarbons with air or oxygen to form hydroxy-group containing compounds and in the decomposition of hydroperoxides to form hydroxy-group containing compounds. The catalysts comprise transition metal complexes of a porphyrin ring having 1 to 12 halogen substituents on the porphyrin ring, at least one of said halogens being in a meso position and/or the catalyst containing no aryl group in a meso position. The compositions are prepared by halogenating a transition metal complex of a porphyrin. In one embodiment, a complex of a porphyrin with a metal whose porphyrin complexes are not active for oxidation of hydrocarbons is halogenated, thereby to obtain a haloporphyrin complex of that metal, the metal is removed from the haloporphyrin complex to obtain the free base form of the haloporphyrin, and a metal such as iron whose porphyrin complexes are active for oxidation of hydrocarbons and for the decomposition of alkyl hydroperoxides is complexed with the free base to obtain an active catalyst for oxidation of hydrocarbons and decomposition of alkyl hydroperoxides.

Hydrogenation catalysts were derived from Mo(Co)/sub 6//alumina

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

Bowman, R.G.

1979-01-01

Alumina hydrogenation catalysts were derived from mo(CO)/sub 6//alumina with characteristics dependent upon the activation temperature, degree of alumina hydroxylation, and carrier gas used. Decomposition of Mo(CO)/sub 6/ at 100/sup 0/C on partially hydroxylated alumina in helium or hydrogen yielded Mo(CO)/sub 3//alumina, which catalyzed olefin metathesis in helium carrier and both metathesis and hydrogenation in hydrogen carrier. Decomposition of Mo(CO)/sub 6/ on dehydroxylated alumina at 100/sup 0/C in helium and in hydrogen resulted in complete decarbonylation and partial oxidation of molybdenum; this catalyst was 10 times as active as Mo(CO)/sub 3//alumina for hydrogenation. Decomposition of Mo(CO)/sub 6/ on dehydroxylated alumina atmore » 500/sup 0/C in helium gave essentially Mo(0)/alumina, which catalyzed hydrogenation, methanation, and hydrogenolysis in hydrogen. Catalysts activated on dehydroxylated alumina were ten times more active for methanation at 300/sup 0/C than catalyst activated on partially hydroxylated alumina and showed differences in selectivity for cyclopropane hydrogenolysis at 100/sup 0/C.« less

Catalytic decomposition of toxic chemicals over iron group metals supported on carbon nanotubes.

PubMed

Li, Lili; Chen, Can; Chen, Long; Zhu, Zixue; Hu, Jianli

2014-03-18

This study explores catalytic decomposition of phosphine (PH3) using iron group metals (Co, Ni) and metal oxides (Fe2O3, Co(3)O4, NiO) supported on carbon nanotubes (CNTs). The catalysts are synthesized by means of a deposition-precipitation method. The morphology, structure, and composition of the catalysts are characterized using a number of analytical instrumentations, including high-resolution transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, BET surface area measurement, and inductively coupled plasma. The activity of the catalysts in the PH3 decomposition reaction is measured and correlated with their surface and structural properties. The characterization results show that phosphidation occurs on the catalyst surface, and the resulting metal phosphides act as an active phase in the PH3 decomposition reaction. Cobalt phosphide, CoP, is formed on Co/CNTs and Co(3)O4/CNTs, whereas iron phosphide, FeP, is formed on Fe2O3/CNTs. In contrast, phosphorus-rich phosphide NiP2 is formed on Ni/CNTs and NiO/CNTs. The initial activities of the catalysts are shown in the following sequence: Ni/CNTs > Co/CNTs > Co(3)O4/CNTs >NiO/CNTs > Fe2O3/CNTs, whereas activities of metal phosphides are shown in the following order: CoP > NiP2 > FeP. The catalytic activity of metal phosphides is attributed to their electronic properties. Cobalt phosphide formed on Co/CNTs and Co(3)O4/CNTs exhibits not only the highest activity, but also long-term stability in the PH3 decomposition reaction.

Method and apparatus for maintaining the pH in zinc-bromine battery systems

DOEpatents

Grimes, Patrick G.

1985-09-10

A method and apparatus for maintaining the pH level in a zinc-bromine battery features reacting decomposition hydrogen with bromine in the presence of a catalyst. The catalyst encourages the formation of hydrogen and bromine ions. The decomposition hydrogen is therefore consumed, alloying the pH of the system to remain substantially at a given value.

Study on the decomposition of trace benzene over V2O5-WO3/TiO2-based catalysts in simulated flue gas

EPA Science Inventory

Commercial and laboratory-prepared V2O5–WO3/TiO2-based catalysts with different compositions were tested for catalytic decomposition of chlorobenzene （ClBz） in simulated flue gas. Resonance enhanced multiphoton ionization-time of flight mass spectrometry (REMPI-TOFMS) was employe...

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.

Thermal degradation of Shredded Oil Palm Empty Fruit Bunches (SOPEFB) embedded with Cobalt catalyst by Thermogravimetric Analysis (TGA)

NASA Astrophysics Data System (ADS)

Alias, R.; Hamid, N. H.; Jaapar, J.; Musa, M.; Alwi, H.; Halim, K. H. Ku

2018-03-01

Thermal behavior and decomposition kinetics of shredded oil palm empty fruit bunches (SOPEFB) were investigated in this study by using thermogravimetric analysis (TGA). The SOPEFB were analyzed under conditions of temperature 30 °C to 900 °C with nitrogen gas flow at 50 ml/min. The SOPEFB were embedded with cobalt (II) nitrate solution with concentration 5%, 10%, 15% and 20%. The TG/DTG curves shows the degradation behavior of SOPEFB following with char production for each heating rate and each concentration of cobalt catalyst. Thermal degradation occurred in three phases, water drying phase, decomposition of hemicellulose and cellulose phase, and lignin decomposition phase. The kinetic equation with relevant parameters described the activation energy required for thermal degradation at the temperature regions of 200 °C to 350 °C. Activation energy (E) for different heating rate with SOPEFB embedded with different concentration of cobalt catalyst showing that the lowest E required was at SOPEFB with 20% concentration of cobalt catalyst..

Study of removal of ammonia from urine vapor by dual catalyst

NASA Technical Reports Server (NTRS)

Budininkas, P.

1976-01-01

The feasibility of ammonia removal from urine vapor by a low temperature dual-catalyst system was investigated. The process is based on the initial catalytic oxidation of ammonia present in urine vapor to nitrogen and nitrous oxide, followed by a catalytic decomposition of the nitrous oxide formed into its elements. The most active catalysts for the oxidation of ammonia and for the decomposition of N2O, identified in screening tests, were then combined into dual catalyst systems and tested to establish their overall efficiencies for the removal of ammonia from artificial gas mixtures. Dual catalyst systems capable of ammonia removal from the artificial gas mixtures were then tested with the actual urine vapor produced by boiling untreated urine. A suitable dual catalyst bed arrangement was found that achieved the removal of ammonia and organic carbon, and recovered water of good quality from urine vapor.

Pt deposited TiO2 catalyst fabricated by thermal decomposition of titanium complex for solar hydrogen production

NASA Astrophysics Data System (ADS)

Truong, Quang Duc; Le, Thanh Son; Ling, Yong-Chien

2014-12-01

C, N codoped TiO2 catalyst has been synthesized by thermal decomposition of a novel water-soluble titanium complex. The structure, morphology, and optical properties of the synthesized TiO2 catalyst were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and UV-vis diffuse reflectance spectroscopy. The photocatalytic activity of the Pt deposited TiO2 catalysts synthesized at different temperatures was evaluated by means of hydrogen evolution reaction under both UV-vis and visible light irradiation. The investigation results reveal that the photocatalytic H2 evolution rate strongly depended on the crystalline grain size as well as specific surface area of the synthesized catalyst. Our studies successfully demonstrate a simple method for the synthesis of visible-light responsive Pt deposited TiO2 catalyst for solar hydrogen production.

Active sites and mechanisms for H2O2 decomposition over Pd catalysts

PubMed Central

Plauck, Anthony; Stangland, Eric E.; Dumesic, James A.; Mavrikakis, Manos

2016-01-01

A combination of periodic, self-consistent density functional theory (DFT-GGA-PW91) calculations, reaction kinetics experiments on a SiO2-supported Pd catalyst, and mean-field microkinetic modeling are used to probe key aspects of H2O2 decomposition on Pd in the absence of cofeeding H2. We conclude that both Pd(111) and OH-partially covered Pd(100) surfaces represent the nature of the active site for H2O2 decomposition on the supported Pd catalyst reasonably well. Furthermore, all reaction flux in the closed catalytic cycle is predicted to flow through an O–O bond scission step in either H2O2 or OOH, followed by rapid H-transfer steps to produce the H2O and O2 products. The barrier for O–O bond scission is sensitive to Pd surface structure and is concluded to be the central parameter governing H2O2 decomposition activity. PMID:27006504

Synthesis and Stabilization of Supported Metal Catalysts by Atomic Layer Deposition

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

Lu, Junling; Elam, Jeffrey W.; Stair, Peter C.

2013-03-12

Supported metal nanoparticles are among the most important cata-lysts for many practical reactions, including petroleum refining, automobile exhaust treatment, and Fischer–Tropsch synthesis. The catalytic performance strongly depends on the size, composition, and structure of the metal nanoparticles, as well as the underlying support. Scientists have used conventional synthesis methods including impregnation, ion exchange, and deposition–precipitation to control and tune these factors, to establish structure–performance relationships, and to develop better catalysts. Meanwhile, chemists have improved the stability of metal nanoparticles against sintering by the application of protective layers, such as polymers and oxides that encapsulate the metal particle. This often leadsmore » to decreased catalytic activity due to a lack of precise control over the thickness of the protective layer. A promising method of catalyst synthesis is atomic layer deposition (ALD). ALD is a variation on chemical vapor deposition in which metals, oxides, and other materials are deposited on surfaces by a sequence of self-limiting reactions. The self-limiting character of these reactions makes it possible to achieve uniform deposits on high-surface-area porous solids. Therefore, design and synthesis of advanced catalysts on the nanoscale becomes possible through precise control over the structure and composition of the underlying support, the catalytic active sites, and the protective layer. In this Account, we describe our advances in the synthesis and stabilization of supported metal catalysts by ALD. After a short introduction to the technique of ALD, we show several strategies for metal catalyst synthesis by ALD that take advantage of its self-limiting feature. Monometallic and bimetallic catalysts with precise control over the metal particle size, composition, and structure were achieved by combining ALD sequences, surface treatments, and deposition temperature control. Next, we describe ALD oxide overcoats applied with atomically precise thickness control that stabilize metal catalysts while preserving their catalytic function. We also discuss strategies for generation and control over the porosity of the overcoats that allow the embedded metal particles to remain accessible by reactants, and the details for ALD alumina overcoats on metal catalysts. Moreover, using methanol decomposition and oxidative dehydrogenation of ethane as probe reactions, we demonstrate that selectively blocking low coordination metal sites by oxide overcoats can provide another strategy to enhance both the durability and selectivity of metal catalysts.« less

Comparison of the decomposition characteristics of aromatic VOCs using an electron beam hybrid system

NASA Astrophysics Data System (ADS)

Son, Youn-Suk; Kim, Ki-Joon; Kim, Ji-Yong; Kim, Jo-Chun

2010-12-01

We applied a hybrid technique to assess the decomposition characteristics of ethylbenzene and toluene that annexed the catalyst technique with existing electron beam (EB) technology. The removal efficiency of ethylbenzene in the EB-catalyst hybrid turned out to be 30% greater than that of EB-only treatment. We concluded that ethylbenzene was decomposed more easily than toluene by EB irradiation. We compared the independent effects of the EB-catalyst hybrid and catalyst-only methods, and observed that the efficiency of the EB-catalyst hybrid demonstrated approximately 6% improvement for decomposing toluene and 20% improvement for decomposing ethylbenzene. The G-values for ethylbenzene increased with initial concentration and reactor type: for example, the G-values by reactor type at 2800 ppmC were 7.5-10.9 (EB-only) and 12.9-25.7 (EB-catalyst hybrid). We also observed a significant decrease in by-products as well as in the removal efficiencies associated with the EB-catalyst hybrid technique.

Characteristics of back corona discharge in a honeycomb catalyst and its application for treatment of volatile organic compounds.

PubMed

Feng, Fada; Zheng, Yanyan; Shen, Xinjun; Zheng, Qinzhen; Dai, Shaolong; Zhang, Xuming; Huang, Yifan; Liu, Zhen; Yan, Keping

2015-06-02

The main technical challenges for the treatment of volatile organic compounds (VOCs) with plasma-assisted catalysis in industrial applications are large volume plasma generation under atmospheric pressure, byproduct control, and aerosol collection. To solve these problems, a back corona discharge (BCD) configuration has been designed to evenly generate nonthermal plasma in a honeycomb catalyst. Voltage-current curves, discharge images, and emission spectra have been used to characterize the plasma. Grade particle collection results and flow field visualization in the discharge zones show not only that the particles can be collected efficiently, but also that the pressure drop of the catalyst layer is relatively low. A three-stage plasma-assisted catalysis system, comprising a dielectric barrier discharge (DBD) stage, BCD stage, and catalyst stage, was built to evaluate toluene treatment performance by BCD. The ozone analysis results indicate that BCD enhances the ozone decomposition by collecting aerosols and protecting the Ag-Mn-O catalyst downstream from aerosol contamination. The GC and FTIR results show that BCD contributes to toluene removal, especially when the specific energy input is low, and the total removal efficiency reaches almost 100%. Furthermore, this removal results in the emission of fewer byproducts.

Application of microscopy technology in thermo-catalytic methane decomposition to hydrogen

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

Mei, Irene Lock Sow, E-mail: irene.sowmei@gmail.com; Lock, S. S. M., E-mail: serenelock168@gmail.com; Abdullah, Bawadi, E-mail: bawadi-abdullah@petronas.com.my

2015-07-22

Hydrogen production from the direct thermo-catalytic decomposition of methane is a promising alternative for clean fuel production because it produces pure hydrogen without any CO{sub x} emissions. However, thermal decomposition of methane can hardly be of any practical and empirical interest in the industry unless highly efficient and effective catalysts, in terms of both specific activity and operational lifetime have been developed. In this work, bimetallic Ni-Pd on gamma alumina support have been developed for methane cracking process by using co-precipitation and incipient wetness impregnation method. The calcined catalysts were characterized to determine their morphologies and physico-chemical properties by usingmore » Brunauer-Emmett-Teller method, Field Emission Scanning Electron Microscopy, Energy-dispersive X-ray spectroscopy and Thermogravimetric Analysis. The results suggested that that the catalyst which is prepared by the co-precipitation method exhibits homogeneous morphology, higher surface area, have uniform nickel and palladium dispersion and higher thermal stability as compared to the catalyst which is prepared by wet impregnation method. This characteristics are significant to avoid deactivation of the catalysts due to sintering and carbon deposition during methane cracking process.« less

Computational Elucidation of Selectivities and Mechanisms Performed by Organometallic and Bioinorganic Catalysts

NASA Astrophysics Data System (ADS)

Grandner, Jessica Marie

Computational methods were used to determine the mechanisms and selectivities of organometallic-catalyzed reactions. The first half of the dissertation focuses on the study of metathesis catalysts in collaboration with the Grubbs group at CalTech. Chapter 1 describes the studies of the decomposition modes of several ruthenium-based metathesis catalysts. These studies were performed to better understand the decomposition of such catalysts in order to prevent decomposition (Chapter 1.2) or utilize decomposed catalysts for alternative reactions (Chapter 1.1). Chapter 2.1 describes the computational investigation of the origins of stereoretentive metathesis with ruthenium-based metathesis catalysts. These findings were then used to computationally design E-selective metathesis catalysts (Chapter 2.2). While the first half of the dissertation was centered around ruthenium catalysts, the second half of the dissertation pertains to iron-catalyzed reaction, in particular, iron-catalyzed reactions by P450 enzymes. The elements of Chapter 3 concentrate on the stereo- and chemo-selectivity of P450-catalyzed C-H hydroxylations. By combining multiple computational methods, the inherent activity of the iron-oxo catalyst and the influence of the active site on such reactions were illuminated. These discoveries allow for the engineering of new substrates and mutant enzymes for tailored C-H hydroxylation. While the mechanism of C-H hydroxylations catalyzed by P450 enzymes has been well studied, there are several P450-catalyzed transformations for which the mechanism is unknown. The components of Chapter 4 describe the use of computations to determine the mechanisms of complex, multi-step reactions catalyzed by P450s. The determination of these mechanisms elucidates how these enzymes react with various functional groups and substrate architectures and allows for a better understanding of how drug-like compounds may be broken down by human P450s.

Reactions catalyzed by haloporphyrins

DOEpatents

Ellis, P.E. Jr.; Lyons, J.E.

1996-02-06

The invention provides novel methods for the oxidation of hydrocarbons with oxygen-containing gas to form hydroxy-group containing compounds and for the decomposition of hydroperoxides to form hydroxy-group containing compounds. The catalysts used in the methods of the invention comprise transition metal complexes of a porphyrin ring having 1 to 12 halogen substituents on the porphyrin ring, at least one of said halogens being in a meso position and/or the catalyst containing no aryl group in a meso position. The catalyst compositions are prepared by halogenating a transition metal complex of a porphyrin. In one embodiment, a complex of a porphyrin with a metal whose porphyrin complexes are not active for oxidation of alkanes is halogenated, thereby to obtain a haloporphyrin complex of that metal, the metal is removed from the haloporphyrin complex to obtain the free base form of the haloporphyrin, and a metal such as iron whose porphyrin complexes are active for oxidation of alkanes and for the decomposition of alkyl hydroperoxides is complexed with the free base to obtain an active catalyst for oxidation of alkanes and decomposition of alkyl hydroperoxides.

Reactions catalyzed by haloporphyrins

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1996-01-01

The invention provides novel methods for the oxidation of hydrocarbons with oxygen-containing gas to form hydroxy-group containing compounds and for the decomposition of hydroperoxides to form hydroxygroup containing compounds. The catalysts used in the methods of the invention comprise transition metal complexes of a porphyrin ring having 1 to 12 halogen substituents on the porphyrin ring, at least one of said halogens being in a meso position and/or the catalyst containing no aryl group in a meso position. The catalyst compositions are prepared by halogenating a transition metal complex of a porphyrin. In one embodiment, a complex of a porphyrin with a metal whose porphyrin complexes are not active for oxidation of alkanes is halogenated, thereby to obtain a haloporphyrin complex of that metal, the metal is removed from the haloporphyrin complex to obtain the free base form of the haloporphyrin, and a metal such as iron whose porphyrin complexes are active for oxidation of alkanes and for the decomposition of alkyl hydroperoxides is complexed with the free base to obtain an active catalyst for oxidation of alkanes and decomposition of alkyl hydroperoxides.

Enhanced Thermal Decomposition Properties of CL-20 through Space-Confining in Three-Dimensional Hierarchically Ordered Porous Carbon.

PubMed

Chen, Jin; He, Simin; Huang, Bing; Wu, Peng; Qiao, Zhiqiang; Wang, Jun; Zhang, Liyuan; Yang, Guangcheng; Huang, Hui

2017-03-29

High energy and low signature properties are the future trend of solid propellant development. As a new and promising oxidizer, hexanitrohexaazaisowurtzitane (CL-20) is expected to replace the conventional oxidizer ammonium perchlorate to reach above goals. However, the high pressure exponent of CL-20 hinders its application in solid propellants so that the development of effective catalysts to improve the thermal decomposition properties of CL-20 still remains challenging. Here, 3D hierarchically ordered porous carbon (3D HOPC) is presented as a catalyst for the thermal decomposition of CL-20 via synthesizing a series of nanostructured CL-20/HOPC composites. In these nanocomposites, CL-20 is homogeneously space-confined into the 3D HOPC scaffold as nanocrystals 9.2-26.5 nm in diameter. The effect of the pore textural parameters and surface modification of 3D HOPC as well as CL-20 loading amount on the thermal decomposition of CL-20 is discussed. A significant improvement of the thermal decomposition properties of CL-20 is achieved with remarkable decrease in decomposition peak temperature (from 247.0 to 174.8 °C) and activation energy (from 165.5 to 115.3 kJ/mol). The exceptional performance of 3D HOPC could be attributed to its well-connected 3D hierarchically ordered porous structure, high surface area, and the confined CL-20 nanocrystals. This work clearly demonstrates that 3D HOPC is a superior catalyst for CL-20 thermal decomposition and opens new potential for further applications of CL-20 in solid propellants.

Furfural production from biomass pretreatment hydrolysate using vapor-releasing reactor system.

PubMed

Liu, Lu; Chang, Hou-Min; Jameel, Hasan; Park, Sunkyu

2018-03-01

Biomass hydrolysate from autohydrolysis pretreatment was used for furfural production considering it is in rich of xylose, xylo-oligomers, and other decomposition products from hemicellulose structure. By using the vapor-releasing reactor system, furfural was protected from degradation by separating it from the reaction media. The maximum furfural yield of 73% was achieved at 200 °C for biomass hydrolysate without the use of the catalyst. This is because the presence of organic acids such as acetic acid in hydrolysate functioned as a catalyst. According to the results in this study, biomass hydrolysate with a vapor-releasing system proves to be efficient for furfural production. The biorefinery process which allows the separation of xylose-rich autohydrolysate from other parts from biomass feedstock also improves the overall application of the biomass. Copyright © 2018 Elsevier Ltd. All rights reserved.

OXIDATION OF METHANOL USING OZONE ON TITANIA-SUPPORTED VANADIUM CATALYST

EPA Science Inventory

Catalytic ozone decomposition of methanol has been conducted at mild temperatures of 100 to 250°C using V2O5/TiO2 catalyst prepared by either sol-gel or wet impregnation methods. The catalysts were characterized using XRD, surface area measurements, and desorption of CH3OH. Gas p...

From a Decomposition Product to an Efficient and Versatile Catalyst: The [Ru(η5-indenyl)(PPh3)2Cl] Story

PubMed Central

2014-01-01

Conspectus One of the most important challenges in catalyst design is the synthesis of stable promoters without compromising their activity. For this reason, it is important to understand the factors leading to decomposition of such catalysts, especially if side-products negatively affect the activity and selectivity of the starting complex. In this context, the understanding of termination and decomposition processes in olefin metathesis is receiving significant attention from the scientific community. For example, the decomposition of ruthenium olefin metathesis precatalysts in alcohol solutions can occur during either the catalyst synthesis or the metathesis process, and such decomposition has been found to be common for Grubbs-type precatalysts. These decomposition products are usually hydridocarbonyl complexes, which are well-known to be active in several transformations such as hydrogenation, terminal alkene isomerization, and C–H activation chemistry. The reactivity of these side products can be unwanted, and it is therefore important to understand how to avoid them and maybe also important to keep an open mind and think of ways to use these in other catalytic reactions. A showcase of these decomposition studies is reported in this Account. These reports analyze the stability of ruthenium phenylindenylidene complexes, highly active olefin metathesis precatalysts, in basic alcohol solutions. Several different decomposition processes can occur under these conditions depending on the starting complex and the alcohol used. These indenylidene-bearing metathesis complexes display a completely different behavior compared with that of other metathesis precatalysts and show an alternative competitive alcoholysis pathway, where rather than forming the expected hydrido carbonyl complexes, the indenylidene fragment is transformed into a η1-indenyl, which then rearranges to its η5-indenyl form. In particular, [RuCl(η5-(3-phenylindenylidene)(PPh3)2] has been found to be extremely active in numerous transformations (at least 20) as well as compatible with a broad range of reaction conditions, rendering it a versatile catalytic tool. It should be stated that the η5-phenyl indenyl ligand shows enhanced catalytic activity over related half-sandwich ruthenium complexes. The analogous half-sandwich (cyclopentadienyl and indenyl) ruthenium complexes show lower activity in transfer hydrogenation and allylic alcohol isomerization reactions. In addition, this catalyst allows access to new phenylindenyl ruthenium complexes, which can be achieved in a very straightforward manner and have been successfully used in catalysis. This Account provides an overview of how mechanistic insights into decomposition and stability of a well-known family of ruthenium metathesis precatalysts has resulted in a series of novel and versatile ruthenium complexes with unexpected reactivity. PMID:25264626

Catalytic conversion of hydrocarbons to hydrogen and high-value carbon

DOEpatents

Shah, Naresh; Panjala, Devadas; Huffman, Gerald P.

2005-04-05

The present invention provides novel catalysts for accomplishing catalytic decomposition of undiluted light hydrocarbons to a hydrogen product, and methods for preparing such catalysts. In one aspect, a method is provided for preparing a catalyst by admixing an aqueous solution of an iron salt, at least one additional catalyst metal salt, and a suitable oxide substrate support, and precipitating metal oxyhydroxides onto the substrate support. An incipient wetness method, comprising addition of aqueous solutions of metal salts to a dry oxide substrate support, extruding the resulting paste to pellet form, and calcining the pellets in air is also discloses. In yet another aspect, a process is provided for producing hydrogen from an undiluted light hydrocarbon reactant, comprising contacting the hydrocarbon reactant with a catalyst as described above in a reactor, and recovering a substantially carbon monoxide-free hydrogen product stream. In still yet another aspect, a process is provided for catalytic decomposition of an undiluted light hydrocarbon reactant to obtain hydrogen and a valuable multi-walled carbon nanotube coproduct.

Efficient Method for the Determination of the Activation Energy of the Iodide-Catalyzed Decomposition of Hydrogen Peroxide

ERIC Educational Resources Information Center

Sweeney, William; Lee, James; Abid, Nauman; DeMeo, Stephen

2014-01-01

An experiment is described that determines the activation energy (E[subscript a]) of the iodide-catalyzed decomposition reaction of hydrogen peroxide in a much more efficient manner than previously reported in the literature. Hydrogen peroxide, spontaneously or with a catalyst, decomposes to oxygen and water. Because the decomposition reaction is…

Catalysts for Efficient Production of Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Sun, Ted X.; Dong, Yi

2009-01-01

Several metal alloys have shown promise as improved catalysts for catalytic thermal decomposition of hydrocarbon gases to produce carbon nanotubes (CNTs). Heretofore almost every experiment on the production of carbon nanotubes by this method has involved the use of iron, nickel, or cobalt as the catalyst. However, the catalytic-conversion efficiencies of these metals have been observed to be limited. The identification of better catalysts is part of a continuing program to develop means of mass production of high-quality carbon nanotubes at costs lower than those achieved thus far (as much as $100/g for purified multi-wall CNTs or $1,000/g for single-wall CNTs in year 2002). The main effort thus far in this program has been the design and implementation of a process tailored specifically for high-throughput screening of alloys for catalyzing the growth of CNTs. The process includes an integral combination of (1) formulation of libraries of catalysts, (2) synthesis of CNTs from decomposition of ethylene on powders of the alloys in a pyrolytic chemical-vapor-decomposition reactor, and (3) scanning- electron-microscope screening of the CNTs thus synthesized to evaluate the catalytic efficiencies of the alloys. Information gained in this process is put into a database and analyzed to identify promising alloy compositions, which are to be subjected to further evaluation in a subsequent round of testing. Some of these alloys have been found to catalyze the formation of carbon nano tubes from ethylene at temperatures as low as 350 to 400 C. In contrast, the temperatures typically required for prior catalysts range from 550 to 750 C.

Nanoscale Silicon as a Catalyst for Graphene Growth: Mechanistic Insight from in Situ Raman Spectroscopy

DOE PAGES

Share, Keith; Carter, Rachel E.; Nikolaev, Pavel; ...

2016-06-08

Nanoscale carbons are typically synthesized by thermal decomposition of a hydrocarbon at the surface of a metal catalyst. Whereas the use of silicon as an alternative to metal catalysts could unlock new techniques to seamlessly couple carbon nanostructures and semiconductor materials, stable carbide formation renders bulk silicon incapable of the precipitation and growth of graphitic structures. In this article, we provide evidence supported by comprehensive in situ Raman experiments that indicates nanoscale grains of silicon in porous silicon (PSi) scaffolds act as catalysts for hydrocarbon decomposition and growth of few-layered graphene at temperatures as low as 700 K. Self-limiting growthmore » kinetics of graphene with activation energies measured between 0.32–0.37 eV elucidates the formation of highly reactive surface-bound Si radicals that aid in the decomposition of hydrocarbons. Nucleation and growth of graphitic layers on PSi exhibits striking similarity to catalytic growth on nickel surfaces, involving temperature dependent surface and subsurface diffusion of carbon. Lastly, this work elucidates how the nanoscale properties of silicon can be exploited to yield catalytic properties distinguished from bulk silicon, opening an important avenue to engineer catalytic interfaces combining the two most technologically important materials for modern applications—silicon and nanoscale carbons.« less

In-situ and self-distributed: A new understanding on catalyzed thermal decomposition process of ammonium perchlorate over Nd{sub 2}O{sub 3}

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

Zou, Min, E-mail: zoumin3362765@163.com; Wang, Xin, E-mail: wangx@mail.njust.edu.cn; Jiang, Xiaohong, E-mail: jxh0668@sina.com

2014-05-01

Catalyzed thermal decomposition process of ammonium perchlorate (AP) over neodymium oxide (Nd{sub 2}O{sub 3}) was investigated. Catalytic performances of nanometer-sized Nd{sub 2}O{sub 3} and micrometer-sized Nd{sub 2}O{sub 3} were evaluated by differential scanning calorimetry (DSC). In contrast to universal concepts, catalysts in different sizes have nearly similar catalytic activities. Based on structural and morphological variation of the catalysts during the reaction, combined with mass spectrum analyses and studies of unmixed style, a new understanding of this catalytic process was proposed. We believed that the newly formed chloride neodymium oxide (NdOCl) was the real catalytic species in the overall thermal decompositionmore » of AP over Nd{sub 2}O{sub 3}. Meanwhile, it was the “self-distributed” procedure which occurred within the reaction that also worked for the improvement of overall catalytic activities. This work is of great value in understanding the roles of micrometer-sized catalysts used in heterogeneous reactions, especially the solid–solid reactions which could generate a large quantity of gaseous species. - Graphical abstract: In-situ and self-distributed reaction process in thermal decomposition of AP catalyzed by Nd{sub 2}O{sub 3}. - Highlights: • Micro- and nano-Nd{sub 2}O{sub 3} for catalytic thermal decomposition of AP. • No essential differences on their catalytic performances. • Structural and morphological variation of catalysts digs out catalytic mechanism. • This catalytic process is “in-situ and self-distributed” one.« less

Utilization of a by-product produced from oxidative desulfurization process over Cs-mesoporous silica catalysts.

PubMed

Kim, Hyeonjoo; Jeong, Kwang-Eun; Jeong, Soon-Yong; Park, Young-Kwon; Kim, Do Heui; Jeon, Jong-Ki

2011-02-01

We investigated the use of Cs-mesoporous silica catalysts to upgrade a by-product of oxidative desulfurization (ODS). Cs-mesoporous silica catalysts were characterized through N2 adsorption, XRD, CO2-temperature-programmed desorption, and XRF. Cs-mesoporous silica prepared by the direct incorporation method showed higher catalytic performance than a Cs/MCM-41 catalyst by impregnation method for the catalytic decomposition of sulfone compounds produced from ODS process.

Synthesis of Water-Soluble Palladium Nanoparticles Stabilized by Sulfonated N-Heterocyclic Carbenes.

PubMed

Asensio, Juan M; Tricard, Simon; Coppel, Yannick; Andrés, Román; Chaudret, Bruno; de Jesús, Ernesto

2017-09-27

A strategy involving the decomposition of palladium(II) organometallic complexes with sulfonated N-heterocyclic carbene ligands leads to the formation of stable and water-soluble Pd nanoparticles. Three different methodologies (thermal decomposition, reduction under 13 CO atmosphere, and reduction with H 2 ) gave particles with different shapes and sizes, ranging from 1.5 to 7 nm. The structures of the organometallic intermediates and organic decomposition products were elucidated by NMR spectroscopy. To check the accessibility of the surface, the nanoparticles were tested as catalysts for the chemoselective hydrogenation of styrene in water. An effect of the particle size on the catalyst activity was observed. The aqueous phase was recycled up to ten times without any precipitation of metallic palladium. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Combustion engine system

NASA Technical Reports Server (NTRS)

Houseman, John (Inventor); Voecks, Gerald E. (Inventor)

1986-01-01

A flow through catalytic reactor which selectively catalytically decomposes methanol into a soot free hydrogen rich product gas utilizing engine exhaust at temperatures of 200 to 650 C to provide the heat for vaporizing and decomposing the methanol is described. The reactor is combined with either a spark ignited or compression ignited internal combustion engine or a gas turbine to provide a combustion engine system. The system may be fueled entirely by the hydrogen rich gas produced in the methanol decomposition reactor or the system may be operated on mixed fuels for transient power gain and for cold start of the engine system. The reactor includes a decomposition zone formed by a plurality of elongated cylinders which contain a body of vapor permeable, methanol decomposition catalyst preferably a shift catalyst such as copper-zinc.

Production of furfural from palm oil empty fruit bunches: kinetic model comparation

NASA Astrophysics Data System (ADS)

Panjaitan, J. R. H.; Monica, S.; Gozan, M.

2017-05-01

Furfural is a chemical compound that can be applied to pharmaceuticals, cosmetics, resins and cleaning compound which can be produced by acid hydrolysis of biomass. Indonesia’s demand for furfural in 2010 reached 790 tons that still imported mostly 72% from China. In this study, reaction kinetic models of furfural production from oil palm empty fruit bunches with submitting acid catalyst at the beginning of the experiment will be determine. Kinetic data will be obtained from hydrolysis of empty oil palm bunches using sulfuric acid catalyst 3% at temperature 170°C, 180°C and 190°C for 20 minutes. From this study, the kinetic model to describe the production of furfural is the kinetic model where generally hydrolysis reaction with an acid catalyst in hemicellulose and furfural will produce the same decomposition product which is formic acid with different reaction pathways. The activation energy obtained for the formation of furfural, the formation of decomposition products from furfural and the formation of decomposition products from hemicellulose is 8.240 kJ/mol, 19.912 kJ/mol and -39.267 kJ / mol.

Catalytic thermal decomposition of methane to COx-free hydrogen and carbon nanotubes over MgO supported bimetallic group VIII catalysts

NASA Astrophysics Data System (ADS)

Awadallah, A. E.; Aboul-Enein, A. A.; El-Desouki, D. S.; Aboul-Gheit, A. K.

2014-03-01

Bimetallic Ni-Fe, Ni-Co and Fe-Co supported on MgO catalysts with a total metals content of 50 wt.% were evaluated for decomposition of methane to CO/CO2 free hydrogen and carbon nanomaterials. The catalytic runs were carried out at 700 °C under atmospheric pressure using fixed bed horizontal flow reactor. The materials were characterized by XRD, TEM, Raman spectroscopy, surface analysis and TGA-DTG. The data showed that the bimetallic 25% Fe-25%Co/MgO catalyst exhibited remarkable higher activity and stability up to ˜10 h time-on-stream with respect to H2 production. However, the catalytic activity and durability was greatly declined after incorporating 25%Ni to either 25%Fe or 25%Co/MgO catalysts at all time on stream. The main reason for the catalytic inhibition of Ni containing catalysts is consuming NiO during the formation of rock-salt MgxNi(1-x)O solid solution. However, the almost complete segregation of Fe2O3 and Co3O4 oxides played an important role for the high activity of the Fe-Co based catalyst. TEM images illustrate that the accumulated carbon over all catalysts are multi-walled carbon nanotubes in nature. The TG data showed that a higher yield of MWCNTs was achieved over bimetallic Fe-Co catalyst compared to the Ni-Fe or Ni-Co containing catalysts.

BASE-CATALYZED DESTRUCTION OF PCBS-NEW DONORS, NEW TRANSFER AGENTS/CATALYSTS

EPA Science Inventory

The use of hydrogen transfer agents and catalysts to improve the base-catalyzed decomposition of polychlorinated biphenyls (PCBs) was investigated. The reaction proceeded only in the presence of base, but the rate of PCB disappearance increased with increasing amount of hydrogen ...

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

Matsumura, Yukihiko; Nuessle, F.W.; Antal, M.J. Jr.

Recently, carbonaceous materials including activated carbon were proven to be effective catalysts for hazardous waste gasification in supercritical water. Using coconut shell activated carbon catalyst, complete decomposition of industrial organic wastes including methanol and acetic acid was achieved. During this process, the total mass of the activated carbon catalyst changes by two competing processes: a decrease in weight via gasification of the carbon by supercritical water, or an increase in weight by deposition of carbonaceous materials generated by incomplete gasification of the biomass feedstocks. The deposition of carbonaceous materials does not occur when complete gasification is realized. Gasification of themore » activated carbon in supercritical water is often favored, resulting in changes in the quality and quantity of the catalyst. To thoroughly understand the hazardous waste decomposition process, a more complete understanding of the behavior of activated carbon in pure supercritical water is needed. The gasification rate of carbon by water vapor at subcritical pressures was studied in relation to coal gasification and generating activated carbon.« less

Hydrogen and carbon nanotube production via catalytic decomposition of methane

NASA Astrophysics Data System (ADS)

Deniz, Cansu; Karatepe, Nilgün

2013-09-01

The future energy demand is expected to increase significantly due to an increasing world population and demands for higher standards of living and better air quality. Hydrogen is considered as an energy carrier because of its high conversion efficiency and low pollutant emissions. It can be produced from various sources and transformed into electricity and other energy forms with a low pollution. The catalytic decomposition of hydrocarbon has been seen as a really useful method for production of pure hydrogen and for the environmental concern. The objective of this study was to assess the impact of catalyst composition and processing parameters on COx-free hydrogen production and to produce an available solid form of co-product carbon as carbon nanotubes via catalytic decomposition of methane. The optimum experimental conditions for methane decomposition have been investigated. Fe, Co and Ni are used as catalysts (nano materials) over different substrates as SiO2 and MgO to produce hydrogen at optimum temperatures.

Formic acid decomposition on Pt1/Cu (111) single platinum atom catalyst: Insights from DFT calculations and energetic span model analysis

NASA Astrophysics Data System (ADS)

Wang, Ying-Fan; Li, Kun; Wang, Gui-Chang

2018-04-01

Inspired by the recent surface experimental results that the monatomic Pt catalysts has more excellent hydrogen production that Cu(111) surface, the mechanism of decomposition of formic acid on Cu(111) and single atom Pt1/Cu(111) surface was studied by periodic density functional theory calculations in the present work. The results show that the formic acid tends to undergo dehydrogenation on both surfaces to obtain the hydrogen product of the target product, and the selectivity and catalytic activity of Pt1/Cu (111) surface for formic acid dehydrogenation are better. The reason is that the single atom Pt1/Cu(111) catalyst reduces the reaction energy barrier (i.e., HCOO → CO2 + H) of the critical step of the dehydrogenation reaction due to the fact that the single atom Pt1/Cu(111) catalyst binds formate weakly compared to that of Cu (111) one. Moreover, it was found that the Pt1/Cu (111) binds CO more strongly than that of Cu (111) one and thus leading to the difficult for the formation of CO. These two factors would make the single Pt atom catalyst had the high selectivity for the H2 production. It is hoped that the present work may help people to design the efficient H2 production from HCOOH decomposition by reduce the surface binding strength of HCOO species, for example, using the low coordination number active site like single atom or other related catalytic system.

Experimental investigation of the catalytic decomposition and combustion characteristics of a non-toxic ammonium dinitramide (ADN)-based monopropellant thruster

NASA Astrophysics Data System (ADS)

Chen, Jun; Li, Guoxiu; Zhang, Tao; Wang, Meng; Yu, Yusong

2016-12-01

Low toxicity ammonium dinitramide (ADN)-based aerospace propulsion systems currently show promise with regard to applications such as controlling satellite attitude. In the present work, the decomposition and combustion processes of an ADN-based monopropellant thruster were systematically studied, using a thermally stable catalyst to promote the decomposition reaction. The performance of the ADN propulsion system was investigated using a ground test system under vacuum, and the physical properties of the ADN-based propellant were also examined. Using this system, the effects of the preheating temperature and feed pressure on the combustion characteristics and thruster performance during steady state operation were observed. The results indicate that the propellant and catalyst employed during this work, as well as the design and manufacture of the thruster, met performance requirements. Moreover, the 1 N ADN thruster generated a specific impulse of 223 s, demonstrating the efficacy of the new catalyst. The thruster operational parameters (specifically, the preheating temperature and feed pressure) were found to have a significant effect on the decomposition and combustion processes within the thruster, and the performance of the thruster was demonstrated to improve at higher feed pressures and elevated preheating temperatures. A lower temperature of 140 °C was determined to activate the catalytic decomposition and combustion processes more effectively compared with the results obtained using other conditions. The data obtained in this study should be beneficial to future systematic and in-depth investigations of the combustion mechanism and characteristics within an ADN thruster.

Effects of Nd-, Pr-, Tb- and Y-doping on the structural, textural, electrical and N2O decomposition activity of mesoporous NiO nanoparticles

NASA Astrophysics Data System (ADS)

Abu-Zied, Bahaa M.; Bawaked, Salem M.; Kosa, Samia A.; Ali, Tarek T.; Schwieger, Wilhelm; Aqlan, Faisal M.

2017-10-01

Recently, nickel oxide, NiO, promoted with various dopants showed an interesting activity behavior in N2O direct decomposition. In this paper, the activity of a series of rare earth (Nd, Pr, Tb and Y) doped NiO catalysts was investigated for this reaction. These catalysts have been prepared by the calcination of their corresponding oxalate mixtures, which have been synthesized via the microwave-assisted precipitation route using oxalic acid as precipitant. Characterization of the obtained catalysts was carried out by using various physico-chemical techniques including TGA, FT-IR, XRD, FE-SEM, TEM, TPR, XPS and electrical conductivity. The results obtained revealed the nanocrystalline nature of the prepared catalysts. Moreover, the presence of the various dopants has led to a noticeable decrease of the NiO crystallites size, mesoporosity development and an increase of its surface area and pore volume. There is a substantial activity increase upon doping NiO with the various rare earth oxides. Such activity increase is associated with the structural modifications as well as the electrical conductivity increase of these catalysts.

Behaviors of glucose decomposition during acid-catalyzed hydrothermal hydrolysis of pretreated Gelidium amansii.

PubMed

Jeong, Tae Su; Choi, Chang Ho; Lee, Ji Ye; Oh, Kyeong Keun

2012-07-01

Acid-catalyzed hydrothermal hydrolysis is one path to cellulosic glucose and subsequently to its dehydration end products such as hydroxymethyl furfural (HMF), formic acid and levulinic acid. The effect of sugar decomposition not only lowers the yield of fermentable sugars but also forms decomposition products that inhibit subsequent fermentation. The present experiments were conducted with four different acid catalysts (H(2)SO(4), HNO(3), HCl, and H(3)PO(4)) at various acid normalities (0.5-2.1N) in batch reactors at 180-210 °C. From the results, H(2)SO(4) was the most suitable catalyst for glucose production, but glucose decomposition occurred during the hydrolysis. The glucose production was maximized at 160.7 °C, 2.0% (w/v) H(2)SO(4), and 40 min, but resulted in a low glucan yield of 33.05% due to the decomposition reactions, which generated formic acid and levulinic acid. The highest concentration of levulinic acid, 7.82 g/L, was obtained at 181.2 °C, 2.0% (w/v) H(2)SO(4), and 40 min. Copyright © 2012 Elsevier Ltd. All rights reserved.

Nanostructured Co3O4 grown on nickel foam: An efficient and readily recyclable 3D catalyst for heterogeneous peroxymonosulfate activation.

PubMed

Yuan, Ruixia; Hu, Lin; Yu, Peng; Wang, Huaiyuan; Wang, Zhaohui; Fang, Jingyun

2018-05-01

Cobalt-based heterogeneous catalyst has been recognized as one of most efficient activators for peroxymonosulfate (PMS) decomposition, but usually suffers from the poor stability and difficulty to recover and reuse. Here easily recyclable cobalt oxide (Co 3 O 4 ) nanowires and nanoflowers grown on nickel foam (NF) are fabricated by a hydrothermal and calcination method. The prepared 3D Co 3 O 4 /NF catalyst is characterized and applied as a heterogeneous catalyst for PMS activation to generate sulfate radicals for decomposition of Acid Orange 7 (AO7). The results show that the AO7 degradation rate increases with cobalt loading and PMS dosage, but decreases with the increase of solution pH. The Co 3 O 4 /NF catalyst using 2 mM Co(NO 3 ) 2 ·6H 2 O as cobalt source exhibits highest activity, and almost complete decolorization could be achieved within 30 min. The diverse effects of coexisting anions (SO 4 2- , HCO 3 - , NO 3 - and Cl - ) on AO7 degradation are observed and explained. After 10 consecutive runs, excellent catalytic reactivity of the catalyst remains while the level of leached cobalt during the catalyst usage is much lower than the maximum allowable concentration in drinking and natural water. More importantly, the macroscopic Co 3 O 4 /NF catalyst shows advantage of easy recycling after application compared to traditional catalysts. It is believed that the as-prepared Co 3 O 4 /NF is promising to be an effective and green heterogeneous catalyst for PMS activation to degrade organic pollutants for environmental application. Copyright © 2018 Elsevier Ltd. All rights reserved.

Selective Hydrogenation of Acetylene and Physicochemical Properties of Pd-Fe/Al2O3 Bimetallic Catalysts

NASA Astrophysics Data System (ADS)

Stytsenko, V. D.; Mel'nikov, D. P.; Tkachenko, O. P.; Savel'eva, E. V.; Semenov, A. P.; Kustov, L. M.

2018-05-01

The selective hydrogenation of acetylene on Pd-Fe/Al2O3 catalysts prepared by decomposition of ferrocene on reduced Pd/Al2O3 was studied. The effect of the conditions of treatment of the Pd-ferrocene/ Al2O3 precursor on the catalyst activity and selectivity was investigated, and the optimum conditions were determined at which the Pd-Fe/Al2O3 catalyst has higher selectivity than Pd/Al2O3 without any loss of activity.

Stable hydrogen production from ethanol through steam reforming reaction over nickel-containing smectite-derived catalyst.

PubMed

Yoshida, Hiroshi; Yamaoka, Ryohei; Arai, Masahiko

2014-12-25

Hydrogen production through steam reforming of ethanol was investigated with conventional supported nickel catalysts and a Ni-containing smectite-derived catalyst. The former is initially active, but significant catalyst deactivation occurs during the reaction due to carbon deposition. Side reactions of the decomposition of CO and CH4 are the main reason for the catalyst deactivation, and these reactions can relatively be suppressed by the use of the Ni-containing smectite. The Ni-containing smectite-derived catalyst contains, after H2 reduction, stable and active Ni nanocrystallites, and as a result, it shows a stable and high catalytic performance for the steam reforming of ethanol, producing H2.

Stable Hydrogen Production from Ethanol through Steam Reforming Reaction over Nickel-Containing Smectite-Derived Catalyst

PubMed Central

Yoshida, Hiroshi; Yamaoka, Ryohei; Arai, Masahiko

2014-01-01

Hydrogen production through steam reforming of ethanol was investigated with conventional supported nickel catalysts and a Ni-containing smectite-derived catalyst. The former is initially active, but significant catalyst deactivation occurs during the reaction due to carbon deposition. Side reactions of the decomposition of CO and CH4 are the main reason for the catalyst deactivation, and these reactions can relatively be suppressed by the use of the Ni-containing smectite. The Ni-containing smectite-derived catalyst contains, after H2 reduction, stable and active Ni nanocrystallites, and as a result, it shows a stable and high catalytic performance for the steam reforming of ethanol, producing H2. PMID:25547495

Patched bimetallic surfaces are active catalysts for ammonia decomposition.

PubMed

Guo, Wei; Vlachos, Dionisios G

2015-10-07

Ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material's structure. Core-shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core-shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N-H bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design.

Patched bimetallic surfaces are active catalysts for ammonia decomposition

NASA Astrophysics Data System (ADS)

Guo, Wei; Vlachos, Dionisios G.

2015-10-01

Ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material's structure. Core-shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core-shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N-H bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design.

Uncovering the Roles of Oxygen in Cr(III) Photoredox Catalysis.

PubMed

Higgins, Robert F; Fatur, Steven M; Shepard, Samuel G; Stevenson, Susan M; Boston, David J; Ferreira, Eric M; Damrauer, Niels H; Rappé, Anthony K; Shores, Matthew P

2016-04-27

A combined experimental and theoretical investigation aims to elucidate the necessary roles of oxygen in photoredox catalysis of radical cation based Diels-Alder cycloadditions mediated by the first-row transition metal complex [Cr(Ph2phen)3](3+), where Ph2phen = bathophenanthroline. We employ a diverse array of techniques, including catalysis screening, electrochemistry, time-resolved spectroscopy, and computational analyses of reaction thermodynamics. Our key finding is that oxygen acts as a renewable energy and electron shuttle following photoexcitation of the Cr(III) catalyst. First, oxygen quenches the excited Cr(3+)* complex; this energy transfer process protects the catalyst from decomposition while preserving a synthetically useful 13 μs excited state and produces singlet oxygen. Second, singlet oxygen returns the reduced catalyst to the Cr(III) ground state, forming superoxide. Third, the superoxide species reduces the Diels-Alder cycloadduct radical cation to the final product and reforms oxygen. We compare the results of these studies with those from cycloadditions mediated by related Ru(II)-containing complexes and find that the distinct reaction pathways are likely part of a unified mechanistic framework where the photophysical and photochemical properties of the catalyst species lead to oxygen-mediated photocatalysis for the Cr-containing complex but radical chain initiation for the Ru congener. These results provide insight into how oxygen can participate as a sustainable reagent in photocatalysis.

Enhancement of nitric oxide decomposition efficiency achieved with lanthanum-based perovskite-type catalyst.

PubMed

Pan, Kuan Lun; Chen, Mei Chung; Yu, Sheng Jen; Yan, Shaw Yi; Chang, Moo Been

2016-06-01

Direct decompositions of nitric oxide (NO) by La0.7Ce0.3SrNiO4, La0.4Ba0.4Ce0.2SrNiO4, and Pr0.4Ba0.4Ce0.2SrNiO4 are experimentally investigated, and the catalysts are tested with different operating parameters to evaluate their activities. Experimental results indicate that the physical and chemical properties of La0.7Ce0.3SrNiO4 are significantly improved by doping with Ba and partial substitution with Pr. NO decomposition efficiencies achieved with La0.4Ba0.4Ce0.2SrNiO4 and Pr0.4Ba0.4Ce0.2SrNiO4 are 32% and 68%, respectively, at 400 °C with He as carrier gas. As the temperature is increased to 600 °C, NO decomposition efficiencies achieved with La0.4Ba0.4Ce0.2SrNiO4 and Pr0.4Ba0.4Ce0.2SrNiO4, respectively, reach 100% with the inlet NO concentration of 1000 ppm while the space velocity is fixed at 8000 hr(-1). Effects of O2, H2O(g), and CO2 contents and space velocity on NO decomposition are also explored. The results indicate that NO decomposition efficiencies achieved with La0.4Ba0.4Ce0.2SrNiO4 and Pr0.4Ba0.4Ce0.2SrNiO4, respectively, are slightly reduced as space velocity is increased from 8000 to 20,000 hr(-1) at 500 °C. In addition, the activities of both catalysts (La0.4Ba0.4Ce0.2SrNiO4 and Pr0.4Ba0.4Ce0.2SrNiO4) for NO decomposition are slightly reduced in the presence of 5% O2, 5% CO2, or 5% H2O(g). For durability test, with the space velocity of 8000 hr(-1) and operating temperature of 600 °C, high N2 yield is maintained throughout the durability test of 60 hr, revealing the long-term stability of Pr0.4Ba0.4Ce0.2SrNiO4 for NO decomposition. Overall, Pr0.4Ba0.4Ce0.2SrNiO4 shows good catalytic activity for NO decomposition. Nitrous oxide (NO) not only causes adverse environmental effects such as acid rain, photochemical smog, and deterioration of visibility and water quality, but also harms human lungs and respiratory system. Pervoskite-type catalysts, including La0.7Ce0.3SrNiO4, La0.4Ba0.4Ce0.2SrNiO4, and Pr0.4Ba0.4Ce0.2SrNiO4, are applied for direct NO decomposition. The results show that NO decomposition can be enhanced as La0.7Ce0.3SrNiO4 is substituted with Ba and/or Pr. At 600 °C, NO decomposition efficiencies achieved with La0.4Ba0.4Ce0.2SrNiO4 and Pr0.4Ba0.4Ce0.2SrNiO4 reach 100%, demonstrating high activity and good potential for direct NO decomposition. Effects of O2, H2O(g), and CO2 contents on catalytic activities are also evaluated and discussed.

Thermal behavior and kinetic study for catalytic co-pyrolysis of biomass with plastics.

PubMed

Zhang, Xuesong; Lei, Hanwu; Zhu, Lei; Zhu, Xiaolu; Qian, Moriko; Yadavalli, Gayatri; Wu, Joan; Chen, Shulin

2016-11-01

The present study aims to investigate the thermal decomposition behaviors and kinetics of biomass (cellulose/Douglas fir sawdust) and plastics (LDPE) in a non-catalytic and catalytic co-pyrolysis over ZSM-5 catalyst by using a thermogravimetric analyzer (TGA). It was found that there was a positive synergistic interaction between biomass and plastics according to the difference of weight loss (ΔW), which could decrease the formation of solid residue at the end of the experiment. The first order reaction model well fitted for both non-catalytic and catalytic co-pyrolysis of biomass with plastics. The activation energy (E) of Cellulose-LDPE-Catalyst and DF-LDPE-Catalyst are only 89.51 and 54.51kJ/mol, respectively. The kinetics analysis showed that adding catalyst doesn't change the decomposition mechanism. As a result, the kinetic study on catalytic co-pyrolysis of biomass with plastics was suggested that the catalytic co-pyrolysis is a promising technique that can significantly reduce the energy input. Copyright © 2016 Elsevier Ltd. All rights reserved.

Catalyzed sodium chlorate candles

NASA Technical Reports Server (NTRS)

Malich, C. W.; Wydeven, T.

1972-01-01

The catalytic effect of cobalt powder on chlorate decomposition has been confirmed. Catalysis is enhanced by oxidation of the metal during burning. Catalysts other than cobalt compounds should also be effective; the complete elimination of fuel has shown that the oxidation of cobalt during decomposition is not a vital factor in the improved performance of catalyzed candles.

PROCESS OF COATING WITH NICKEL BY THE DECOMPOSITION OF NICKEL CARBONYL

DOEpatents

Hoover, T.B.

1959-04-01

An improved process is presented for the deposition of nickel coatings by the thermal decomposition of nickel carbonyl vapor. The improvement consists in incorporating a small amount of hydrogen sulfide gas in the nickel carbonyl plating gas. It is postulated that the hydrogen sulfide functions as a catalyst. i

Hydrogen production and purification for fuel cell applications

NASA Astrophysics Data System (ADS)

Chin, Soo Yin

The increased utilization of proton-exchange membrane (PEM) fuel cells as an alternative to internal combustion engines is expected to increase the demand for hydrogen, which is used as the energy source in these systems. Currently, production of hydrogen for fuel cells is primarily achieved via steam reforming, partial oxidation or autothermal reforming of natural gas, or steam reforming of methanol. However, in all of these processes CO is a by-product that must be subsequently removed due to its adverse effects on the Pt-based electrocatalysts of the PEM fuel cell. Our efforts have focused on production of CO-free hydrogen via catalytic decomposition of hydrocarbons and purification of H2 via the preferential oxidation of CO. The catalytic decomposition of hydrocarbons is an attractive alternative for the production of H2. Previous studies utilizing methane have shown that this approach can indeed produce CO-free hydrogen, with filamentous carbon formed as the by-product and deposited on the catalyst. We have further extended this approach to the decomposition of ethane. In addition to hydrogen and filamentous carbon however, methane is also formed in this case as a by-product. Studies conducted at different temperatures and space velocities suggest that hydrogen is the primary product while methane is formed in a secondary step. Ni/SiO2 catalysts are active for ethane decomposition at temperatures above 500°C. Although the yield of hydrogen increases with temperature, the catalyst deactivation rate also accelerates at higher temperatures. The preferential oxidation of CO is currently used for the purification of CO-contaminated hydrogen streams due to its efficiency and simplicity. Conventional Pt catalysts used for this reaction have been shown to effectively remove CO, but have limited selectivity (i.e., substantial amounts of H 2 also react with O2). Our work focused on alternative catalytic materials, such as Ru and bimetallic Ru-based catalysts (Pt-Ru, Ru-Sn). We have investigated the effects of various synthetic parameters (namely, supports, pretreatment conditions and precursors) on the performance of supported Ru catalysts. Kinetic results indicate that use of a nitrate precursor, SiO 2 support and a direct H2 treatment results in a highly dispersed catalyst that is active and selective towards CO. The results of extensive characterization studies indicate that a combination of particle size and residual precursor anion poisoning effects are responsible for the observed performance differences. Bimetallic Ru-Sn catalysts were also examined. Fresh catalyst exhibit lower activity for the preferential oxidation of CO as compared to fresh monometallic Ru. However, the activity of these bimetallic catalysts can be improved significantly by aging under reaction conditions, eventually becoming higher than that of monometallic Ru. By conducting a series of kinetic measurements following treatments with different components of the reacting gas mixture, we were able to deconvolute the effect of the different components and demonstrate that the observed improvement in activity is caused by the interaction of CO and H2O with the catalyst.

Palladium-atom catalyzed formic acid decomposition and the switch of reaction mechanism with temperature.

PubMed

He, Nan; Li, Zhen Hua

2016-04-21

Formic acid decomposition (FAD) reaction has been an innovative way for hydrogen energy. Noble metal catalysts, especially palladium-containing nanoparticles, supported or unsupported, perform well in this reaction. Herein, we considered the simplest model, wherein one Pd atom is used as the FAD catalyst. With high-level theoretical calculations of CCSD(T)/CBS quality, we investigated all possible FAD pathways. The results show that FAD catalyzed by one Pd atom follows a different mechanism compared with that catalyzed by surfaces or larger clusters. At the initial stage of the reaction, FAD follows a dehydration route and is quickly poisoned by CO due to the formation of very stable PdCO. PdCO then becomes the actual catalyst for FAD at temperatures approximately below 1050 K. Beyond 1050 K, there is a switch of catalyst from PdCO to Pd atom. The results also show that dehydration is always favoured over dehydrogenation on either the Pd-atom or PdCO catalyst. On the Pd-atom catalyst, neither dehydrogenation nor dehydration follows the formate mechanism. In contrast, on the PdCO catalyst, dehydrogenation follows the formate mechanism, whereas dehydration does not. We also systematically investigated the performance of 24 density functional theory methods. We found that the performance of the double hybrid mPW2PLYP functional is the best, followed by the B3LYP, B3PW91, N12SX, M11, and B2PLYP functionals.

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

Methanol decomposition reactions over a boron-doped graphene supported Ru-Pt catalyst.

PubMed

Damte, Jemal Yimer; Lyu, Shang-Lin; Leggesse, Ermias Girma; Jiang, Jyh Chiang

2018-04-04

The decomposition of methanol is currently attracting research attention due to the potential widespread applications of its end products. In this work, density functional theory (DFT) calculations have been performed to investigate the adsorption and decomposition of methanol on a Ru-Pt/boron doped graphene surface. We find that the most favorable reaction pathway is methanol (CH3OH) decomposition through O-H bond breaking to form methoxide (CH3O) as the initial step, followed by further dehydrogenation steps which generate formaldehyde (CH2O), formyl (CHO), and carbon monoxide (CO). The calculations illustrate that CH3OH and CO groups prefer to adsorb at the Ru-top sites, while CH2OH, CH3O, CH2O, CHO, and H2 groups favor the Ru-Pt bridge sites, indicating the preference of Ru atoms to adsorb the active intermediates or species having lone-pair electrons. Based on the results, it is found that the energy barrier for CH3OH decomposition through the initial O-H bond breaking is less than its desorption energy of 0.95 eV, showing that CH3OH prefers to undergo decomposition to CH3O rather than direct desorption. The study provides in-depth theoretical insights into the potentially enhanced catalytic activity of Ru-Pt/boron doped graphene surfaces for methanol decomposition reactions, thereby contributing to the understanding and designing of an efficient catalyst under optimum conditions.

Co-production of hydrogen and carbon nanotubes on nickel foam via methane catalytic decomposition

NASA Astrophysics Data System (ADS)

Ping, Dan; Wang, Chaoxian; Dong, Xinfa; Dong, Yingchao

2016-04-01

The co-production of COx-free hydrogen and carbon nanotubes (CNTs) was achieved on 3-dimensional (3D) macroporous nickel foam (NF) via methane catalytic decomposition (MCD) over nano-Ni catalysts using chemical vapor deposition (CVD) technique. By a simple coating of a NiO-Al2O3 binary mixture sol followed by a drying-calcination-reduction treatment, NF supported composite catalysts (denoted as NiyAlOx/NF) with Al2O3 transition-layer incorporated with well-dispersed nano-Ni catalysts were successfully prepared. The effects of Ni loading, calcination temperature and reaction temperature on the performance for simultaneous production of COx-free hydrogen and CNTs were investigated in detail. Catalysts before and after MCD were characterized by XRD, TPR, SEM, TEM, TG and Raman spectroscopy technology. Results show that increasing Ni loading, lowering calcination temperature and optimizing MCD reaction temperature resulted in high production efficiency of COx-free H2 and carbon, but broader diameter distribution of CNTs. Through detailed parameter optimization, the catalyst with a Ni/Al molar ratio of 0.1, calcination temperature of 550 °C and MCD temperature of 650 °C was favorable to simultaneously produce COx-free hydrogen with a growth rate as high as 10.3% and CNTs with uniform size on NF.

Efficient decomposition of formaldehyde at room temperature over Pt/honeycomb ceramics with ultra-low Pt content.

PubMed

Nie, Longhui; Zheng, Yingqiu; Yu, Jiaguo

2014-09-14

Pt/honeycomb ceramic (Pt/HC) catalysts with ultra-low Pt content (0.005-0.055 wt%) were for the first time prepared by an impregnation of honeycomb ceramics with Pt precursor and NaBH4-reduction combined method. The microstructures, morphologies and textural properties of the resulting samples were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). The obtained Pt/HC catalysts were used for catalytic oxidative decomposition of formaldehyde (HCHO) at room temperature. It was found that the as-prepared Pt/HC catalysts can efficiently decompose HCHO in air into CO2 and H2O at room temperature. The catalytic activity of the Pt/HC catalysts increases with increasing the Pt loading in the range of 0.005-0.013 wt%, and the further increase of the Pt loading does not obviously improve catalytic activity. From the viewpoint of cost and catalytic performance, 0.013 wt% Pt loading is the optimal Pt loading amount, and the Pt/HC catalyst with 0.013 wt% Pt loading also exhibited good catalytic stability. Considering practical applications, this work will provide new insights into the low-cost and large-scale fabrication of advanced catalytic materials for indoor air purification.

Synthesis and Electrocatalytic Activity of Ammonium Nickel Phosphate, [NH4]NiPO4·6H2O, and β-Nickel Pyrophosphate, β-Ni2P2O7: Catalysts for Electrocatalytic Decomposition of Urea.

PubMed

Meguerdichian, Andrew G; Jafari, Tahereh; Shakil, Md R; Miao, Ran; Achola, Laura A; Macharia, John; Shirazi-Amin, Alireza; Suib, Steven L

2018-02-19

Electrocatalytic decomposition of urea for the production of hydrogen, H 2, for clean energy applications, such as in fuel cells, has several potential advantages such as reducing carbon emissions in the energy sector and environmental applications to remove urea from animal and human waste facilities. The study and development of new catalyst materials containing nickel metal, the active site for urea decomposition, is a critical aspect of research in inorganic and materials chemistry. We report the synthesis and application of [NH 4 ]NiPO 4 ·6H 2 O and β-Ni 2 P 2 O 7 using in situ prepared [NH 4 ] 2 HPO 4 . The [NH 4 ]NiPO 4 ·6H 2 O is calcined at varying temperatures and tested for electrocatalytic decomposition of urea. Our results indicate that [NH 4 ]NiPO 4 ·6H 2 O calcined at 300 °C with an amorphous crystal structure and, for the first time applied for urea electrocatalytic decomposition, had the greatest reported electroactive surface area (ESA) of 142 cm 2 /mg and an onset potential of 0.33 V (SCE) and was stable over a 24-h test period.

Combustion Products Evaluation from Hull Insulation Materials Coated with Fire Retardant Paints.

DTIC Science & Technology

1980-09-08

Musick and F.W. Williams, "Catalytic Decomposition of Halogenated Hydro- carbons over Hopcalite Catalyst," I and EC Product R&D, 13, 175 (1974). 22...J.K. Musick and F.W. Williams, " Hopcalite Catalyst for Catalytic Oxidation of Gases and Aerosols," I and EC Product R&D, 14, 284 (1975). 20

Perfluoropolyalkylether decomposition on catalytic aluminas

NASA Technical Reports Server (NTRS)

Morales, Wilfredo

1994-01-01

The decomposition of Fomblin Z25, a commercial perfluoropolyalkylether liquid lubricant, was studied using the Penn State Micro-oxidation Test, and a thermal gravimetric/differential scanning calorimetry unit. The micro-oxidation test was conducted using 440C stainless steel and pure iron metal catalyst specimens, whereas the thermal gravimetric/differential scanning calorimetry tests were conducted using catalytic alumina pellets. Analysis of the thermal data, high pressure liquid chromatography data, and x-ray photoelectron spectroscopy data support evidence that there are two different decomposition mechanisms for Fomblin Z25, and that reductive sites on the catalytic surfaces are responsible for the decomposition of Fomblin Z25.

Influence of Temperature and Catalyst on the Decomposition of Potassium Chlorate in a Simple DTA-Apparatus.

ERIC Educational Resources Information Center

Wiederholt, Erwin

1983-01-01

DTA is a technique in which the temperature difference between sample/reference is measured as a function of temperature, while both are subject to a controlled temperature program. Use of a simple DTA-apparatus in demonstrating catalytic effects of manganese dioxide and aluminum oxide on decomposition temperature of potassium chlorate is…

Pretreatment of Platinum/Tin Oxide-Catalyst

NASA Technical Reports Server (NTRS)

Hess, Robert V.; Paulin, Patricia A.; Miller, Irvin M.; Schryer, David R.; Sidney, Barry D.; Wood, George M.; Upchurch, Billy T.; Brown, Kenneth G.

1987-01-01

Addition of CO to He pretreatment doubles catalytic activity. In sealed, high-energy, pulsed CO2 laser, CO and O2 form as decomposition products of CO2 in laser discharge zone. Products must be recombined, because oxygen concentration of more than few tenths of percent causes rapid deterioration of power, ending in unstable operation. Promising low-temperature catalyst for combining CO and O2 is platinum on tin oxide. New development increases activity of catalyst so less needed for recombination process.

Solar photolysis of water

NASA Technical Reports Server (NTRS)

Ryason, P. R. (Inventor)

1977-01-01

Hydrogen is produced by the solar photolysis of water in a first photooxidation vessel with a transparent wall in the presence of a water soluble photooxidizable reagent and an insoluble hydrogen recombination catalyst. Simultaneously oxygen is produced in a second photoreduction reactor with a transparent wall in the presence of an insoluble photoreduction reagent catalyst. When spent, the solution from the first reactor is fed into the second reactor. A reaction occurs in the dark in which the redox reagents are regenerated, and the regenerated photooxidation reagent solution is recycled to the first reactor. The photoreduction-catalyst is a bifunctional reagent catalyst including a transition metal salt together with a hydroxyl or chlorohydroxyl decomposition catalyst of high area.

Catalysts for the decomposition of hydrazine and its derivatives and a method for its production

NASA Technical Reports Server (NTRS)

Sasse, R.

1986-01-01

Catalysts of various types are used to decompose hydrazine and its derivatives. One type of catalyst is made as follows: the aluminum is dissolved out of an alloy of cobalt or nickel/aluminum so that a structure is produced that is chemically active for the monergol and that has a large active surface. The objective was to avoid difficulties and to create a catalyst that not only has a short start time but that can also be manufactured easily and relatively inexpensively. The solution to this task is to coat the base structure of the catalyst with oxides of copper, cobalt and cerium or oxides of copper, cobalt and cerite earth.

Effect of H2O2 injection patterns on catalyst bed characteristics

NASA Astrophysics Data System (ADS)

Kang, Hongjae; Lee, Dahae; Kang, Shinjae; Kwon, Sejin

2017-01-01

The decomposition process of hydrogen peroxide can be applied to a bipropellant thruster, as well as to monopropellant thruster. To provide a framework for the optimal design of the injector and catalyst bed depending on a type of thruster, this research scrutinizes the effect of injection patterns of the propellant on the performance of the catalyst bed. A showerhead injector and impinging jet injector were tested with a 50 N monopropellant thruster. Manganese oxide/γ-alumina catalyst and manganese oxide/lanthanum-doped alumina catalyst were prepared and tested. The showerhead injector provided a fast response time, suitable for pulse mode operation. The impinging jet injector mitigated the performance instability and catalyst attrition that is favorable for large scale bipropellant thrusters. The design of a dual catalyst bed was conceptually proposed based on the data obtained from firing tests.

Low-temperature conversion of ammonia to nitrogen in water with ozone over composite metal oxide catalyst.

PubMed

Chen, Yunnen; Wu, Ye; Liu, Chen; Guo, Lin; Nie, Jinxia; Chen, Yu; Qiu, Tingsheng

2018-04-01

As one of the most important water pollutants, ammonia nitrogen emissions have increased year by year, which has attracted people's attention. Catalytic ozonation technology, which involves production of ·OH radical with strong oxidation ability, is widely used in the treatment of organic-containing wastewater. In this work, MgO-Co 3 O 4 composite metal oxide catalysts prepared with different fabrication conditions have been systematically evaluated and compared in the catalytic ozonation of ammonia (50mg/L) in water. In terms of high catalytic activity in ammonia decomposition and high selectivity for gaseous nitrogen, the catalyst with MgO-Co 3 O 4 molar ratio 8:2, calcined at 500°C for 3hr, was the best one among the catalysts we tested, with an ammonia nitrogen removal rate of 85.2% and gaseous nitrogen selectivity of 44.8%. In addition, the reaction mechanism of ozonation oxidative decomposition of ammonia nitrogen in water with the metal oxide catalysts was discussed. Moreover, the effect of coexisting anions on the degradation of ammonia was studied, finding that SO 4 2- and HCO 3 - could inhibit the catalytic activity while CO 3 2- and Br - could promote it. The presence of coexisting cations had very little effect on the catalytic ozonation of ammonia nitrogen. After five successive reuses, the catalyst remained stable in the catalytic ozonation of ammonia. Copyright © 2017. Published by Elsevier B.V.

Platinum Nanoparticle Decorated SiO2 Microfibers as Catalysts for Micro Unmanned Underwater Vehicle Propulsion.

PubMed

Chen, Bolin; Garland, Nathaniel T; Geder, Jason; Pruessner, Marius; Mootz, Eric; Cargill, Allison; Leners, Anne; Vokshi, Granit; Davis, Jacob; Burns, Wyatt; Daniele, Michael A; Kogot, Josh; Medintz, Igor L; Claussen, Jonathan C

2016-11-16

Micro unmanned underwater vehicles (UUVs) need to house propulsion mechanisms that are small in size but sufficiently powerful to deliver on-demand acceleration for tight radius turns, burst-driven docking maneuvers, and low-speed course corrections. Recently, small-scale hydrogen peroxide (H 2 O 2 ) propulsion mechanisms have shown great promise in delivering pulsatile thrust for such acceleration needs. However, the need for robust, high surface area nanocatalysts that can be manufactured on a large scale for integration into micro UUV reaction chambers is still needed. In this report, a thermal/electrical insulator, silicon oxide (SiO 2 ) microfibers, is used as a support for platinum nanoparticle (PtNP) catalysts. The mercapto-silanization of the SiO 2 microfibers enables strong covalent attachment with PtNPs, and the resultant PtNP-SiO 2 fibers act as a robust, high surface area catalyst for H 2 O 2 decomposition. The PtNP-SiO 2 catalysts are fitted inside a micro UUV reaction chamber for vehicular propulsion; the catalysts can propel a micro UUV for 5.9 m at a velocity of 1.18 m/s with 50 mL of 50% (w/w) H 2 O 2 . The concomitance of facile fabrication, economic and scalable processing, and high performance-including a reduction in H 2 O 2 decomposition activation energy of 40-50% over conventional material catalysts-paves the way for using these nanostructured microfibers in modern, small-scale underwater vehicle propulsion systems.

New Pt/Alumina model catalysts for STM and in situ XPS studies

NASA Astrophysics Data System (ADS)

Nartova, Anna V.; Gharachorlou, Amir; Bukhtiyarov, Andrey V.; Kvon, Ren I.; Bukhtiyarov, Valerii I.

2017-04-01

The new Pt/alumina model catalysts for STM and in situ XPS studies based on thin alumina film formed over the conductive substrate are proposed. Procedure of platinum deposition developed for porous alumina was adapted for the model alumina support. The set of Pt/AlOx-film samples with the different mean platinum particle size was prepared. Capabilities of in situ XPS investigations of the proposed catalysts were demonstrated in study of NO decomposition on platinum nanoparticles. It is shown that proposed model catalysts behave similarly to Pt/γ-Al2O3 and provide the new opportunities for the instrumental studies of platinum catalysts due to resolving several issues (charging, heating, screening) that are typical for the investigation of the porous oxide supported catalysts.

Vapor-Phase Catalytic Oxidation of Mixed Volatile Organic Compounds

DTIC Science & Technology

1989-09-01

18 3. Hopcalite . . . . . . . . . 18 4. Potassium Chloride/Copper Oxide . . . 19 5. Vanadium Pentoxide . . . . . . . 19 6. Potassium...decomposition of 19 halogenated hydrocarbons, associated with submarine burners, using a hopcalite catalyst. Bond, et al. (Reference 9) have studied the...The catalyst can be easily regenerated, but deactivation occurs within a matter of minutes. 3. Hopcalite This mineral, containing primarily CuD and

AN INVESTIGATION OF CFC12 (CCI2F2) DECOMPOSITION ON TIO2 CATALYST

EPA Science Inventory

The catalytic oxidation of CFC12 was studied over a titania (TiO2) catalyst in a fixed-bed reactor at temperatures ranging from 200 to 400 degrees C and space velocity of 10,500 h-1. Results showed substantially complete conversion of CFC12 (>90%) to CO2 and halogen acids at and...

Insights into perfluorooctane sulfonate photodegradation in a catalyst-free aqueous solution

PubMed Central

Lyu, Xian-Jin; Li, Wen-Wei; Lam, Paul K. S.; Yu, Han-Qing

2015-01-01

Photodegradation in the absence of externally added chemicals could be an attractive solution for the removal of perfluorooctane sulfonate (PFOS) in aqueous environment, but the low decomposition rate presents a severe challenge and the underlying mechanisms are unclear. In this study, we demonstrated that PFOS could be effectively degraded in a catalyst-free aqueous solution via a reduction route. Under appropriate pH and temperature conditions, a rapid PFOS photodegradation, with a pseudo-first-order decomposition rate constant of 0.91 h−1, was achieved. In addition, hydrated electrons were considered to be the major photo-generated reductive species responsible for PFOS photodegradation in this system. Its production and reduction ability could be significantly affected by the environmental conditions such as pH, temperature and presence of oxidative species. This study gives insights into the PFOS photodegradation process and may provide useful information for developing catalyst-free photodegradation systems for decomposing PFOS and other persistent water contaminants. PMID:25879866

Structural characteristics of mixed oxides MOx/SiO2 affecting photocatalytic decomposition of methylene blue

NASA Astrophysics Data System (ADS)

Gun'ko, V. M.; Blitz, J. P.; Bandaranayake, B.; Pakhlov, E. M.; Zarko, V. I.; Sulym, I. Ya.; Kulyk, K. S.; Galaburda, M. V.; Bogatyrev, V. M.; Oranska, O. I.; Borysenko, M. V.; Leboda, R.; Skubiszewska-Zięba, J.; Janush, W.

2012-06-01

A series of photocatalysts based on silica (nanoparticulate) supported titania, ceria, and ceria/zirconia were synthesized and characterized by a variety of techniques including surface area measurements, X-ray diffraction, Fourier transform infrared spectroscopy, zeta potential, surface charge density, and photocatalytic behavior toward methylene blue decomposition. Thermal treatment at 600 °C increases the anatase content of the titania based catalysts detected by XRD. Changes in the infrared spectra before and after thermal treatment indicate that at low temperature there are more tbnd Sisbnd Osbnd Titbnd bonds than at high temperature. As these bonds break upon heating the SiO2 and TiO2 separate, allowing the TiO2 anatase phase to form. This results in an increased catalytic activity for the thermally treated samples. Nearly all titania based samples exhibit a negative surface charge density at pH 7 (initial pH of photocatalytic studies) which aids adsorption of methylene blue. The crystallinity of ceria and ceria/zirconia based catalysts are in some cases limited, and in others non-existent. Even though the energy band gap (Eg) can be lower for these catalysts than for the titania based catalysts, their photocatalytic properties are inferior.

Patched bimetallic surfaces are active catalysts for ammonia decomposition

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

Guo, Wei; Vlachos, Dionisios G.

In this study, ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material’s structure. Core–shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core–shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N-Hmore » bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design.« less

Patched bimetallic surfaces are active catalysts for ammonia decomposition

DOE PAGES

Guo, Wei; Vlachos, Dionisios G.

2015-10-07

In this study, ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material’s structure. Core–shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core–shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N-Hmore » bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design.« less

A systematic study on photocatalysis of antipyrine: Catalyst characterization, parameter optimization, reaction mechanism a toxicity evolution to plankton.

PubMed

Gong, Han; Chu, Wei; Chen, Meijuan; Wang, Qinxing

2017-04-01

The toxicity of antipyrine (AP) in the photodegradation using UV/CoFe 2 O 4 /TiO 2 was investigated by analyzing the characteristic of the catalyst, the effect of parameters (light source wavelength, catalyst dose, pH and initial AP concentration), the reaction mechanism (the organic intermediates, TOC reduction and inorganic ions release) and the newly proposed low-dosage-high-effective radical reaction approach. The catalyst shows the optimal removal efficiency under the conditions of wavelength at 350 nm, the catalyst dose at 0.5 g/L, and pH value at 5.5. Ten organic intermediates were identified, and five of them were newly reported in AP treatment process. Hydroxylation, demethylation and the cleavage of the pentacyclic ring were included in the decomposition pathways. The ring opening was certified by the 45% TOC reduction and 60% ammonia release during the process. The parent compound AP and its degradation products show positive effects on the growth of the algae. However, acute toxicity of AP was detected on brine shrimps Artemia salina. The toxicity was eliminated gradually with the decomposition of AP and the generation of the byproducts. The results indicate that the photocatalysis process is effective in AP removal, TOC reduction and toxicity elimination. Copyright © 2017 Elsevier Ltd. All rights reserved.

XPS and Raman studies of Pt catalysts supported on activated carbon

NASA Astrophysics Data System (ADS)

Tyagi, Deepak; Varma, Salil; Bharadwaj, S. R.

2018-04-01

Activated carbon is a widely used support for dispersing noble metals in addition to its many applications. We have prepared platinum catalyst supported on activated carbon for HI decomposition reaction of I-S thermochemical process of hydrogen generation. These catalysts were characterized by XPS and Raman before and after using for the reaction. It was observed that platinum is present in zero oxidation state, while carbon is present is both sp2 and sp3 hybridized forms along with some amount of it bonded to oxygen.

Method of preparing meso-haloalkylporphyrins

DOEpatents

Wijesekera, Tilak; Lyons, James E.; Ellis, Jr., Paul E.; Bhinde, Manoj V.

1998-01-01

Transition metal complexes of meso-haloalkylporphyrins, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides. Also disclosed is a process for the preparation of meso-halocarbyl-porphyrins which comprises contacting a halocarbyl dipyrromethane with a halocarbyl-substituted aldehyde in the presence of an acid granular solid catalyst. Also disclosed is a process for the preparation of meso-halocarbyl-porphyrins which comprises contacting a halocarbyl dipyrromethane with a halocarbyl-substituted aldehyde in the presence of an acid granular solic catalyst.

Hydrazine Catalyst Production: Sustaining S-405 Technology

NASA Technical Reports Server (NTRS)

Wucherer, E. J.; Cook, Timothy; Stiefel, Mark; Humphries, Randy, Jr.; Parker, Janet

2003-01-01

The development of the iridium-based Shell 405 catalyst for spontaneous decomposition of hydrazine was one of the key enabling technologies for today's spacecraft and launch vehicles. To ensure that this crucial technology was not lost when Shell elected to exit the business, Aerojet, supported by NASA, has developed a dedicated catalyst production facility that will supply catalyst for future spacecraft and launch vehicle requirements. We have undertaken a program to transfer catalyst production from Shell Chemical USA (Houston, TX) to Aerojet's Redmond, WA location. This technology transition was aided by Aerojet's 30 years of catalyst manufacturing experience and NASA diligence and support in sustaining essential technologies. The facility has produced and tested S-405 catalyst to existing Shell 405 specifications and standards. Our presentation will describe the technology transition effort including development of the manufacturing facility, capture of the manufacturing process, test equipment validation, initial batch build and final testing.

Temperature-dependent Study of Isobutanol Decomposition

DTIC Science & Technology

2012-11-01

dimensional Al2O3 alumina CO2 carbon dioxide FTIR Fourier transform infrared Pd palladium Rh rhodium TPD temperature-programmed desorption TPO...that increasing temperature promotes aldehyde formation on the surface of each catalyst. In addition, it is shown that palladium (Pd) activates the...formation of aldehydes and CO2 at a lower temperature than a rhodium (Rh) catalyst. 15. SUBJECT TERMS Isobutanol, FTIR, spectroscopy 16. SECURITY

Study on the decomposition of trace benzene over V2O5–WO3/TiO2-based catalysts in simulated flue gas

EPA Science Inventory

Trace levels (1 and 10 ppm) of gaseous benzene were catalytically decomposed in a fixed-bed catalytic reactor with monolithic oxides of vanadium and tungsten supported on titanium oxide (V2O5–WO3/TiO2) catalysts under conditions simulating the cooling of waste incineration flue g...

Spatially and size selective synthesis of Fe-based nanoparticles on ordered mesoporous supports as highly active and stable catalysts for ammonia decomposition.

PubMed

Lu, An-Hui; Nitz, Joerg-Joachim; Comotti, Massimiliano; Weidenthaler, Claudia; Schlichte, Klaus; Lehmann, Christian W; Terasaki, Osamu; Schüth, Ferdi

2010-10-13

Uniform and highly dispersed γ-Fe(2)O(3) nanoparticles with a diameter of ∼6 nm supported on CMK-5 carbons and C/SBA-15 composites were prepared via simple impregnation and thermal treatment. The nanostructures of these materials were characterized by XRD, Mössbauer spectroscopy, XPS, SEM, TEM, and nitrogen sorption. Due to the confinement effect of the mesoporous ordered matrices, γ-Fe(2)O(3) nanoparticles were fully immobilized within the channels of the supports. Even at high Fe-loadings (up to about 12 wt %) on CMK-5 carbon no iron species were detected on the external surface of the carbon support by XPS analysis and electron microscopy. Fe(2)O(3)/CMK-5 showed the highest ammonia decomposition activity of all previously described Fe-based catalysts in this reaction. Complete ammonia decomposition was achieved at 700 °C and space velocities as high as 60,000 cm(3) g(cat)(-1) h(-1). At a space velocity of 7500 cm(3) g(cat)(-1) h(-1), complete ammonia conversion was maintained at 600 °C for 20 h. After the reaction, the immobilized γ-Fe(2)O(3) nanoparticles were found to be converted to much smaller nanoparticles (γ-Fe(2)O(3) and a small fraction of nitride), which were still embedded within the carbon matrix. The Fe(2)O(3)/CMK-5 catalyst is much more active than the benchmark NiO/Al(2)O(3) catalyst at high space velocity, due to its highly developed mesoporosity. γ-Fe(2)O(3) nanoparticles supported on carbon-silica composites are structurally much more stable over extended periods of time but less active than those supported on carbon. TEM observation reveals that iron-based nanoparticles penetrate through the carbon layer and then are anchored on the silica walls, thus preventing them from moving and sintering. In this way, the stability of the carbon-silica catalyst is improved. Comparison with the silica supported iron oxide catalyst reveals that the presence of a thin layer of carbon is essential for increased catalytic activity.

Catalytic oxidative desulfurization of liquid hydrocarbon fuels using air

NASA Astrophysics Data System (ADS)

Sundararaman, Ramanathan

Conventional approaches to oxidative desulfurization of liquid hydrocarbons involve use of high-purity, expensive water soluble peroxide for oxidation of sulfur compounds followed by post-treatment for removal of oxidized sulfones by extraction. Both are associated with higher cost due to handling, storage of oxidants and yield loss with extraction and water separation, making the whole process more expensive. This thesis explores an oxidative desulfurization process using air as an oxidant followed by catalytic decomposition of sulfones thereby eliminating the aforementioned issues. Oxidation of sulfur compounds was realized by a two step process in which peroxides were first generated in-situ by catalytic air oxidation, followed by catalytic oxidation of S compounds using the peroxides generated in-situ completing the two step approach. By this technique it was feasible to oxidize over 90% of sulfur compounds present in real jet (520 ppmw S) and diesel (41 ppmw S) fuels. Screening of bulk and supported CuO based catalysts for peroxide generation using model aromatic compound representing diesel fuel showed that bulk CuO catalyst was more effective in producing peroxides with high yield and selectivity. Testing of three real diesel fuels obtained from different sources for air oxidation over bulk CuO catalyst showed different level of effectiveness for generating peroxides in-situ which was consistent with air oxidation of representative model aromatic compounds. Peroxides generated in-situ was then used as an oxidant to oxidize sulfur compounds present in the fuel over MoO3/SiO2 catalyst. 81% selectivity of peroxides for oxidation of sulfur compounds was observed on MoO3/SiO2 catalyst at 40 °C and under similar conditions MoO3/Al2O3 gave only 41% selectivity. This difference in selectivity might be related to the difference in the nature of active sites of MoO3 on SiO2 and Al2O 3 supports as suggested by H2-TPR and XRD analyses. Testing of supported and bulk MgO catalysts for decomposition of sulfones showed that these catalysts are effective in decomposing oxidized sulfur compounds such as dibenzothiophene sulfone and 3-methyl benzothiophene sulfone to biphenyl and isopropyl benzene respectively and SO2. Study of catalyst structure-activity relationship revealed that in the range of 40--140 nm of MgO, crystallite size plays a critical role on activity of the catalyst for sulfone decomposition. In testing other alkali oxides, it was demonstrated that CaO was effective as a reagent in decomposing oxidized sulfur compounds in a crude oil at a much lower temperature than used for MgO based catalyst. Preliminary data on potential regeneration scheme of spent CaO is also discussed.

Dechlorination of polychlorinated biphenyls by iron and its oxides.

PubMed

Sun, Yifei; Liu, Xiaoyuan; Kainuma, Masashi; Wang, Wei; Takaoka, Masaki; Takeda, Nobuo

2015-10-01

The decomposition efficiency of polychlorinated biphenyls (PCBs) was determined using elemental iron (Fe) and three iron (hydr)oxides, i.e., α-Fe2O3, Fe3O4, and α-FeOOH, as catalysts. The experiments were performed using four distinct PCB congeners (PCB-209, PCB-153, and the coplanar PCB-167 and PCB-77) at temperatures ranging from 180 °C to 380 °C and under an inert, oxidizing or reducing atmosphere composed of N2, N2+O2, or N2+H2. From these three options N2 showed to provide the best reaction atmosphere. Among the iron compounds tested, Fe3O4 showed the highest activity for decomposing PCBs. The decomposition efficiencies of PCB-209, PCB-167, PCB-153, and PCB-77 by Fe3O4 in an N2 atmosphere at 230 °C were 88.5%, 82.5%, 69.9%, and 66.4%, respectively. Other inorganic chlorine (Cl) products which were measured by the amount of inorganic Cl ions represented 82.5% and 76.1% of the reaction products, showing that ring cleavage of PCBs was the main elimination process. Moreover, the dechlorination did not require a particular hydrogen donor. We used X-ray photoelectron spectroscopy to analyze the elemental distribution at the catalyst's surface. The O/Fe ratio influenced upon the decomposition efficiency of PCBs: the lower this ratio, the higher the decomposition efficiency. X-ray absorption near edge structure spectra showed that α-Fe2O3 effectively worked as a catalyst, while Fe3O4 and α-FeOOH were consumed as reactants, as their final state is different from their initial state. Finally, a decomposition pathway was postulated in which the Cl atoms in ortho-positions were more difficult to eliminate than those in the para- or meta-positions. Copyright © 2015 Elsevier Ltd. All rights reserved.

On the Structure Sensitivity of Formic Acid Decomposition on Cu Catalysts

DOE PAGES

Li, Sha; Scaranto, Jessica; Mavrikakis, Manos

2016-08-03

Catalytic decomposition of formic acid (HCOOH) has attracted substantial attention since HCOOH is a major by-product in biomass reforming, a promising hydrogen carrier, and also a potential low temperature fuel cell feed. Despite the abundance of experimental studies for vapor-phase HCOOH decomposition on Cu catalysts, the reaction mechanism and its structure sensitivity is still under debate. In this work, self-consistent, periodic density functional theory calculations were performed on three model surfaces of copper—Cu(111), Cu(100) and Cu(211), and both the HCOO (formate)-mediated and COOH (carboxyl)-mediated pathways were investigated for HCOOH decomposition. The energetics of both pathways suggest that the HCOO-mediated routemore » is more favorable than the COOH-mediated route on all three surfaces, and that HCOOH decomposition proceeds through two consecutive dehydrogenation steps via the HCOO intermediate followed by the recombinative desorption of H 2. On all three surfaces, HCOO dehydrogenation is the likely rate determining step since it has the highest transition state energy and also the highest activation energy among the three catalytic steps in the HCOO pathway. The reaction is structure sensitive on Cu catalysts since the examined three Cu facets have dramatically different binding strengths for the key intermediate HCOO and varied barriers for the likely rate determining step—HCOO dehydrogenation. Cu(100) and Cu(211) bind HCOO much more strongly than Cu(111), and they are also characterized by potential energy surfaces that are lower in energy than that for the Cu(111) facet. Coadsorbed HCOO and H represents the most stable state along the reaction coordinate, indicating that, under reaction conditions, there might be a substantial surface coverage of the HCOO intermediate, especially at under-coordinated step, corner or defect sites. Therefore, under reaction conditions, HCOOH decomposition is predicted to occur most readily on the terrace sites of Cu nanoparticles. Finally, as a result, we hereby present an example of a fundamentally structure-sensitive reaction, which may present itself as structure-insensitive in typical varied particle-size experiments.« less

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

Activation of Hydrogen Peroxide by Iron-Containing Minerals and Catalysts in Circumneutral pH Solutions: Implications for ex situ and in situ Treatment of Contaminated Water and Soil

NASA Astrophysics Data System (ADS)

Pham, Anh Le Tuan

The decomposition of hydrogen peroxide (H2O2) on iron minerals can generate hydroxyl radical (•OH), a strong oxidant capable of transforming a wide range of contaminants. This reaction is critical to ex situ advanced oxidation processes employed in waste treatment systems, as well as in situ chemical oxidation processes used for soil and groundwater remediation. Unfortunately, the process in the ex situ treatment systems is relatively inefficient at circumneutral pH values. In this research, the development of iron-containing catalysts with improved efficiency was investigated. In addition, little is known about the factors that control the performance of in situ treatment systems. Another aim of this dissertation was to elucidate those factors to provide a basis for improving the efficiency of the remediation method. Two types of silica- and alumina-containing iron (hydr)oxide catalysts were synthesized by sol-gel processing techniques (Chapter 2). Relative to iron oxides, such as hematite and goethite, these catalysts were 10 to 80 times more effective in catalyzing the production of •OH from H2O2 under circumneutral conditions. The higher efficiency makes these catalysts promising candidates for ex situ advanced oxidation processes. Moreover, because alumina and silica alter the reactivity of the iron oxides with H2O2, understanding the activity of iron associated with natural aluminosilicates and silica-containing minerals in the subsurface is crucial to explaining the variability of •OH production observed in in situ treatment systems. In addition to the sol-gel technique used in Chapter 2, silica-containing iron (hydr)oxide catalysts were synthesized by immobilizing iron oxide onto mesoporous silica supports, such as SBA-15 (Chapter 5). The iron-containing SBA-15 was 10 times more effective than iron oxides in catalyzing the production of •OH from H2O2. Moreover, this catalyst could be employed for selective oxidation of small organic contaminants based on size exclusion. However, a major drawback of the mesoporous silica-based catalysts is their instability under circumneutral conditions (Chapter 6). The dissolution of mesoporous silica materials raises questions about their use for water treatment, because silica dissolution might compromise the behavior of the material. To gain insight into factors that control H2O2 persistence and •OH yield in in situ processes, the decomposition of H2O2 and transformation of contaminants were investigated in the presence of iron-containing minerals and aquifer materials (Chapter 3). Consistent with the observation described in Chapter 2, iron-containing aluminosilicates were more effective than iron oxides in converting H2O2 into •OH. In both iron-containing mineral and aquifer material systems, the yield of •OH was inversely correlated with the rate of H 2O2 decomposition. In the aquifer material systems, the yield also inversely correlated with the Mn content, consistent with the fact that the decomposition of H2O2 on manganese oxides does not produce •OH. The inverse correlation between Mn content and H2O2 loss rate and •OH yield suggests that the amount of Mn in aquifer materials could serve as a proxy for predicting H2O2 decomposition rates and contaminant oxidation efficiency. In addition to the surface and structure properties of iron solids, the presence of solutes, such as dissolved silica, also affected the decomposition of H2O2 (Chapter 4). The adsorption of dissolved silica onto mineral surfaces altered the catalytic sites, thereby decreasing the reactivity of iron- and manganese-containing minerals with H2O 2. Therefore, the presence of dissolved SiO2 could lead to greater persistence of H2O2 in groundwater, which should be considered in the design of in situ H2O 2-based treatment systems. In addition to in situ treatment, dissolved silica also can affect the reactivity of iron-containing catalysts used in ex situ processes. Therefore, its presence in contaminated industrial wastewater should be considered when ex situ treatment systems are designed.

Achieving significantly enhanced visible-light photocatalytic efficiency using a polyelectrolyte: the composites of exfoliated titania nanosheets, graphene, and poly(diallyl-dimethyl-ammonium chloride)

NASA Astrophysics Data System (ADS)

Zhang, Qian; An, Qi; Luan, Xinglong; Huang, Hongwei; Li, Xiaowei; Meng, Zilin; Tong, Wangshu; Chen, Xiaodong; Chu, Paul K.; Zhang, Yihe

2015-08-01

A high-performance visible-light-active photocatalyst is prepared using the polyelectrolyte/exfoliated titania nanosheet/graphene oxide (GO) precursor by flocculation followed by calcination. The polyelectrolyte poly(diallyl-dimethyl-ammonium chloride) serves not only as an effective binder to precipitate GO and titania nanosheets, but also boosts the overall performance of the catalyst significantly. Unlike most titania nanosheet-based catalysts reported in the literature, the composite absorbs light in the UV-Vis-NIR range. Its decomposition rate of methylene blue is 98% under visible light. This novel strategy of using a polymer to enhance the catalytic performance of titania nanosheet-based catalysts affords immense potential in designing and fabricating next-generation photocatalysts with high efficiency.A high-performance visible-light-active photocatalyst is prepared using the polyelectrolyte/exfoliated titania nanosheet/graphene oxide (GO) precursor by flocculation followed by calcination. The polyelectrolyte poly(diallyl-dimethyl-ammonium chloride) serves not only as an effective binder to precipitate GO and titania nanosheets, but also boosts the overall performance of the catalyst significantly. Unlike most titania nanosheet-based catalysts reported in the literature, the composite absorbs light in the UV-Vis-NIR range. Its decomposition rate of methylene blue is 98% under visible light. This novel strategy of using a polymer to enhance the catalytic performance of titania nanosheet-based catalysts affords immense potential in designing and fabricating next-generation photocatalysts with high efficiency. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03256c

Synthesis, characterization and photocatalytic activity of porous manganese oxide doped titania for toluene decomposition.

PubMed

Jothiramalingam, R; Wang, M K

2007-08-17

The present study describes the photocatalytic degradation of toluene in gas phase on different porous manganese oxide doped titanium dioxide. As synthesized birnessite and cryptomelane type porous manganese oxide were doped with titania and tested for photocatalytic decomposition of toluene in gas phase. The effects of the inlet concentration of toluene, flow rate (retention time) were examined and the relative humidity was maintained constantly. Thermal and textural characterization of manganese oxide doped titania materials were characterized by X-ray diffraction (XRD), thermogravemetry (TG), BET and TEM-EDAX studies. The aim of the present study is to synthesize the porous manganese oxide doped titania and to study its photocatalytic activity for toluene degradation in gas phase. Cryptomelane doped titania catalyst prepared in water medium [K-OMS-2 (W)] is shown the good toluene degradation with lower catalysts loading compared to commercial bulk titania in annular type photo reactor. The higher photocatalytic activity due to various factors such as catalyst preparation method, experimental conditions, catalyst loading, surface area, etc. In the present study manganese oxide OMS doped titania materials prepared by both aqueous and non-aqueous medium, aqueous medium prepared catalyst shows the good efficiency due to the presence of OH bonded groups on the surface of catalyst. The linear forms of different kinetic equations were applied to the adsorption data and their goodness of fit was evaluated based on the R2 and standard error. The goodness to the linear fit was observed for Elovich model with high R2 (>or=0.9477) value.

Preparation of Fischer-Tropsch catalysts from cobalt/iron hydrotalcites

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

Howard, B.H.; Boff, J.J.; Zarochak, M.F.

1995-12-31

Compounds with the (hydrotalcites) have properties that make them attractive as precursors for Fischer-Tropsch catalysts. A series of single-phase hydrotalcites with cobalt/iron atom ratios ranging from 75/25 to 25/75 has been synthesized. Mixed cobalt/iron oxides have been prepared from these hydrotalcites by controlled thermal decomposition. Thermal decomposition at temperatures below 600 {degrees}C typically produced a single-phase mixed metal oxide with a spinel structure. The BET surface areas of the spinal samples have been found to be as high as about 150 m{sup 2}/g. Appropriate reducing pretreatments have been developed for several of these spinels and their activity, selectivity, and activitymore » and selectivity maintenance have been examined at 13 MPa in a fixed-bed microreactor.« less

Parametric studies of diethyl phosphoramidate photocatalytic decomposition over TiO2.

PubMed

Sun, Bo; Vorontsov, Alexander V; Smirniotis, Panagiotis G

2011-02-28

The present study is focused on influences of parameters including pH, temperature, TiO(2) catalyst concentration, and reactant concentration on the rate of photocatalytic diethyl phosphoramidate (DEPA) decomposition with Hombikat UV 100 (HK) and Degussa P25 (P25) TiO(2). Total mineralization of DEPA is observed. Two regimes of pH, namely in acid and near-neutral environments were found where maximum total carbon (TC) decomposition was observed. The electrostatic effects on adsorption over the TiO(2) surface explain the above phenomena. The maximum rate is observed for P25 at DEPA concentration 1.3 mM whereas the rate grows continuously with DEPA concentration rise for HK. The temperature dependence of TC decomposition rate in the range of 15-63°C with both HK and P25 follows the Arrhenius equation. The activation energy for total carbon decomposition with HK and P25 are 29.5±1.0 and 24.3±3.1 kJ/mol, respectively. The decomposition rate of DEPA is larger over P25 than over HK. The rate over P25 increases faster than that with HK for each unit of the titania added when the TiO(2) concentration is less than 375 mg/l. The higher light absorption and particles aggregation of P25 are responsible for the decrease of reaction rate we observed at catalyst concentration above a certain level. In contrast, the rate over HK increases monotonically with the concentration of the photocatalyst used. Copyright © 2010 Elsevier B.V. All rights reserved.

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

Mei, Donghai; Lebarbier, Vanessa M.; Rousseau, Roger

In a combined experimental and first-principles density functional theory (DFT) study, benzene steam reforming (BSR) over MgAl 2O 4 supported Rh and Ir catalysts was investigated. Experimentally, it has been found that both highly dispersed Rh and Ir clusters (1-2 nm) on the MgAl 2O 4 spinel support are stable during the BSR in the temperature range of 700-850°C. Compared to the Ir/MgAl 2O 4 catalyst, the Rh/MgAl 2O 4 catalyst is more active with higher benzene turnover frequency and conversion. At typical steam conditions with the steam-to-carbon ratio > 12, the benzene conversion is only a weak function ofmore » the H 2O concentration in the feed. This suggests that the initial benzene decomposition step rather than the benzene adsorption is most likely the rate-determined step in BSR over supported Rh and Ir catalysts. In order to understand the differences between the two catalysts, we followed with a comparative DFT study of initial benzene decomposition pathways over two representative model systems for each supported metal (Rh and Ir) catalysts. A periodic terrace (111) surface and an amorphous 50-atom metal cluster with a diameter of 1.0 nm were used to represent the two supported model catalysts under low and high dispersion conditions. Our DFT results show that the decreasing catalyst particle size enhances the benzene decomposition on supported Rh catalysts by lowering both C-C and C-H bond scission. The activation barriers of the C-C and the C-H bond scission decrease from 1.60 and 1.61 eV on the Rh(111) surface to 1.34 and 1.26 eV on the Rh50 cluster. For supported Ir catalysts, the decreasing particle size only affects the C-C scission. The activation barrier of the C-C scission of benzene decreases from 1.60 eV on the Ir(111) surface to 1.35 eV on the Ir50 cluster while the barriers of the C-H scission are practically the same. The experimentally measured higher BSR activity on the supported highly dispersed Rh catalyst can be rationalized by the thermodynamic limitation for the very first C-C bond scission of benzene on the small Ir50 catalyst. The C-C bond scission of benzene on the small Ir50 catalyst is highly endothermic although the barrier is competitive with the barriers of both the C-C and the C-H bond-breakings on the small Rh50 catalyst. The calculations also imply that, for the supported Rh catalysts the C-C and C-H bond scissions are competitive, independently of the Rh cluster sizes. After the initial dissociation step via either the C-C or the C-H bond scission, the C-H bond breaking seems to be more favorable rather than the C-C bond breaking on the larger Rh terrace surface. This work was financially supported by the United States Department of Energy’s Office of Biomass Program’s. Computing time was granted by a user project at the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.« less

Genesis of supported carbon-coated Co nanoparticles with controlled magnetic properties, prepared by decomposition of chelate complexes

NASA Astrophysics Data System (ADS)

Tarasov, Konstantin; Beaunier, Patricia; Che, Michel; Marceau, Eric; Li, Yanling

2011-05-01

Following procedures formerly developed for the preparation of supported heterogeneous catalysts, carbon-coated cobalt nanoparticles dispersed on porous alumina have been prepared by impregnation of γ-Al2O3 with (NH4)2[Co(EDTA)] and thermal decomposition in inert atmosphere. Below 350 °C, Co(II) ions are complexed in a hexa-coordinated way by the EDTA ligand. The thermal treatment at 400-900 °C leads to the EDTA ligand decomposition and recovering of the support porosity, initially clogged by the impregnated salt. According to X-ray absorption spectroscopy, and due to in situ redox reactions between the organic ligand and Co(II), both oxidic and metallic cobalt phases are formed. Characterisation by transmission electron microscopy, X-ray diffraction and magnetic measurements reveals that an increase in the treatment temperature leads to an increase of the degree of cobalt reduction as well as to a growth of the cobalt metal particles. As a consequence, the samples prepared at 400-700 °C exhibit superparamagnetism and a saturation magnetisation of 1.7-6.5 emu g-1 at room temperature, whilst the sample prepared at 900 °C has a weak coercivity (0.1 kOe) and a saturation magnetisation of 12 emu g-1. Metal particles are homogeneously dispersed on the support and appear to be protected by carbon; its elimination by a heating in H2 at 400 °C is demonstrated to cause sintering of the metal particles. The route investigated here can be of interest for obtaining porous magnetic adsorbents or carriers with high magnetic moments and low coercivities, in which the magnetic nanoparticles are protected from chemical aggression and sintering by their coating.

Dual redox catalysts for oxygen reduction and evolution reactions: towards a redox flow Li-O2 battery.

PubMed

Zhu, Yun Guang; Jia, Chuankun; Yang, Jing; Pan, Feng; Huang, Qizhao; Wang, Qing

2015-06-11

A redox flow lithium-oxygen battery (RFLOB) by using soluble redox catalysts with good performance was demonstrated for large-scale energy storage. The new device enables the reversible formation and decomposition of Li2O2 via redox targeting reactions in a gas diffusion tank, spatially separated from the electrode, which obviates the passivation and pore clogging of the cathode.

Selective Transformation of Various Nitrogen-Containing Exhaust Gases toward N2 over Zeolite Catalysts.

PubMed

Zhang, Runduo; Liu, Ning; Lei, Zhigang; Chen, Biaohua

2016-03-23

In this review we focus on the catalytic removal of a series of N-containing exhaust gases with various valences, including nitriles (HCN, CH3CN, and C2H3CN), ammonia (NH3), nitrous oxide (N2O), and nitric oxides (NO(x)), which can cause some serious environmental problems, such as acid rain, haze weather, global warming, and even death. The zeolite catalysts with high internal surface areas, uniform pore systems, considerable ion-exchange capabilities, and satisfactory thermal stabilities are herein addressed for the corresponding depollution processes. The sources and toxicities of these pollutants are introduced. The important physicochemical properties of zeolite catalysts, including shape selectivity, surface area, acidity, and redox ability, are described in detail. The catalytic combustion of nitriles and ammonia, the direct catalytic decomposition of N2O, and the selective catalytic reduction and direct catalytic decomposition of NO are systematically discussed, involving the catalytic behaviors as well as mechanism studies based on spectroscopic and kinetic approaches and molecular simulations. Finally, concluding remarks and perspectives are given. In the present work, emphasis is placed on the structure-performance relationship with an aim to design an ideal zeolite-based catalyst for the effective elimination of harmful N-containing compounds.

Fe/N/C composite in Li-O2 battery: studies of catalytic structure and activity toward oxygen evolution reaction.

PubMed

Shui, Jiang-Lan; Karan, Naba K; Balasubramanian, Mahalingam; Li, Shu-You; Liu, Di-Jia

2012-10-10

Atomically dispersed Fe/N/C composite was synthesized and its role in controlling the oxygen evolution reaction during Li-O(2) battery charging was studied by use of a tetra(ethylene glycol) dimethyl ether-based electrolyte. Li-O(2) cells using Fe/N/C as the cathode catalyst showed lower overpotentials than α-MnO(2)/carbon catalyst and carbon-only material. Gases evolved during the charge step contained only oxygen for Fe/N/C cathode catalyst, whereas CO(2) was also detected in the case of α-MnO(2)/C or carbon-only material; this CO(2) was presumably generated from electrolyte decomposition. Our results reiterate the catalytic effect in reducing overpotentials, which not only enhances battery efficiency but also improves its lifespan by reducing or eliminating electrolyte decomposition. The structure of the Fe/N/C catalyst was characterized by transmission electron microscopy, scanning transmission electron microscopy, inductively coupled plasma optical emission spectroscopy, and X-ray absorption spectroscopy. Iron was found to be uniformly distributed within the carbon matrix, and on average, Fe was coordinated by 3.3 ± 0.6 and 2.2 ± 0.3 low Z elements (C/N/O) at bond distances of ~1.92 and ~2.09 Å, respectively.

NOx Direct Decomposition: Potentially Enhanced Thermodynamics and Kinetics on Chemically Modified Ferroelectric Surfaces

NASA Astrophysics Data System (ADS)

Kakekhani, Arvin; Ismail-Beigi, Sohrab

2014-03-01

NOx are regulated pollutants produced during automotive combustion. As part of an effort to design catalysts for NOx decomposition that operate in oxygen rich environment and permit greater fuel efficiency, we study chemistry of NOx on (001) ferroelectric surfaces. Changing the polarization at such surfaces modifies electronic properties and leads to switchable surface chemistry. Using first principles theory, our previous work has shown that addition of catalytic RuO2 monolayer on ferroelectric PbTiO3 surface makes direct decomposition of NO thermodynamically favorable for one polarization. Furthermore, the usual problem of blockage of catalytic sites by strong oxygen binding is overcome by flipping polarization that helps desorb the oxygen. We describe a thermodynamic cycle for direct NO decomposition followed by desorption of N2 and O2. We provide energy barriers and transition states for key steps of the cycle as well as describing their dependence on polarization direction. We end by pointing out how a switchable order parameter of substrate,in this case ferroelectric polarization, allows us to break away from some standard compromises for catalyst design(e.g. the Sabatier principle). This enlarges the set of potentially catalytic metals. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.

Steam Reforming of Ethylene Glycol over MgAl₂O₄ Supported Rh, Ni, and Co Catalysts

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

Mei, Donghai; Lebarbier, Vanessa M.; Xing, Rong

Steam reforming of ethylene glycol (EG) over MgAl₂O₄ supported metal (15 wt.% Ni, 5 wt.% Rh, and 15 wt.% Co) catalysts were investigated using combined experimental and theoretical methods. Compared to highly active Rh and Ni catalysts with 100% conversion, the steam reforming activity of EG over the Co catalyst is comparatively lower with only 42% conversion under the same reaction conditions (500°C, 1 atm, 119,000 h⁻¹, S/C=3.3 mol). However, CH₄ selectivity over the Co catalyst is remarkably lower. For example, by varying the gas hour space velocity (GHSV) such that complete conversion is achieved for all the catalysts, CH₄more » selectivity for the Co catalyst is only 8%, which is much lower than the equilibrium CH₄ selectivity of ~ 24% obtained for both the Rh and Ni catalysts. Further studies show that varying H₂O concentration over the Co catalyst has a negligible effect on activity, thus indicating zero-order dependence on H₂O. These experimental results suggest that the supported Co catalyst is a promising EG steam reforming catalyst for high hydrogen production. To gain mechanistic insight for rationalizing the lower CH₃ selectivity observed for the Co catalyst, the initial decomposition reaction steps of ethylene glycol via C-O, O-H, C-H, and C-C bond scissions on the Rh(111), Ni(111) and Co(0001) surfaces were investigated using density functional theory (DFT) calculations. Despite the fact that the bond scission sequence in the EG decomposition on the three metal surfaces varies, which leads to different reaction intermediates, the lower CH₄ selectivity over the Co catalyst, as compared to the Rh and Ni catalysts, is primarily due to the higher barrier for CH₄ formation. The higher S/C ratio enhances the Co catalyst stability, which can be elucidated by the facile water dissociation and an alternative reaction path to remove the CH species as a coking precursor via the HCOH formation. This work was financially supported by the United States Department of Energy (DOE)’s Bioenergy Technologies Office (BETO) and performed at the Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle Memorial Institute. Computing time and advanced catalyst characterization use was granted by a user proposal at the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL). EMSL is a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at PNNL.« less

Thermocatalytic process for CO.sub.2-free production of hydrogen and carbon from hydrocarbons

DOEpatents

Muradov, Nazim Z [Melbourne, FL

2011-08-23

A novel process and apparatus are disclosed for sustainable CO.sub.2-free production of hydrogen and carbon by thermocatalytic decomposition (dissociation, pyrolysis, cracking) of hydrocarbon fuels over carbon-based catalysts in the absence of air and/or water. The apparatus and thermocatalytic process improve the activity and stability of carbon catalysts during the thermocatalytic process and produce both high purity hydrogen (at least, 99.0 volume %) and carbon, from any hydrocarbon fuel, including sulfurous fuels. In a preferred embodiment, production of hydrogen and carbon is achieved by both internal and external activation of carbon catalysts. Internal activation of carbon catalyst is accomplished by recycling of hydrogen-depleted gas containing unsaturated and aromatic hydrocarbons back to the reactor. External activation of the catalyst can be achieved via surface gasification with hot combustion gases during catalyst heating. The process and apparatus can be conveniently integrated with any type of fuel cell to generate electricity.

Controlling the bond scission sequence of oxygenates for energy applications

NASA Astrophysics Data System (ADS)

Stottlemyer, Alan L.

The so called "Holy Grail" of heterogeneous catalysis is a fundamental understanding of catalyzed chemical transformations which span multidimensional scales of both length and time, enabling rational catalyst design. Such an undertaking is realizable only with an atomic level understanding of bond formation and destruction with respect to intrinsic properties of the metal catalyst. In this study, we investigate the bond scission sequence of small oxygenates (methanol, ethanol, ethylene glycol) on bimetallic transition metal catalysts and transition metal carbide catalysts. Oxygenates are of interest both as hydrogen carriers for reforming to H2 and CO and as fuels in direct alcohol fuel cells (DAFC). To address the so-called "materials gap" and "pressure gap" this work adopted three parallel research approaches: (1) ultra high vacuum (UHV) studies including temperature programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) on polycrystalline surfaces; (2) DFT studies including thermodynamic and kinetic calculations; (3) electrochemical studies including cyclic voltammetry (CV) and chronoamperometry (CA). Recent studies have suggested that tungsten monocarbide (WC) may behave similarly to Pt for the electrooxidation of oxygenates. TPD was used to quantify the activity and selectivity of oxygenate decomposition for WC and Pt-modifiedWC (Pt/WC) as compared to Pt. While decomposition activity was generally higher on WC than on Pt, scission of the C-O bond resulted in alkane/alkene formation on WC, an undesired product for DAFC. When Pt was added to WC by physical vapor deposition C-O bond scission was limited, suggesting that Pt synergistically modifies WC to improve the selectivity toward C-H bond scission to produce H2 and CO. Additionally, TPD confirmed WC and Pt/WC to be more CO tolerant than Pt. HREELS results verified that surface intermediates were different on Pt/WC as compared to Pt or WC and evidence of aldehyde intermediates was observed on the Pt and Pt/WC surfaces. For CH3OH decomposition, DFT calculations suggested that the bond scission sequence could be controlled using monolayer coverage of Pt on WC. The Ni/Pt bimetallic system was studied as an example for using oxygenates as a hydrogen source. There are two well characterized surface structures for the Ni/Pt system: the surface configuration, in which the Ni atoms reside primarily on the surface of the Pt bulk, and the subsurface configuration, in which the second atomic layer is enriched in Ni atoms and the surface is enriched in Pt atoms. These configurations are denoted NiPtPt and PtNiPt, respectively. DFT results revealed that trends established for the Ni/Pt(111) system extend to the Ni/Pt(100) analogue. TPD studies revealed that the NiPtPt surface was more active for oxygenate reforming than the Pt or PtNiPt surfaces. HREELS confirmed the presence of strongly bound reaction intermediates, including aldehyde-like species, and suggested that the first decomposition step was likely O-H bond scission. Thus, the binding energies of the deprotonated reaction intermediates are important parameters in controlling the decomposition pathways of oxygenates. These studies have demonstrated that the bond scission sequence of oxygenate decomposition can be controlled using bimetallic and transition metal carbide catalysts. While this study has focused on oxygenate decomposition for energy applications, the principles and methodology applied herein are universally applicable to the development of novel and marketable value-added products. The value in such a methodology is in the combination of both calculations to predict catalytic and chemical properties, and experiments to fine-tune theoretical predictions.

Ferroelectric based catalysis: Switchable surface chemistry

NASA Astrophysics Data System (ADS)

Kakekhani, Arvin; Ismail-Beigi, Sohrab

2015-03-01

We describe a new class of catalysts that uses an epitaxial monolayer of a transition metal oxide on a ferroelectric substrate. The ferroelectric polarization switches the surface chemistry between strongly adsorptive and strongly desorptive regimes, circumventing difficulties encountered on non-switchable catalytic surfaces where the Sabatier principle dictates a moderate surface-molecule interaction strength. This method is general and can, in principle, be applied to many reactions, and for each case the choice of the transition oxide monolayer can be optimized. Here, as a specific example, we show how simultaneous NOx direct decomposition (into N2 and O2) and CO oxidation can be achieved efficiently on CrO2 terminated PbTiO3, while circumventing oxygen (and sulfur) poisoning issues. One should note that NOx direct decomposition has been an open challenge in automotive emission control industry. Our method can expand the range of catalytically active elements to those which are not conventionally considered for catalysis and which are more economical, e.g., Cr (for NOx direct decomposition and CO oxidation) instead of canonical precious metal catalysts. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.

A New Bioinspired Perchlorate Reduction Catalyst with Significantly Enhanced Stability via Rational Tuning of Rhenium Coordination Chemistry and Heterogeneous Reaction Pathway.

PubMed

Liu, Jinyong; Han, Mengwei; Wu, Dimao; Chen, Xi; Choe, Jong Kwon; Werth, Charles J; Strathmann, Timothy J

2016-06-07

Rapid reduction of aqueous ClO4(-) to Cl(-) by H2 has been realized by a heterogeneous Re(hoz)2-Pd/C catalyst integrating Re(O)(hoz)2Cl complex (hoz = oxazolinyl-phenolato bidentate ligand) and Pd nanoparticles on carbon support, but ClOx(-) intermediates formed during reactions with concentrated ClO4(-) promote irreversible Re complex decomposition and catalyst deactivation. The original catalyst design mimics the microbial ClO4(-) reductase, which integrates Mo(MGD)2 complex (MGD = molybdopterin guanine dinucleotide) for oxygen atom transfer (OAT). Perchlorate-reducing microorganisms employ a separate enzyme, chlorite dismutase, to prevent accumulation of the destructive ClO2(-) intermediate. The structural intricacy of MGD ligand and the two-enzyme mechanism for microbial ClO4(-) reduction inspired us to improve catalyst stability by rationally tuning Re ligand structure and adding a ClOx(-) scavenger. Two new Re complexes, Re(O)(htz)2Cl and Re(O)(hoz)(htz)Cl (htz = thiazolinyl-phenolato bidentate ligand), significantly mitigate Re complex decomposition by slightly lowering the OAT activity when immobilized in Pd/C. Further stability enhancement is then obtained by switching the nanoparticles from Pd to Rh, which exhibits high reactivity with ClOx(-) intermediates and thus prevents their deactivating reaction with the Re complex. Compared to Re(hoz)2-Pd/C, the new Re(hoz)(htz)-Rh/C catalyst exhibits similar ClO4(-) reduction activity but superior stability, evidenced by a decrease of Re leaching from 37% to 0.25% and stability of surface Re speciation following the treatment of a concentrated "challenge" solution containing 1000 ppm of ClO4(-). This work demonstrates the pivotal roles of coordination chemistry control and tuning of individual catalyst components for achieving both high activity and stability in environmental catalyst applications.

Carbon nanotube synthesis via the catalytic chemical vapor deposition of methane in the presence of iron, molybdenum, and iron-molybdenum alloy thin layer catalysts

NASA Astrophysics Data System (ADS)

Yahyazadeh, Arash; Khoshandam, Behnam

In this study, we documented the catalytic chemical vapor deposition synthesis of carbon nanotubes (CNTs) using ferrocene and molybdenum hexacarbonyl as catalyst nanoparticle precursors and methane as a nontoxic and economical carbon source for the first time. Field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, wavelength dispersive X-ray spectrometry and transmission electron microscopy of the thin layer catalyst as a simple and cost effective catalyst preparation after methane decomposition reaction, along with Fourier transform infrared spectroscopy and Raman spectroscopy confirmed the growth of CNTs, from bimetallic nanoparticles, which are converted into iron-molybdenum alloy nanoparticles at 700 °C for pretreatment by hydrogen after chemical vapor deposition of thin layers. An investigation of the weight percentages of the chemical elements present in the CNTs synthesized from iron-molybdenum catalyst using quartz sheet substrate at 750 °C, confirmed a significant carbon yield of 75.4% which represents high catalyst activity. Additionally, multi-walled carbon nanotubes (∼16-55 nm in diameter and 1.2 μm in length) were observed in the iron-molybdenum alloy sample after methane decomposition reaction at 750 °C for 35 min. To show the role of iron and molybdenum coated on silicon substrate as two thin layer catalysts, samples were considered for CNTs growth (diameter ∼47-69 nm) at 800 °C and 830 °C, respectively. Moreover, the effect of hydrogen pretreatment was evaluated in terms of active metal coating properly. The best graphitic structure due to Raman spectroscopy outcomes (ID/IG ratio) was obtained for iron coated on a quartz sheet, which was estimated at 0.8505. Thermogravimetric analysis proved the thermal stability of the synthesized CNTs using iron thin-layer catalyst up to 350 °C.

Monolithic catalyst beds for hydrazine reactors

NASA Technical Reports Server (NTRS)

1973-01-01

A monolithic catalyst bed for monopropellant hydrazine decomposition was evaluated. The program involved the evaluation of a new hydrazine catalyst concept wherein open-celled foamed materials are used as supports for the active catalysts. A high-surface-area material is deposited upon the open-celled foamed material and is then coated with an active metal to provide a spontaneous catalyst. Only a fraction of the amount of expensive active metal in currently available catalysts is needed to promote monolithic catalyst. Numerous parameters were evaluated during the program, and the importance of additional parameters became obvious only while the program was in progress. A demonstration firing (using a 2.2-Newton (N)(0.5-lbf) reactor) successfully accumulated 7,700 seconds of firing time and 16 ambient temperature starts without degradation. Based on the excellent results obtained throughout the program and the demonstrated life capability of the monolithic foam, it is recommended that additional studies be conducted to further exploit the advantages of this concept.

Conversion of glycerol to polyglycerol over waste duck-bones as a catalyst in solvent free etherification process

NASA Astrophysics Data System (ADS)

Ayoub, Muhammad; Sufian, Suriati; Mekuria Hailegiorgis, Sintayehu; Ullah, Sami; Uemura, Yoshimitsu

2017-08-01

The alkaline catalyst derived from the duck-bones was used for conversion of glycerol to polyglycerol via solvent free etherification process. The physicochemical properties of prepared materials were duck-bones were systematically investigated as a catalyst by latest techniques of Thermo gravimetric analysis (TGA), X-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) surface properties. TGA showed different trends of duck-bones decomposition from room temperature to 1000C. XRD pattern showed a clear and sharp peaks of a crystalline phase of CaO. The activity of the catalysts was in line with the basic amount of the strong base sites, surface area, and crystalline phase in the catalysts. The prepared catalyst derived from duck-bones provided high activity (99 %) for glycerol conversion and around 68 % yield for polyglycerol production. These ample wastes of duck-bones have good potential to be used as polyglycerol production catalysts due to have high quantity of Ca compare to other types of bones like cow, chicken and fish bones.

Towards a practical setup for hydrogen production from formic acid.

PubMed

Sponholz, Peter; Mellmann, Dörthe; Junge, Henrik; Beller, Matthias

2013-07-01

Formic acid cracker: A mini plant that allows for continuous formic acid decomposition to hydrogen and carbon dioxide under ambient conditions is presented. By using an in situ-formed ruthenium catalyst, unprecedented turnover numbers over 1,000,000 are achieved. The active catalyst is formed in situ from commercially available [RuCl2 (benzene)]2 and 1,2-bisdiphenylphosphinoethane. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of impurities in polybutene on the quality of alkenylsuccinic anhydrides

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

Yarmolyuk, B.M.; Pustovit, V.E.; Bereza, L.I.

1984-03-01

Synthesis of alkenylsuccini anhydrides (ASAs) was carried out in thermostable ampules at 230/sup 0/C in the course of 12 hours at an MA:PB molar ratio of 1.3:1 in a medium of prepurified petroleum xylene (30%). Freshly distilled maleic anhydride and industrial specimens of polybutene were used in the experiments. It was established that the main impurities which are formed in the production of polybutene and in its processing are ions of sodium, peroxide compounds and products of decomposition of the polymerization catalyst. The concentration of sodium ion was determined by an atomic adsorption method on an A-3000 instrument, the concentrationmore » of peroxides was determined by iodometry (3), and the concentration of catalyst decomposition products was determined from the amount of mechanical impurities.« less

Iridium-catalyst-based autonomous bubble-propelled graphene micromotors with ultralow catalyst loading.

PubMed

Wang, Hong; Sofer, Zdeněk; Eng, Alex Yong Sheng; Pumera, Martin

2014-11-10

A novel concept of an iridium-based bubble-propelled Janus-particle-type graphene micromotor with very high surface area and with very low catalyst loading is described. The low loading of Ir catalyst (0.54 at %) allows for fast motion of graphene microparticles with high surface area of 316.2 m(2)  g(-1). The micromotor was prepared with a simple and scalable method by thermal exfoliation of iridium-doped graphite oxide precursor composite in hydrogen atmosphere. Oxygen bubbles generated from the decomposition of hydrogen peroxide at the iridium catalytic sites provide robust propulsion thrust for the graphene micromotor. The high surface area and low iridium catalyst loading of the bubble-propelled graphene motors offer great possibilities for dramatically enhanced cargo delivery. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Decomposition Studies of Tetraphenylborate Slurries

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

Crawford, C.L.

1997-05-06

This report details the decomposition of aqueous (K,Na) slurries in concentrated salt solutions using a more complete candidate catalyst recipe, extended testing temperatures (40-70 degrees C) and test durations of approximately 1500 hours (9 weeks). This study uses recently developed High-Pressure Liquid Chromatography (HPLC) methods for analysis of tetraphenylborate (TPB-), triphenylborane (3PB) and diphenylborinic acid (2PB). All of the present tests involve non-radioactive simulants and do not include investigations of radiolysis effects.

Synthesis, characterization, and catalytic activity in Suzuki coupling and catalase-like reactions of new chitosan supported Pd catalyst.

PubMed

Baran, Talat; Inanan, Tülden; Menteş, Ayfer

2016-07-10

The aim of this study is to analyze the synthesis of a new chitosan supported Pd catalyst and examination of its catalytic activity in: Pd catalyst was synthesized using chitosan as a biomaterial and characterized with FTIR, TG/DTG, XRD, (1)H NMR, (13)C NMR, SEM-EDAX, ICP-OES, Uv-vis spectroscopies, and magnetic moment, along with molar conductivity analysis. Biomaterial supported Pd catalyst indicated high activity and long life time as well as excellent turnover number (TON) and turnover frequency (TOF) values in Suzuki reaction. Biomaterial supported Pd catalyst catalyzed H2O2 decomposition reaction with considerable high activity using comparatively small loading catalyst (10mg). Redox potential of biomaterial supported Pd catalyst was still high without negligible loss (13% decrease) after 10 cycles in reusability tests. As a consequence, eco-friendly biomaterial supported Pd catalyst has superior properties such as high thermal stability, long life time, easy removal from reaction mixture and durability to air, moisture and high temperature. Copyright © 2016 Elsevier Ltd. All rights reserved.

Porphyrins and metal complexes thereof having haloalkyl side chains

DOEpatents

Wijesekera, Tilak; Lyons, James E.; Ellis, Jr., Paul E.; Bhinde, Manoj V.

1997-01-01

Transition metal complexes of meso-haloalkylporphyrins, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides.

Hydrogen production using thermocatalytic decomposition of methane on Ni30/activated carbon and Ni30/carbon black.

PubMed

Srilatha, K; Viditha, V; Srinivasulu, D; Ramakrishna, S U B; Himabindu, V

2016-05-01

Hydrogen is an energy carrier of the future need. It could be produced from different sources and used for power generation or as a transport fuel which mainly in association with fuel cells. The primary challenge for hydrogen production is reducing the cost of production technologies to make the resulting hydrogen cost competitive with conventional fuels. Thermocatalytic decomposition (TCD) of methane is one of the most advantageous processes, which will meet the future demand, hence an attractive route for COx free environment. The present study deals with the production of hydrogen with 30 wt% of Ni impregnated in commercially available activated carbon and carbon black catalysts (samples coded as Ni30/AC and Ni30/CB, respectively). These combined catalysts were not attempted by previous studies. Pure form of hydrogen is produced at 850 °C and volume hourly space velocity (VHSV) of 1.62 L/h g on the activity of both the catalysts. The analysis (X-ray diffraction (XRD)) of the catalysts reveals moderately crystalline peaks of Ni, which might be responsible for the increase in catalytic life along with formation of carbon fibers. The activity of carbon black is sustainable for a longer time compared to that of activated carbon which has been confirmed by life time studies (850 °C and 54 sccm of methane).

Catalytic effect on ultrasonic decomposition of cellulose

NASA Astrophysics Data System (ADS)

Nomura, Shinfuku; Wakida, Kousuke; Mukasa, Shinobu; Toyota, Hiromichi

2018-07-01

Cellulase used as a catalyst is introduced into the ultrasonic welding method for cellulose decomposition in order to obtain glucose. By adding cellulase in the welding process, filter paper decomposes cellulose into glucose, 5-hydroxymethylfurfural (5-HMF), furfural, and oligosaccharides. The amount of glucose from hydrolysis was increased by ultrasonic welding in filter paper immersed in water. Most glucose was obtained by 100 W ultrasonic irradiation; however, when was applied 200 W, the dehydration of the glucose itself occurred, and was converted into 5-HMF owing to the thermolysis of ultrasonics. Therefore, there is an optimum welding power for the production of glucose from cellulose decomposition.

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.

Ambient temperature NO oxidation over Cr-based amorphous mixed oxide catalysts: effects from the second oxide components

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

Wang, Aiyong; Lin, Bo; Zhang, Hanlei

2017-01-01

Three series of Cr-based mixed oxides (Cr-Co, Cr-Fe, and Cr-Ni oxides) with high specific surface areas and amorphous textures were synthesized using a novel sol-gel method. These mixed oxides, in comparison to their pure metal oxide (CrOx, Co3O4, FeOx and NiO) counterparts, display enhanced performance for catalytic oxidation of low-concentration NO at room temperature. The best performing catalysts achieve 100% NO conversion for ~30 h of operation at a high space velocity of 45,000 ml g-1 h-1. The amorphous structure was found to be critical for these catalysts to maintain high activity and durability. Control of Cr/M (M=Co, Fe andmore » Ni) molar ratio, nitrate precursor decomposition temperature and catalyst calcination temperature was key to the synthesis of these highly active catalysts.« less

Porphyrins and metal complexes thereof having haloalkyl side chains

DOEpatents

Wijesekera, T.; Lyons, J.E.; Ellis, P.E. Jr.; Bhinde, M.V.

1997-03-04

Transition metal complexes of meso-haloalkylporphyrins, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides. 7 figs.

Three-dimensional carbon fibers and method and apparatus for their production

DOEpatents

Muradov, Nazim Z [Melbourne, FL

2012-02-21

This invention relates to novel three-dimensional (3D) carbon fibers which are original (or primary) carbon fibers (OCF) with secondary carbon filaments (SCF) grown thereon, and, if desired, tertiary carbon filaments (TCF) are grown from the surface of SCF forming a filamentous carbon network with high surface area. The methods and apparatus are provided for growing SCF on the OCF by thermal decomposition of carbonaceous gases (CG) over the hot surface of the OCF without use of metal-based catalysts. The thickness and length of SCF can be controlled by varying operational conditions of the process, e.g., the nature of CG, temperature, residence time, etc. The optional activation step enables one to produce 3D activated carbon fibers with high surface area. The method and apparatus are provided for growing TCF on the SCF by thermal decomposition of carbonaceous gases over the hot surface of the SCF using metal catalyst particles.

Statistical Ring Opening Metathesis Copolymerization of Norbornene and Cyclopentene by Grubbs' 1st-Generation Catalyst.

PubMed

Nikovia, Christiana; Maroudas, Andreas-Philippos; Goulis, Panagiotis; Tzimis, Dionysios; Paraskevopoulou, Patrina; Pitsikalis, Marinos

2015-08-27

Statistical copolymers of norbornene (NBE) with cyclopentene (CP) were prepared by ring-opening metathesis polymerization, employing the 1st-generation Grubbs' catalyst, in the presence or absence of triphenylphosphine, PPh₃. The reactivity ratios were estimated using the Finemann-Ross, inverted Finemann-Ross, and Kelen-Tüdos graphical methods, along with the computer program COPOINT, which evaluates the parameters of binary copolymerizations from comonomer/copolymer composition data by integrating a given copolymerization equation in its differential form. Structural parameters of the copolymers were obtained by calculating the dyad sequence fractions and the mean sequence length, which were derived using the monomer reactivity ratios. The kinetics of thermal decomposition of the copolymers along with the respective homopolymers was studied by thermogravimetric analysis within the framework of the Ozawa-Flynn-Wall and Kissinger methodologies. Finally, the effect of triphenylphosphine on the kinetics of copolymerization, the reactivity ratios, and the kinetics of thermal decomposition were examined.

A trimodal porous carbon as an effective catalyst for hydrogen production by methane decomposition.

PubMed

Shen, Yi; Lua, Aik Chong

2016-01-15

A new type of porous carbon with an interconnected trimodal pore system is synthesized by a nanocasting method using nanoparticulated bimodal micro-mesoporous silica particles as the template. The synthesized template and carbon material are characterized using transmission electron microscopy (TEM), field emission electron scanning microscopy (FESEM) and nitrogen adsorption-desorption test. The synthesized carbon material has an extremely high surface area, a large pore volume and an interconnected pore structure, which could provide abundant active sites and space for chemical reactions and minimize the diffusion resistance of the reactants. The resulting carbon is used as the catalyst for hydrogen production by the thermal decomposition of methane. The catalytic results show that the as-synthesized carbon in this study produces much higher methane conversion and hydrogen yield than the commercial carbon materials. Copyright © 2015 Elsevier Inc. All rights reserved.

Thermal Decomposition Behaviors and Burning Characteristics of AN/RDX-Based Composite Propellants Supplemented with MnO2 and Fe2O3

NASA Astrophysics Data System (ADS)

Kohga, Makoto; Naya, Tomoki

2015-10-01

Ammonium nitrate (AN)-based composite propellants have gained popularity because of the clean burning nature of AN as an oxidizer. However, such propellants have several disadvantages such as poor ignition and low burning rate. The burning characteristics of the AN propellant were improved when a portion of this propellant was replaced by an energetic material and the addition of a catalyst. In this study, RDX (1,3,5-trinitroperhydro-1,3,5-triazine) was used as the energetic material, and Fe2O3 and MnO2 were used as catalysts. The burning characteristics of the AN/RDX propellants supplemented with catalysts were investigated, and the effects of the replacement of AN by RDX and the catalyst addition were evaluated.

Evaluation and characterization of the methane-carbon dioxide decomposition reaction

NASA Technical Reports Server (NTRS)

Davenport, R. J.; Schubert, F. H.; Shumar, J. W.; Steenson, T. S.

1975-01-01

A program was conducted to evaluate and characterize the carbon dioxide-methane (CO2-CH4) decomposition reaction, i.e., CO2 + CH4 = 2C + 2H2O. The primary objective was to determine the feasibility of applying this reaction at low temperatures as a technique for recovering the oxygen (O2) remaining in the CO2 which exits mixed with CH4 from a Sabatier CO2 reduction subsystem (as part of an air revitalization system of a manned spacecraft). A test unit was designed, fabricated, and assembled for characterizing the performance of various catalysts for the reaction and ultraviolet activation of the CH4 and CO2. The reactor included in the test unit was designed to have sufficient capacity to evaluate catalyst charges of up to 76 g (0.17 lb). The test stand contained the necessary instrumentation and controls to obtain the data required to characterize the performance of the catalysts and sensitizers tested: flow control and measurement, temperature control and measurement, product and inlet gas analysis, and pressure measurement. A product assurance program was performed implementing the concepts of quality control and safety into the program effort.

Ethylene dissociation on flat and stepped Ni(1 1 1): A combined STM and DFT study

NASA Astrophysics Data System (ADS)

Vang, Ronnie T.; Honkala, Karoliina; Dahl, Søren; Vestergaard, Ebbe K.; Schnadt, Joachim; Lægsgaard, Erik; Clausen, Bjerne S.; Nørskov, Jens K.; Besenbacher, Flemming

2006-01-01

The dissociative adsorption of ethylene (C 2H 4) on Ni(1 1 1) was studied by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The STM studies reveal that ethylene decomposes exclusively at the step edges at room temperature. However, the step edge sites are poisoned by the reaction products and thus only a small brim of decomposed ethylene is formed. At 500 K decomposition on the (1 1 1) facets leads to a continuous growth of carbidic islands, which nucleate along the step edges. DFT calculations were performed for several intermediate steps in the decomposition of ethylene on both Ni(1 1 1) and the stepped Ni(2 1 1) surface. In general the Ni(2 1 1) surface is found to have a higher reactivity than the Ni(1 1 1) surface. Furthermore, the calculations show that the influence of step edge atoms is very different for the different reaction pathways. In particular the barrier for dissociation is lowered significantly more than the barrier for dehydrogenation, and this is of great importance for the bond-breaking selectivity of Ni surfaces. The influence of step edges was also probed by evaporating Ag onto the Ni(1 1 1) surface. STM shows that the room temperature evaporation leads to a step flow growth of Ag islands, and a subsequent annealing at 800 K causes the Ag atoms to completely wet the step edges of Ni(1 1 1). The blocking of the step edges is shown to prevent all decomposition of ethylene at room temperature, whereas the terrace site decomposition at 500 K is confirmed to be unaffected by the Ag atoms. Finally a high surface area NiAg alloy catalyst supported on MgAl 2O 4 was synthesized and tested in flow reactor measurements. The NiAg catalyst has a much lower activity for ethane hydrogenolysis than a similar Ni catalyst, which can be rationalized by the STM and DFT results.

Effects of Potassium loading and thermal aging on K/Pt/Al2O3 high-temperature lean NOx trap catalysts

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

Luo, Jinyong; Gao, Feng; Kim, Do Heui

2014-03-31

The effects of K loading and thermal aging on the structural properties and high temperature performance of Pt/K/Al2O3 lean NOx trap (LNT) catalysts were investigated using in situ X-ray diffraction (XRD), temperature-programmed decomposition/desorption of NOx (NOx-TPD), transmission electron microscopy (TEM), NO oxidation and NOx storage tests. In situ XRD results demonstrate that KNO3 becomes extremely mobile on the Al2O3 surface, and experiences complex transformations between orthorhombic and rhombohedral structures, accompanied by sintering, melting and thermal decomposition upon heating. NOx storage results show an optimum K loading around 10% for the best performance at high temperatures. At lower K loadings wheremore » the majority of KNO3 stays as a surface layer, the strong interaction between KNO3 and Al2O3 promotes KNO3 decomposition and deteriorates high-temperature performance. At K loadings higher than 10%, the performance drop is not caused by NOx diffusion limitations as for the case of barium-based LNTs, but rather from the blocking of Pt sites by K species, which adversely affects NO oxidation. Thermal aging at 800 ºC severely deactivates the Pt/K/Al2O3 catalysts due to Pt sintering. However, in the presence of potassium, some Pt remains in a dispersed and oxidized form. These Pt species interact strongly with K and, therefore, do not sinter. After a reduction treatment, these Pt species remain finely dispersed, contributing to a partial recovery of NOx storage performance.« less

The use of ultrasmall iron(0) nanoparticles as catalysts for the selective hydrogenation of unsaturated C-C bonds.

PubMed

Kelsen, Vinciane; Wendt, Bianca; Werkmeister, Svenja; Junge, Kathrin; Beller, Matthias; Chaudret, Bruno

2013-04-28

The performance of well-defined ultrasmall iron(0) nanoparticles (NPs) as catalysts for the selective hydrogenation of unsaturated C-C and C=X bonds is reported. Monodisperse iron nanoparticles of about 2 nm size are synthesized by the decomposition of {Fe(N[Si(CH3)3]2)2}2 under dihydrogen. They are found to be active for the hydrogenation of various alkenes and alkynes under mild conditions and weakly active for C=O bond hydrogenation.

A comparative study of alumina-supported Ni catalysts prepared by photodeposition and impregnation methods on the catalytic ozonation of 2,4-dichlorophenoxyacetic acid

NASA Astrophysics Data System (ADS)

Rodríguez, Julia L.; Valenzuela, Miguel A.; Tiznado, Hugo; Poznyak, Tatiana; Chairez, Isaac; Magallanes, Diana

2017-02-01

The heterogeneous catalytic ozonation on unsupported and supported oxides has been successfully tested for the removal of several refractory compounds in aqueous solution. In this work, alumina-supported nickel catalysts prepared by photodeposition and impregnation methods were compared in the catalytic ozonation of 2,4-dichlorophenoxyacetic acid (2,4-D). The catalysts were characterized by high-resolution electron microscopy and X-ray photoelectron spectroscopy. The photochemical decomposition of Ni acetylacetonate to produce Ni(OH)2, NiO, and traces of Ni° deposited on alumina was achieved in the presence of benzophenone as a sensitizer. A similar surface composition was found with the impregnated catalyst after its reduction with hydrogen at 500 °C and exposed to ambient air. Results indicated a higher initial activity and maleic acid (byproduct) concentration with the photodeposited catalyst (1 wt% Ni) compared to the impregnated catalyst (3 wt% Ni). These findings suggest the use of the photodeposition method as a simple and reliable procedure for the preparation of supported metal oxide/metal catalysts under mild operating conditions.

Electromagnetic Characterization of Carbon Nanotube Films Subject to an Oxidative Treatment at Elevated Temperature (Preprint)

DTIC Science & Technology

2010-07-01

response to the tip causes a redistribution of charge on the tip in order to maintain the equipotential surface of the sphere, and also results in a shift...can be obtained. In some instances these treatments lead to uncapping of nanotubes. Geng et al. [25] have shown that the surfaces of SWNT bundles...20] discovered a new and catalyst-free method for the growth of CNTs: surface decomposition of silicon carbide (SiC). This thermal decomposition

Characterization of the Field Emission Properties of Carbon Nanotubes Formed on Silicon Carbide Substrates by Surface Decomposition

DTIC Science & Technology

2006-03-01

chemical vapor deposition (CVD) with methane as the feed gas . CNT growth specifics included using iron nitrate in an isopropanol solution as the...with residual oxygen gas in the chamber used for growth ([24], [25], [13]). Specific conditions for producing CNTs through the decomposition of...resulting in CNT formation is given by (2.30), (2.31), and (2.32) [24]. The oxygen gas acting as a catalyst to the chemical reaction is purported to be

Alkane oxidation with porphyrins and metal complexes thereof having haloalkyl side chains

DOEpatents

Wijesekera, Tilak; Lyons, James E.; Ellis, Jr., Paul E.; Bhinde, Manoj V.

1998-01-01

Transition metal complexes of meso-haloalkylporphyrins, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides.

Efficient catalytic decomposition of formic acid for the selective generation of H2 and H/D exchange with a water-soluble rhodium complex in aqueous solution.

PubMed

Fukuzumi, Shunichi; Kobayashi, Takeshi; Suenobu, Tomoyoshi

2008-01-01

Formic acid (HCOOH) decomposes efficiently to afford H2 and CO2 selectively in the presence of a catalytic amount of a water-soluble rhodium aqua complex, [Rh(III)(Cp*)(bpy)(H2O)]2+ (Cp*=pentamethylcyclopentadienyl, bpy=2,2'-bipyridine) in aqueous solution at 298 K. No CO was produced in this catalytic decomposition of HCOOH. The decomposition rate reached a maximum value at pH 3.8. No deterioration of the catalyst was observed during the catalytic decomposition of HCOOH, and the catalytic activity remained the same for the repeated addition of HCOOH. The rhodium-hydride complex was detected as the catalytic active species that undergoes efficient H/D exchange with water. When the catalytic decomposition of HCOOH was performed in D2O, D2 was produced selectively. Such an efficient H/D exchange and the observation of a deuterium kinetic isotope effect in the catalytic decomposition of DCOOH in H2O provide valuable mechanistic insight into this efficient and selective decomposition process.

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.

Warm Cleanup of Coal-Derived Syngas: Multicontaminant Removal Process Demonstration

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

Spies, Kurt A.; Rainbolt, James E.; Li, Xiaohong S.

Warm cleanup of coal- or biomass-derived syngas requires sorbent and catalytic beds to protect downstream processes and catalysts from fouling. Sulfur is particularly harmful because even parts-per-million amounts are sufficient to poison downstream synthesis catalysts. Zinc oxide (ZnO) is a conventional sorbent for sulfur removal; however, its operational performance using real gasifier-derived syngas and in an integrated warm cleanup process is not well reported. In this paper, we report the optimal temperature for bulk desulfurization to be 450oC, while removal of sulfur to parts-per-billion levels requires a lower temperature of approximately 350oC. Under these conditions, we found that sulfur inmore » the form of both hydrogen sulfide and carbonyl sulfide could be absorbed equally well using ZnO. For long-term operation, sorbent regeneration is desirable to minimize process costs. Over the course of five sulfidation and regeneration cycles, a ZnO bed lost about a third of its initial sulfur capacity, however sorbent capacity stabilized. Here, we also demonstrate, at the bench-scale, a process and materials used for warm cleanup of coal-derived syngas using five operations: 1) Na2CO3 for HCl removal, 2) regenerable ZnO beds for bulk sulfur removal, 3) a second ZnO bed for trace sulfur removal, 4) a Ni-Cu/C sorbent for multi-contaminant inorganic removal, and 5) a Ir-Ni/MgAl2O4 catalyst employed for ammonia decomposition and tar and light hydrocarbon steam reforming. Syngas cleanup was demonstrated through successful long-term performance of a poison-sensitive, Cu-based, water-gas-shift catalyst placed downstream of the cleanup process train. The tar reformer is an important and necessary operation with this particular gasification system; its inclusion was the difference between deactivating the water-gas catalyst with carbon deposition and successful 100-hour testing using 1 LPM of coal-derived syngas.« less

Chiral copper(II) complex-catalyzed reactions of partially protected carbohydrates.

PubMed

Allen, C Liana; Miller, Scott J

2013-12-20

Catalyst-controlled regioselective functionalization of partially protected saccharide molecules is a highly important yet under-developed area of carbohydrate chemistry. Such reactions allow for the reduction of protecting group manipulation steps required in syntheses involving sugars. Herein, an approach to these processes using enantiopure copper-bis(oxazoline) catalysts to control couplings of electrophiles to various partially protected sugars is reported. In a number of cases, divergent regioselectivity was observed as a function of the enantiomer of catalyst that is used.

ZnO/Ag nanocomposite: an efficient catalyst for degradation studies of textile effluents under visible light.

PubMed

Saravanan, R; Karthikeyan, N; Gupta, V K; Thirumal, E; Thangadurai, P; Narayanan, V; Stephen, A

2013-05-01

Degradation of model organic dye and industry effluent was studied using different weight percentages of Ag into ZnO as a catalyst. In this study, the catalysts were prepared by thermal decomposition method, which was employed for the first time in the preparation of ZnO/Ag nanocomposite catalysts. The physical and chemical properties of the prepared samples were studied using various techniques. The specific surface area, which plays an important role in the photocatalytic degradation, was studied using BET analysis and 10 wt.% Ag into ZnO showed the best degrading efficiency. The optical absorption (UV-vis) and emission (PL) properties of the samples were studied and results suggest better photocatalytic properties for 10 wt.% Ag sample compared to other samples. Crown Copyright © 2013. Published by Elsevier B.V. All rights reserved.

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

Haydary, J., E-mail: juma.haydary@stuba.sk; Susa, D.; Dudáš, J.

Highlights: ► Pyrolysis of aseptic packages was carried out in a laboratory flow reactor. ► Distribution of tetrapak into the product yields was obtained. ► Composition of the pyrolysis products was estimated. ► Secondary thermal and catalytic decomposition of tars was studied. ► Two types of catalysts (dolomite and red clay marked AFRC) were used. - Abstract: Pyrolysis of aseptic packages (tetrapak cartons) in a laboratory apparatus using a flow screw type reactor and a secondary catalytic reactor for tar cracking was studied. The pyrolysis experiments were realized at temperatures ranging from 650 °C to 850 °C aimed at maximizingmore » of the amount of the gas product and reducing its tar content. Distribution of tetrapak into the product yields at different conditions was obtained. The presence of H{sub 2}, CO, CH{sub 4}, CO{sub 2} and light hydrocarbons, HCx, in the gas product was observed. The Aluminum foil was easily separated from the solid product. The rest part of char was characterized by proximate and elemental analysis and calorimetric measurements. The total organic carbon in the tar product was estimated by elemental analysis of tars. Two types of catalysts (dolomite and red clay marked AFRC) were used for catalytic thermal tar decomposition. Three series of experiments (without catalyst in a secondary cracking reactor, with dolomite and with AFRC) at temperatures of 650, 700, 750, 800 and 850 °C were carried out. Both types of catalysts have significantly affected the content of tars and other components in pyrolytic gases. The effect of catalyst on the tetrapack distribution into the product yield on the composition of gas and on the total organic carbon in the tar product is presented in this work.« less

Pyrolysis of aseptic packages (tetrapak) in a laboratory screw type reactor and secondary thermal/catalytic tar decomposition.

PubMed

Haydary, J; Susa, D; Dudáš, J

2013-05-01

Pyrolysis of aseptic packages (tetrapak cartons) in a laboratory apparatus using a flow screw type reactor and a secondary catalytic reactor for tar cracking was studied. The pyrolysis experiments were realized at temperatures ranging from 650 °C to 850 °C aimed at maximizing of the amount of the gas product and reducing its tar content. Distribution of tetrapak into the product yields at different conditions was obtained. The presence of H2, CO, CH4, CO2 and light hydrocarbons, HCx, in the gas product was observed. The Aluminum foil was easily separated from the solid product. The rest part of char was characterized by proximate and elemental analysis and calorimetric measurements. The total organic carbon in the tar product was estimated by elemental analysis of tars. Two types of catalysts (dolomite and red clay marked AFRC) were used for catalytic thermal tar decomposition. Three series of experiments (without catalyst in a secondary cracking reactor, with dolomite and with AFRC) at temperatures of 650, 700, 750, 800 and 850 °C were carried out. Both types of catalysts have significantly affected the content of tars and other components in pyrolytic gases. The effect of catalyst on the tetrapack distribution into the product yield on the composition of gas and on the total organic carbon in the tar product is presented in this work. Copyright © 2013 Elsevier Ltd. All rights reserved.

Synthesis and characterization of nanoscale molybdenum sulfide catalysts by controlled gas phase decomposition of Mo(CO){sub 6} and H{sub 2}S

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

Close, M.R.; Petersen, J.L.; Kugler, E.L.

1999-04-05

Molybdenum sulfide catalysts with surface areas ranging from 16 to 120 m{sup 2}/g were prepared by the thermal decomposition of Mo(CO){sub 6} and H{sub 2}S vapors in a specially designed tubular reactor system. The gas phase decomposition (GPD) reactions performed at 500--1100 C produced only MoS{sub 2} when excess H{sub 2}S was used. The optimum temperature range for the high-yield production of MoS{sub 2} was from 500 to 700 C. By controlling the decomposition temperature, the Mo(CO){sub 6} partial pressure, or the inert gas flow rate, the surface area, oxidation state, chemical composition, and the grain size of the molybdenummore » sulfide product(s) were modified. At reactor temperatures between 300 and 400 C, lower valent molybdenum sulfide materials, which were sulfur deficient relative to MoS{sub 2}, were obtained with formal molybdenum oxidation states intermediate to those found for Chevrel phase compounds, M{prime}Mo{sub 6}S{sub 8} (M{prime} = Fe, Ni, Co) and MoS{sub 2}. By lowering the H{sub 2}S flow rate used for the GPD reaction at 1000 C, mixtures containing variable amounts of MoS{sub 2} and Mo{sub 2}S{sub 3} were produced. Thus, through the modification of critical reactor parameters used for these GPD reactions, fundamental material properties were controlled.« less

Adsorption of thiophene on silica-supported Mo clusters

NASA Astrophysics Data System (ADS)

Komarneni, M.; Kadossov, E.; Justin, J.; Lu, M.; Burghaus, U.

2010-07-01

The adsorption/decomposition kinetics/dynamics of thiophene has been studied on silica-supported Mo and MoS x clusters. Two-dimensional cluster formation at small Mo exposures and three-dimensional cluster growth at larger exposures would be consistent with the Auger electron spectroscopy (AES) data. Thermal desorption spectroscopy (TDS) indicates two reaction pathways. H 4C 4S desorbs molecularly at 190-400 K. Two TDS features were evident and could be assigned to molecularly on Mo sites, and S sites adsorbed thiophene. Assuming a standard preexponential factor (ν = 1 × 10 13/s) for first-order kinetics, the binding energies for adsorption on Mo (sulfur) sites amount to 90 (65) kJ/mol for 0.4 ML Mo exposure and 76 (63) kJ/mol for 2 ML Mo. Thus, smaller clusters are more reactive than larger clusters for molecular adsorption of H 4C 4S. The second reaction pathway, the decomposition of thiophene, starts at 250 K. Utilizing multimass TDS, H 2, H 2S, and mostly alkynes are detected in the gas phase as decomposition products. H 4C 4S bond activation results in partially sulfided Mo clusters as well as S and C residuals on the surface. S and C poison the catalyst. As a result, with an increasing number of H 4C 4S adsorption/desorption cycles, the uptake of molecular thiophene decreases as well as the H 2 and H 2S production ceases. Thus, silica-supported sulfided Mo clusters are less reactive than metallic clusters. The poisoned catalyst can be partially reactivated by annealing in O 2. However, Mo oxides also appear to form, which passivate the catalyst further. On the other hand, while annealing a used catalyst in H/H 2, it is poisoned even more (i.e., the S AES signal increases). By means of adsorption transients, the initial adsorption probability, S0, of C 4H 4S has been determined. At thermal impact energies ( Ei = 0.04 eV), S0 for molecular adsorption amounts to 0.43 ± 0.03 for a surface temperature of 200 K. S0 increases with Mo cluster size, obeying the capture zone model. The temperature dependence of S0( Ts) consists of two regions consistent with molecular adsorption of thiophene at low temperatures and its decomposition above 250 K. Fitting S0( Ts) curves allows one to determine the bond activation energy for the first elementary decomposition step of C 4H 4S, which amounts to (79 ± 2) kJ/mol and (52 ± 4) kJ/mol for small and large Mo clusters, respectively. Thus, larger clusters are more active for decomposing C 4H 4S than are smaller clusters.

Report of 1,000 Hour Catalyst Longevity Evaluation

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

Daniel M. Ginosar

2009-06-01

This report presents the results of a 1,000 hour, high-pressure, catalyst longevity test for the decomposition of concentrated sulfuric acid. The reaction is used for both the sulfur-iodine (S-I) cycle and hybrid sulfur cycle. By the time of the delivery date of April 17, 2009, for project milestone no. 2NIN07TC050114, the 1% Pt/TiO2 catalyst had been in the reaction environment for 658 hours. During the first 480 hours of testing, the catalyst activity provided stable, near-equilibrium yields of 46.8% SO2 and 22.8% O2. However, product yields declined at sample exposure times >480 hours. At 658 hours of operation, catalyst activitymore » (based on oxygen yield) declined to 57% relative to the stable period of catalyst activity. Thus, as of April 17, this catalyst did not provide the desired stability level of <10% degradation per 1,000 hours. The experiment was terminated on April 27, after 792 hours, when a fitting failed and the catalyst was displaced from the reactor such that the sample could not be recovered. Oxygen conversion at the end of the experiment was 12.5% and declining, suggesting that at that point, catalyst activity had decreased to 54% of the initial level.« less

Alkane oxidation with porphyrins and metal complexes thereof having haloalkyl side chains

DOEpatents

Wijesekera, T.; Lyons, J.E.; Ellis, P.E. Jr.; Bhinde, M.V.

1998-06-23

Transition metal complexes of meso-haloalkylporphyrins are disclosed, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides. 7 figs.

Biodiesel synthesis using calcined layered double hydroxide catalysts

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

Schumaker, J. Link; Crofcheck, Czarena; TAckett, S. Adam

2008-01-01

The catalytic properties of calcined Li-Al, Mg-Al and Mg-Fe layered double hydroxides (LDHs) were examined in two transesterification reactions, namely, the reaction of glyceryl tributyrate with methanol, and the reaction of soybean oil with methanol. While the Li-Al catalysts showed high activity in these reactions at the reflux temperature of methanol, the Mg-Fe and Mg-Al catalysts exhibited much lower methyl ester yields. CO2 TPD measurements revealed the presence of sites of weak, medium and strong basicity on both Mg-Al and Li-Al catalysts, the latter showing higher concentrations of medium and strong base sites; by implication, these are the main sitesmore » active in transesterification catalyzed by calcined Li-Al LDHs. Maximum activity was observed for the Li-Al catalysts when a calcination temperature of 450-500 aC was applied, corresponding to decomposition of the layered double hydroxide to the mixed oxide without formation of crystalline lithium aluminate phases.« less

A facile self-assembly approach to prepare palladium/carbon nanotubes catalyst for the electro-oxidation of ethanol

NASA Astrophysics Data System (ADS)

Wen, Cuilian; Zhang, Xinyuan; Wei, Ying; Zhang, Teng; Chen, Changxin

2018-02-01

A facile self-assembly approach is reported to prepare palladium/carbon nanotubes (Pd/CNTs) catalyst for the electro-oxidation of ethanol. In this method, the Pd-oleate/CNTs was decomposed into the Pd/CNTs at an optimal temperature of 195 °C in air, in which no inert gas is needed for the thermal decomposition process due to the low temperature used and the decomposed products are also environmental friendly. The prepared Pd/CNTs catalyst has a high metallic Pd0 content and the Pd particles in the catalyst are disperse, uniform-sized with an average size of ˜2.1 nm, and evenly distributed on the CNTs. By employing our strategy, the problems including the exfoliation of the metal particles from the CNTs and the aggregation of the metal particles can be solved. Comparing with the commercial Pd/C one, the prepared Pd/CNTs catalyst exhibits a much higher electrochemical activity and stability for the electro-oxidation of ethanol in the direct ethanol fuel cells.

Effect of Ni-Co Ternary Molten Salt Catalysts on Coal Catalytic Pyrolysis Process

NASA Astrophysics Data System (ADS)

Cui, Xin; Qi, Cong; Li, Liang; Li, Yimin; Li, Song

2017-08-01

In order to facilitate efficient and clean utilization of coal, a series of Ni-Co ternary molten salt crystals are explored and the catalytic pyrolysis mechanism of Datong coal is investigated. The reaction mechanisms of coal are achieved by thermal gravimetric analyzer (TGA), and a reactive kinetic model is constructed. The microcosmic structure and macerals are observed by scanning electron microscope (SEM). The catalytic effects of ternary molten salt crystals at different stages of pyrolysis are analyzed. The experimental results show that Ni-Co ternary molten salt catalysts have the capability to bring down activation energy required by pyrolytic reactions at its initial phase. Also, the catalysts exert a preferable catalytic action on macromolecular structure decomposition and free radical polycondensation reactions. Furthermore, the high-temperature condensation polymerization is driven to decompose further with a faster reaction rate by the additions of Ni-Co ternary molten salt crystal catalysts. According to pyrolysis kinetic research, the addition of catalysts can effectively decrease the activation energy needed in each phase of pyrolysis reaction.

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.

Research on catalysts for long-life closed-cycle CO2 laser oaperation

NASA Technical Reports Server (NTRS)

Sidney, Barry D.; Schryer, David R.; Upchurch, Billy T.; Hess, Robert V.; Wood, George M.

1987-01-01

Long-life, closed-cycle operation of pulsed CO2 lasers requires catalytic CO-O2 recombination both to remove O2, which is formed by discharge-induced CO2 decomposition, and to regenerate CO2. Platinum metal on a tin-oxide substrate (Pt/SnO2) has been found to be an effective catalyst for such recombination in the desired temperature range of 25 to 100 C. This paper presents a description of ongoing research at NASA-Langley on Pt/SnO2 catalyzed CO-O2 recombination. Included are studies with rare-isotope gases since rare-isotope CO2 is desirable as a laser gas for enhanced atmospheric transmission. Results presented include: (1) the effects of various catalyst pretreatment techniques on catalyst efficiency; (2) development of a technique, verified in a 30-hour test, to prevent isotopic scrambling when C(O-18) and (O-18)2 are reacted in the presence of a common-isotope Pt/Sn(O-16)2 catalyst; and (3) development of a mathematical model of a laser discharge prior to catalyst introduction.

Effect of K loadings on nitrate formation/decomposition and on NOx storage performance of K-based NOx storage-reduction catalysts

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

Kim, Do Heui; Mudiyanselage, Kumudu K.; Szanyi, Janos

2013-10-25

We have investigated nitrate formation and decomposition processes, and measured NOx storage performance on Pt-K2O/Al2O3 catalysts as a function of potassium loading. After NO2 adsorption at room temperature, ionic and bidentate nitrates were observed by fourier transform infra-red (FTIR) spectroscopy. The ratio of the former to the latter species increased with increasing potassium loading up to 10 wt%, and then stayed almost constant with additional K, demonstrating a clear dependence of loading on the morphology of the K species. Although both K2O(10)/Al2O3 and K2O(20)/Al2O3 samples have similar nitrate species after NO2 adsorption, the latter has more thermally stable nitrate speciesmore » as evidenced by FTIR and NO2 temperature programmed desorption (TPD) results. With regard to NOx storage performance, the temperature of maximum NOx uptake (Tmax) is 573 K up to a potassium loading of 10 wt%. As the potassium loading increases from 10 wt% to 20 wt%, Tmax shifted from 573 K to 723 K. Moreover, the amount of NO uptake (38 cm3 NOx/g catal) at Tmax increased more than three times, indicating that efficiency of K in storing NOx is enhanced significantly at higher temperature, in good agreement with the NO2 TPD and FTIR results. Thus, a combination of characterization and NOx storage performance results demonstrates an unexpected effect of potassium loading on nitrate formation and decomposition processes; results important for developing Pt-K2O/Al2O3 for potential applications as high temperature NOx storage-reduction catalysts.« less

Control of Effluent Gases from Solid Waste Processing Using Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Fisher, John; Cinke, Martin; Wignarajab, Kanapathipillai

2005-01-01

One of the major problems associated with solid waste processing technologies is the release of effluent gases and contaminants that are in gaseous formed from the processes. A number of other gases, in particular NO(x), SO2, NH3, Hydrocarbons (e.g. CH4) do present hazards to the crew in space habitats. Reduction of mass, power, volume and resupply can be achieved by using catalyst impregnated carbon nanotubes as compared to other catalytic systems. The development and characterization of an innovative approach for the control and elimination of gaseous toxins using single walled carbon nanotubes (SWNTs) promise superior performance over conventional approaches. This is due to the ability to direct the selective uptake of gaseous species based on their controllable pore size, high adsorptive capacity and the effectiveness of carbon nanotubes as catalyst supports for gaseous conversion. For example, SWNTs have high adsorptive capacity for NO and the adsorbed NO can be decomposed to N2 and O2 . Experimental results showing the decomposition of NO on metal impregnated carbon nanotubes is presented. Equivalent System Mass (ESM) comparisons are made of the existing TCCS systems with the carbon nanotube technology for removing NO(x). The potential for methane decomposition using carbon nanotubes catalysts is also discussed.

A Silica-Supported Iron Oxide Catalyst Capable of Activating Hydrogen Peroxide at Neutral pH Values

PubMed Central

Pham, Anh Le-Tuan; Lee, Changha; Doyle, Fiona M.; Sedlak, David L.

2009-01-01

Iron oxides catalyze the conversion of hydrogen peroxide (H2O2) into oxidants capable of transforming recalcitrant contaminants. Unfortunately, the process is relatively inefficient at circumneutral pH values due to competing reactions that decompose H2O2 without producing oxidants. Silica- and alumina-containing iron oxides prepared by sol-gel processing of aqueous solutions containing Fe(ClO4)3, AlCl3 and tetraethyl orthosilicate efficiently catalyzed the decomposition of H2O2 into oxidants capable of transforming phenol at circumneutral pH values. Relative to hematite, goethite and amorphous FeOOH, the silica-iron oxide catalyst exhibited a stoichiometric efficiency, defined as the number of moles of phenol transformed per mole of H2O2 consumed, that was 10 to 40 times higher than that of the iron oxides. The silica-alumina-iron oxide catalyst had a stoichiometric efficiency that was 50 to 80 times higher than that of the iron oxides. The significant enhancement in oxidant production is attributable to the interaction of Fe with Al and Si in the mixed oxides, which alters the surface redox processes, favoring the production of strong oxidants during H2O2 decomposition. PMID:19943668

Studies of Homogeneous and Heterogeneous Hydrazine Decomposition for Monopropellant Propulsion Systems

DTIC Science & Technology

1975-07-25

H WISE D M GOLDEN B J WOOD 0. PERFORMING ORGANIZATION NAME AND ADDRESS IO. -’i)GRAM -LLUENT PROJECT, TASK AREA A WORK UNIT NUMBERSSTANFORD RESEARCH...are retained by the catalyst after exposure to reactants. In these experiments the catalyst was placed in a microreactor apparatus, and a helium...intermediates involved in the reaction are adsorbed on the surface. Following is such a general scheme: k a N2H4(gas) +--4 X + Y (1)2 4 k s s d k 1 X - Pr.ducts

DFT study of hydrogen production from formic acid decomposition on Pd-Au alloy nanoclusters

NASA Astrophysics Data System (ADS)

Liu, D.; Gao, Z. Y.; Wang, X. C.; Zeng, J.; Li, Y. M.

2017-12-01

Recently, it has been reported that the hydrogen production rate of formic acid decomposition can be significantly increased using Pd-Au binary alloy nano-catalysts [Wang et al. J. Mater. Chem. A 1 (2013) 12721-12725]. To explain the reaction mechanism of this alloy catalysis method, formic acid decomposition reactions on pure Pd and Pd-Au alloy nanoclusters are studied via density functional theory simulations. The simulation results indicate that the addition of inert element Au would not influence formic acid decomposition on Pd surface sites of Pd-Au alloy nanoclusters. On the other hand, the existence of Au surface sites brings relative weak hydrogen atom adsorption. On Pd-Au alloy nanoclusters, the dissociated hydrogen atoms from formic acid are easier to combine as hydrogen molecules than that on pure Pd clusters. Via the synergetic effect between Pd and Au, both formic acid decomposition and hydrogen production are events with large probability, which eventually results in high hydrogen production rate.

Noncrystalline structure of Ni-P nanoparticles prepared by liquid pulse discharge.

PubMed

Tan, Yuanyuan; Yu, Hongying; Wu, Zhonghua; Yang, Bin; Gong, Yu; Yan, Shi; Du, Rong; Chen, Zhongjun; Sun, Dongbai

2015-03-01

Noncrystalline nickel phosphide (Ni-P) nanoparticles have drawn great attention due to their high potential as catalysts. However, the structure of noncrystalline Ni-P nanoparticles is still unknown, which may shed light on explaining the catalysis mechanism of the Ni-P nanoparticles. In this paper, noncrystalline Ni-P nanoparticles were synthesized. Their morphology, particle size, element contents, local atomic structures, as well as the catalysis in the thermal decomposition of ammonium perchlorate were studied. The results demonstrate that the as-prepared Ni-P nanoparticles are spherical with an average diameter of about 13.5 nm. The Ni and P contents are, respectively, 78.15% and 21.85%. The noncrystalline nature of the as-prepared Ni-P nanoparticles can be attributed to cross-linkage between P-doping f.c.c.-like Ni centers and Ni3P-like P centers. The locally ordered Ni centers and P centers are the nuclei sites, which can explain well the origin of initial nuclei to form the crystalline phases after high-temperature annealing. The starting temperature of high-temperature decomposition of ammonium perchlorate was found having a significant decrease in the presence of the noncrystalline Ni-P nanoparticles. Therefore, the as-prepared noncrystalline Ni-P nanoparticles can be used as a potential catalyst in the thermal decomposition of ammonium perchlorate.

Decomposition mechanism of chromite in sulfuric acid-dichromic acid solution

NASA Astrophysics Data System (ADS)

Zhao, Qing; Liu, Cheng-jun; Li, Bao-kuan; Jiang, Mao-fa

2017-12-01

The sulfuric acid leaching process is regarded as a promising, cleaner method to prepare trivalent chromium products from chromite; however, the decomposition mechanism of the ore is poorly understood. In this work, binary spinels of Mg-Al, Mg-Fe, and Mg-Cr in the powdered and lump states were synthesized and used as raw materials to investigate the decomposition mechanism of chromite in sulfuric acid-dichromic acid solution. The leaching yields of metallic elements and the changes in morphology of the spinel were studied. The experimental results showed that the three spinels were stable in sulfuric acid solution and that dichromic acid had little influence on the decomposition behavior of the Mg-Al spinel and Mg-Fe spinel because Mg2+, Al3+, and Fe3+ in spinels cannot be oxidized by Cr6+. However, in the case of the Mg-Cr spinel, dichromic acid substantially promoted the decomposition efficiency and functioned as a catalyst. The decomposition mechanism of chromite in sulfuric acid-dichromic acid solution was illustrated on the basis of the findings of this study.

Relationship between the catalytic properties of the products of the oxidative thermolysis of certain complexes and the porous structures of samples in the oxidation reactions of volatile organic compounds

NASA Astrophysics Data System (ADS)

Semushina, Yu. P.; Pechenyuk, S. I.; Kuzmich, L. F.; Knyazeva, A. I.

2017-01-01

The rate of the gas-phase oxidation of ethanol, 2-propanol, acetone, ethyl acetate, dioxane, and benzene with atmospheric oxygen is studied on surfaces of bimetallic oxide catalysts Co-Fe, Cu-Fe, Cr-Co, and Ni-Fe, prepared via thermal decomposition of double complex compounds in air. It is found that the rate of oxidation of volatile compounds depends on the volume of the transient pores in the catalyst sample. The rate of oxidation on the same catalyst at 350°C depends on the nature of the substance in the order: acetone > ethyl acetate > ethanol > propanol > dioxane, benzene.

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

Carbon-free H2 production from ammonia triggered at room temperature with an acidic RuO2/γ-Al2O3 catalyst.

PubMed

Nagaoka, Katsutoshi; Eboshi, Takaaki; Takeishi, Yuma; Tasaki, Ryo; Honda, Kyoko; Imamura, Kazuya; Sato, Katsutoshi

2017-04-01

Ammonia has been suggested as a carbon-free hydrogen source, but a convenient method for producing hydrogen from ammonia with rapid initiation has not been developed. Ideally, this method would require no external energy input. We demonstrate hydrogen production by exposing ammonia and O 2 at room temperature to an acidic RuO 2 /γ-Al 2 O 3 catalyst. Because adsorption of ammonia onto the catalyst is exothermic, the catalyst bed is rapidly heated to the catalytic ammonia autoignition temperature, and subsequent oxidative decomposition of ammonia produces hydrogen. A differential calorimeter combined with a volumetric gas adsorption analyzer revealed a large quantity of heat evolved both with chemisorption of ammonia onto RuO 2 and acidic sites on the γ-Al 2 O 3 and with physisorption of multiple ammonia molecules.

Palladium-tin catalysts for the direct synthesis of H 2O 2 with high selectivity

DOE PAGES

Freakley, Simon J.; He, Qian; Harrhy, Jonathan H.; ...

2016-02-25

The direct synthesis of hydrogen peroxide (H 2O 2 ) from H 2 and O 2 represents a potentially atom-efficient alternative to the current industrial indirect process. We show that the addition of tin to palladium catalysts coupled with an appropriate heat treatment cycle switches off the sequential hydrogenation and decomposition reactions, enabling selectivities of >95% toward H 2O 2 . This effect arises from a tin oxide surface layer that encapsulates small Pd-rich particles while leaving larger Pd-Sn alloy particles exposed. In conclusion, we show that this effect is a general feature for oxide-supported Pd catalysts containing an appropriatemore » second metal oxide component, and we set out the design principles for producing high-selectivity Pd-based catalysts for direct H 2O 2 production that do not contain gold.« less

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

Enhanced photocatalytic activity of ZnO/CuO nanocomposite for the degradation of textile dye on visible light illumination.

PubMed

Saravanan, R; Karthikeyan, S; Gupta, V K; Sekaran, G; Narayanan, V; Stephen, A

2013-01-01

The photocatalytic degradation of organic dyes such as methylene blue and methyl orange in the presence of various percentages of composite catalyst under visible light irradiation was carried out. The catalyst ZnO nanorods and ZnO/CuO nanocomposites of different weight ratios were prepared by new thermal decomposition method, which is simple and cost effective. The prepared catalysts were characterized by different techniques such as X-ray diffraction, transmission electron microscopy, field emission scanning electron microscopy, Fourier transform infrared spectroscopy and UV-visible absorption spectroscopy. Further, the most photocatalytically active composite material was used for degradation of real textile waste water under visible light illumination. The irradiated samples were analysed by total organic carbon and chemical oxygen demand. The efficiency of the catalyst and their photocatalytic mechanism has been discussed in detail. Copyright © 2012 Elsevier B.V. All rights reserved.

Carbon-free H2 production from ammonia triggered at room temperature with an acidic RuO2/γ-Al2O3 catalyst

PubMed Central

Nagaoka, Katsutoshi; Eboshi, Takaaki; Takeishi, Yuma; Tasaki, Ryo; Honda, Kyoko; Imamura, Kazuya; Sato, Katsutoshi

2017-01-01

Ammonia has been suggested as a carbon-free hydrogen source, but a convenient method for producing hydrogen from ammonia with rapid initiation has not been developed. Ideally, this method would require no external energy input. We demonstrate hydrogen production by exposing ammonia and O2 at room temperature to an acidic RuO2/γ-Al2O3 catalyst. Because adsorption of ammonia onto the catalyst is exothermic, the catalyst bed is rapidly heated to the catalytic ammonia autoignition temperature, and subsequent oxidative decomposition of ammonia produces hydrogen. A differential calorimeter combined with a volumetric gas adsorption analyzer revealed a large quantity of heat evolved both with chemisorption of ammonia onto RuO2 and acidic sites on the γ-Al2O3 and with physisorption of multiple ammonia molecules. PMID:28508046

Catalytic Decomposition of Hydroxylammonium Nitrate Ionic Liquid: Enhancement of NO Formation.

PubMed

Chambreau, Steven D; Popolan-Vaida, Denisia M; Vaghjiani, Ghanshyam L; Leone, Stephen R

2017-05-18

Hydroxylammonium nitrate (HAN) is a promising candidate to replace highly toxic hydrazine in monopropellant thruster space applications. The reactivity of HAN aerosols on heated copper and iridium targets was investigated using tunable vacuum ultraviolet photoionization time-of-flight aerosol mass spectrometry. The reaction products were identified by their mass-to-charge ratios and their ionization energies. Products include NH 3 , H 2 O, NO, hydroxylamine (HA), HNO 3 , and a small amount of NO 2 at high temperature. No N 2 O was detected under these experimental conditions, despite the fact that N 2 O is one of the expected products according to the generally accepted thermal decomposition mechanism of HAN. Upon introduction of iridium catalyst, a significant enhancement of the NO/HA ratio was observed. This observation indicates that the formation of NO via decomposition of HA is an important pathway in the catalytic decomposition of HAN.

Nanodiamonds as pH-switchable oxidation and reduction catalysts with enzyme-like activities for immunoassay and antioxidant applications.

PubMed

Chen, T M; Tian, X M; Huang, L; Xiao, J; Yang, G W

2017-10-19

Nanodiamonds (NDs) have recently become a focus of interest from the viewpoints of both science and technology. Their intriguing properties make them suitable as biologically active substrates, in biosensor applications as well as diagnostic and therapeutic biomedical imaging probes. Here, we demonstrate that NDs, as oxidation and reduction catalysts, possess intrinsic enzyme mimetic properties of oxidase, peroxidase and catalase, and these behaviors can be switched by modulating the pH value. NDs not only catalyze the reduction of oxygen (O 2 ) and hydrogen peroxide (H 2 O 2 ) at acidic pH, but also catalyze the dismutation decomposition of H 2 O 2 to produce O 2 at alkaline pH. It was proposed that the molecular mechanism of their peroxidase-like activity is electron-transfer acceleration, the source of which is likely derived from oxygen containing functional groups on their surface. Based on the color reaction, a nanodiamond-based enzyme linked immunosorbent assay (ELISA) was established for the detection of immunoglobulin G (IgG). Surprisingly, NDs display an excellent antioxidant activity due to the protective effect against H 2 O 2 -induced cellular oxidative damage. These findings make NDs a promising enzyme mimetic candidate and expand their applications in biocatalysis, bioassays and nano-biomedicine.

Effect of dry torrefaction on kinetics of catalytic pyrolysis of sugarcane bagasse

NASA Astrophysics Data System (ADS)

Daniyanto, Sutijan, Deendarlianto, Budiman, Arief

2015-12-01

Decreasing world reserve of fossil resources (i.e. petroleum oil, coal and natural gas) encourage discovery of renewable resources as subtitute for fossil resources. Biomass is one of the main natural renewable resources which is promising resource as alternate resources to meet the world's energy needs and raw material to produce chemical platform. Conversion of biomass, as source of energy, fuel and biochemical, is conducted using thermochemical process such as pyrolysis-gasification process. Pyrolysis step is an important step in the mechanism of pyrolysis - gasification of biomass. The objective of this study is to obtain the kinetic reaction of catalytic pyrolysis of dry torrified sugarcane bagasse which used Ca and Mg as catalysts. The model of kinetic reaction is interpreted using model n-order of single reaction equation of biomass. Rate of catalytic pyrolysis reaction depends on the weight of converted biomass into char and volatile matters. Based on TG/DTA analysis, rate of pyrolysis reaction is influenced by the composition of biomass (i.e. hemicellulose, cellulose and lignin) and inorganic component especially alkali and alkaline earth metallic (AAEM). From this study, it has found two equations rate of reaction of catalytic pyrolysis in sugarcane bagasse using catalysts Ca and Mg. First equation is equation of pyrolysis reaction in rapid zone of decomposition and the second equation is slow zone of decomposition. Value of order reaction for rapid decomposition is n > 1 and for slow decomposition is n<1. Constant and order of reactions for catalytic pyrolysis of dry-torrified sugarcane bagasse with presence of Ca tend to higher than that's of presence of Mg.

A quantum chemical study of the decomposition of Keggin-structured heteropolyacids.

PubMed

Janik, Michael J; Bardin, Billy B; Davis, Robert J; Neurock, Matthew

2006-03-09

Heterpolyacids (HPAs) demonstrate catalytic activity for oxidative and acid-catalyzed hydrocarbon conversion processes. Deactivation and thermal instability, however, have prevented their widespread use. Herein, ab initio density functional theory is used to study the thermal decomposition of the Keggin molecular HPA structure through the desorption of constitutional water molecules. The overall reaction energy and activation barrier are computed for the overall reaction HnXM12O40-->Hn-2XM12O39+H2O. and subsequently used to predict the effect of HPA composition on thermal stability. For example, the desorption of a constitutional water molecule is found to be increasingly endothermic in the order silicomolybdic acid (H4SiMo12O40)

An optimization study of PtSn/C catalysts applied to direct ethanol fuel cell: Effect of the preparation method on the electrocatalytic activity of the catalysts

NASA Astrophysics Data System (ADS)

Almeida, T. S.; Palma, L. M.; Leonello, P. H.; Morais, C.; Kokoh, K. B.; De Andrade, A. R.

2012-10-01

The aim of this work was to perform a systematic study of the parameters that can influence the composition, morphology, and catalytic activity of PtSn/C nanoparticles and compare two different methods of nanocatalyst preparation, namely microwave-assisted heating (MW) and thermal decomposition of polymeric precursors (DPP). An investigation of the effects of the reducing and stabilizing agents on the catalytic activity and morphology of Pt75Sn25/C catalysts prepared by microwave-assisted heating was undertaken for optimization purposes. The effect of short-chain alcohols such as ethanol, ethylene glycol, and propylene glycol as reducing agents was evaluated, and the use of sodium acetate and citric acid as stabilizing agents for the MW procedure was examined. Catalysts obtained from propylene glycol displayed higher catalytic activity compared with catalysts prepared in ethylene glycol. Introduction of sodium acetate enhanced the catalytic activity, but this beneficial effect was observed until a critical acetate concentration was reached. Optimization of the MW synthesis allowed for the preparation of highly dispersed catalysts with average sizes lying between 2.0 and 5.0 nm. Comparison of the best catalyst prepared by MW with a catalyst of similar composition prepared by the polymeric precursors method showed that the catalytic activity of the material can be improved when a proper condition for catalyst preparation is achieved.

Coupling molecular catalysts with nanostructured surfaces for efficient solar fuel production

NASA Astrophysics Data System (ADS)

Jin, Tong

Solar fuel generation via carbon dioxide (CO2) reduction is a promising approach to meet the increasing global demand for energy and to minimize the impact of energy consumption on climate change. However, CO2 is thermodynamically stable; its activation often requires the use of appropriate catalysts. In particular, molecular catalysts with well-defined structures and tunability have shown excellent activity in photochemical CO2 reduction. These homogenous catalysts, however, suffer from poor stability under photochemical conditions and difficulty in recycling from the reaction media. Heterogenized molecular catalysts, particularly those prepared by coupling molecular catalysts with solid-state surfaces, have attracted more attention in recent years as potential solutions to address the issues associated with molecular catalysts. In this work, solar CO2 reduction is investigated using systems coupling molecular catalysts with robust nanostructured surfaces. In Chapter 2, heterogenization of macrocyclic cobalt(III) and nickel (II) complexes on mesoporous silica surface was achieved by different methods. Direct ligand derivatization significantly lowered the catalytic activity of Co(III) complex, while grafting the Co(III) complex onto silica surface through Si-O-Co linkage resulted in hybrid catalysts with excellent activity in CO2 reduction in the presence of p-terphenyl as a molecular photosensitizer. An interesting loading effect was observed, in which the optimal activity was achieved at a medium Co(III) surface density. Heterogenization of the Ni(II) complex on silica surface has also been implemented, the poor photocatalytic activity of the hybrid catalyst can be attributed to the intrinsic nature of the homogeneous analogue. This study highlighted the importance of appropriate linking strategies in preparing functional heterogenized molecular catalysts. Coupling molecular complexes with light-harvesting surfaces could avoid the use of expensive molecular photosensitizers. In Chapter 3, effective coupling of the macrocyclic Co(III) complex with titanium dioxide (TiO¬2) nanoparticles was achieved by two deposition methods. The synthesized hybrid photocatalysts were thoroughly characterized with a variety of techniques. Upon UV light irradiation, photoexcited electrons in TiO2 nanoparticles were transferred to the surface Co(III) catalyst for CO2 reduction. Production of carbon monoxide (CO) from CO2 was confirmed by isotope labeling combined with infrared spectroscopy. Deposition of the Co(III) catalyst through Ti-O-Co linkages was essential for the photo-induced electron transfer and CO2-reduction activity using the hybrid photocatalysts. In Chapter 4, molecular Re(I) and Co(II) catalysts were coupled with silicon-based photoelectrodes, including a silicon nanowire (SiNW) photoelectrode, to achieve photoelectrochemical CO2 reduction. Photovoltages between 300-600 mV were obtained using the molecular catalysts on the silicon photoelectrodes. SiNWs exhibited enhanced properties, including significantly higher photovoltages than a planar silicon photoelectrode, the ability to protect one of the molecular catalysts from photo-induced decomposition, and excellent selectivity towards CO production in CO2 reduction. Recent theoretical and experimental work have demonstrated low-energy, binuclear pathways for CO2-to-CO conversion using several molecular catalysts. In such binuclear pathways, two metal centers work cooperatively to achieve two-electron CO2 reduction. Chapter 5 describes our effort to promote the binuclear pathway by grafting the molecular Co(III) catalyst onto silica surfaces. Different linking strategies were attempted to achieve this goal by planting the surface Co(III) sites in close proximity.

Application of sodium carbonate prevents sulphur poisoning of catalysts in automated total mercury analysis

NASA Astrophysics Data System (ADS)

McLagan, David S.; Huang, Haiyong; Lei, Ying D.; Wania, Frank; Mitchell, Carl P. J.

2017-07-01

Analysis of high sulphur-containing samples for total mercury content using automated thermal decomposition, amalgamation, and atomic absorption spectroscopy instruments (USEPA Method 7473) leads to rapid and costly SO2 poisoning of catalysts. In an effort to overcome this issue, we tested whether the addition of powdered sodium carbonate (Na2CO3) to the catalyst and/or directly on top of sample material increases throughput of sulphur-impregnated (8-15 wt%) activated carbon samples per catalyst tube. Adding 5 g of Na2CO3 to the catalyst alone only marginally increases the functional lifetime of the catalyst (31 ± 4 g of activated carbon analyzed per catalyst tube) in relation to unaltered catalyst of the AMA254 total mercury analyzer (17 ± 4 g of activated carbon). Adding ≈ 0.2 g of Na2CO3 to samples substantially increases (81 ± 17 g of activated carbon) catalyst life over the unaltered catalyst. The greatest improvement is achieved by adding Na2CO3 to both catalyst and samples (200 ± 70 g of activated carbon), which significantly increases catalyst performance over all other treatments and enables an order of magnitude greater sample throughput than the unaltered samples and catalyst. It is likely that Na2CO3 efficiently sequesters SO2, even at high furnace temperatures to produce Na2SO4 and CO2, largely negating the poisonous impact of SO2 on the catalyst material. Increased corrosion of nickel sampling boats resulting from this methodological variation is easily resolved by substituting quartz boats. Overall, this variation enables an efficient and significantly more affordable means of employing automated atomic absorption spectrometry instruments for total mercury analysis of high-sulphur matrices.

N, S co-doped carbon spheres with highly dispersed CoO as non-precious metal catalyst for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Chen, Linlin; Guo, Xingpeng; Zhang, Guoan

2017-08-01

It is still a great challenge in preparing non-precious metal catalysts with high activity and long-term stability to substitute for precious metal catalysts for oxygen reduction reaction (ORR) in fuel cells. Herein, we report a novel and facile catalyst-N, S co-doped carbon spheres with highly dispersed CoO (CoO@NS-CSs), where biomass glucose spheres act as carbon precursor and H2S, NH3 derived from the decomposition of thiourea not only provide N, S sources but also can etch carbon spheres to produce nanoporous structure. CoO@NS-CSs catalyst exhibits excellent ORR activity with a high onset potential of 0.946 V vs. RHE (reversible hydrogen electrode) and a half-wave potential of 0.821 V vs. RHE through a four-electron pathway in alkaline solution, which is comparable to commercial Pt/C catalyst (onset potential: 0.926 V vs. RHE, half-wave potential: 0.827 V vs. RHE). Furthermore, both the long-term stability and methanol-tolerance of CoO@NS-CSs catalyst are superior to those of commercial Pt/C catalyst. The excellent ORR performance of CoO@NS-CSs catalyst can be attributed to its micro-mesopore structure, high specific surface area (667 m2 g-1), and highly dispersed CoO. This work manifests that the obtained CoO@NS-CSs catalyst is promising to be applied to fuel cells.

Macrokinetics of carbon nanotubes synthesis by the chemical vapor deposition method

NASA Astrophysics Data System (ADS)

Rukhov, Artem; Dyachkova, Tatyana; Tugolukov, Evgeny; Besperstova, Galina

2017-11-01

A new approach to studying and developing basic processes which take place on the surface of a metal catalyst during the thermal decomposition of carbonaceous substances in the carbon nanotubes synthesis by the chemical vapor deposition method was proposed. In addition, an analysis was made of the interrelationships between these thermal, diffusion, hydrodynamic and other synthesis processes. A strong effect of the catalyst regeneration stage on the stage of nanotube formation has been shown. Based on the developed approach, a mathematical model was elaborated. Comparison of the calculation and the experiment carried out with the NiO-MgO catalyst at propane flow rate of 50 mL/min (standard conditions) and ethanol flow rate 0.3 mL/min (liq.) has revealed a discrepancy of less than 10%.

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

Matsumura, Yukihiko; Nuessle, F.W.; Antal, M.J. Jr.

Recently, carbonaceous materials were proved to be effective catalysts for hazardous waste decomposition in supercritical water. Gasification of the carbonaceous catalyst itself is also expected, however, under supercritical conditions. Thus, it is essential to determine the gasification rate of the carbonaceous materials during this process to determine the active lifetime of the catalysts. For this purpose, the gasification characteristics of granular coconut shell activated carbon in supercritical water alone (600-650{degrees}C, 25.5-34.5 MPa) were investigated. The gasification rate at subatmospheric pressure agreed well with the gasification rate at supercritical conditions, indicating the same reaction mechanism. Methane generation under these conditions ismore » via pyrolysis, and thus is not affected by the water pressure. An iodine number increase of 25% was observed as a result of the supercritical water gasification.« less

In situ spectroscopic studies on vapor phase catalytic decomposition of dimethyl oxalate.

PubMed

Hegde, Shweta; Tharpa, Kalsang; Akuri, Satyanarayana Reddy; K, Rakesh; Kumar, Ajay; Deshpande, Raj; Nair, Sreejit A

2017-03-15

Dimethyl Oxalate (DMO) has recently gained prominence as a valuable intermediate for the production of compounds of commercial importance. The stability of DMO is poor and hence this can result in the decomposition of DMO under reaction conditions. The mechanism of DMO decomposition is however not reported and more so on catalytic surfaces. Insights into the mechanism of decomposition would help in designing catalysts for its effective molecular transformation. It is well known that DMO is sensitive to moisture, which can also be a factor contributing to its decomposition. The present work reports the results of decomposition of DMO on various catalytic materials. The materials studied consist of acidic (γ-Al 2 O 3 ), basic (MgO), weakly acidic (ZnAl 2 O 4 ) and neutral surfaces such as α-Al 2 O 3 and mesoporous precipitated SiO 2 . Infrared spectroscopy is used to identify the nature of adsorption of the molecule on the various surfaces. The spectroscopy study is done at a temperature of 200 °C, which is the onset of gas phase decomposition of DMO. The results indicate that the stability of DMO is lower than the corresponding acid, i.e. oxalic acid. It is also one of the products of decomposition. Spectroscopic data suggest that DMO decomposition is related to surface acidity and the extent of decomposition depends on the number of surface hydroxyl groups. Decomposition was also observed on α-Al 2 O 3 , which was attributed to the residual surface hydroxyl groups. DMO decomposition to oxalic acid was not observed on the basic surface (MgO).

Two-Dimensional Phosphorene-Derived Protective Layers on a Lithium Metal Anode for Lithium-Oxygen Batteries.

PubMed

Kim, Youngjin; Koo, Dongho; Ha, Seongmin; Jung, Sung Chul; Yim, Taeeun; Kim, Hanseul; Oh, Seung Kyo; Kim, Dong-Min; Choi, Aram; Kang, Yongku; Ryu, Kyoung Han; Jang, Minchul; Han, Young-Kyu; Oh, Seung M; Lee, Kyu Tae

2018-05-04

Lithium-oxygen (Li-O 2 ) batteries are desirable for electric vehicles because of their high energy density. Li dendrite growth and severe electrolyte decomposition on Li metal are, however, challenging issues for the practical application of these batteries. In this connection, an electrochemically active two-dimensional phosphorene-derived lithium phosphide is introduced as a Li metal protective layer, where the nanosized protective layer on Li metal suppresses electrolyte decomposition and Li dendrite growth. This suppression is attributed to thermodynamic properties of the electrochemically active lithium phosphide protective layer. The electrolyte decomposition is suppressed on the protective layer because the redox potential of lithium phosphide layer is higher than that of electrolyte decomposition. Li plating is thermodynamically unfavorable on lithium phosphide layers, which hinders Li dendrite growth during cycling. As a result, the nanosized lithium phosphide protective layer improves the cycle performance of Li symmetric cells and Li-O 2 batteries with various electrolytes including lithium bis(trifluoromethanesulfonyl)imide in N,N-dimethylacetamide. A variety of ex situ analyses and theoretical calculations support these behaviors of the phosphorene-derived lithium phosphide protective layer.

Atomic oxygen protective coating with resistance to undercutting at defect sites

NASA Technical Reports Server (NTRS)

Banks, Bruce A. (Inventor); Rutledge, Sharon K. (Inventor)

1994-01-01

Structures composed at least partially of an organic substrate may be protected from oxidation by applying a catalyst onto said substrate for promoting the combination of atomic oxygen to molecular oxygen. The structure may also be protected by applying both a catalyst and an atomic oxygen shielding layer onto the substrate. The structures to be protected include spacecraft surfaces.

Controlled Hydrogen Peroxide Decomposition for a Solid Oxide Fuel Cell (SOFC) Oxidant Source with a Microreactor Model

DTIC Science & Technology

2007-10-01

established assuming first order kinetics weighted via an inputted catalyst mass, Mcat (equation 2). catrxn MCk *−=22OHr (2) The...H2O2 (0-50%w/w) solution heat capacity(J/kg*K) M cat Mcat 0.03 Mass of Catalyst (g) Deffhh2o 7.85E-10 Average effective diffusivity of H2O2 into... Mcat *c Rate Law for Elementary 1st Order Irreversible Reaction (mol/((s*m^3)) r H2O rtb -rt Rate Law for Elementary 1st Order Irreversible Reaction

CVD Growth of Carbon Nanotubes: Structure, Catalyst, and Growth

NASA Technical Reports Server (NTRS)

Delzeit, Lance

2003-01-01

Carbon nanotubes (CNTs) exhibit extraordinary mechanical and unique electronic properties and hence have been receiving much attention in recent years for their potential in nanoelectronics, field emission devices, scanning probes, high strength composites and many more applications. Catalytic decomposition of hydrocarbon feedstock with the aid of supported transition metal catalysts - also known as chemical vapor deposition (CVD) - has become popular to produce single-walled and multi-walled nanotubes (SWNTs, MWNTs) and multiwalled nanofibers (MWNFs). The ability to grow CNTs on patterned substrates and in vertically aligned arrays, and the simplicity of the process, has made CVD growth of CNTs an attractive approach.

Catalyzed pyrolysis of grape and olive bagasse. Influence of catalyst type and chemical treatment

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

Encinar, J.M.; Beltran, F.J.; Ramiro, A.

1997-10-01

Catalyzed pyrolysis of grape and olive bagasse under different experimental conditions has been studied. Variables investigated were temperature and type and concentration of catalysts. Experiments were carried out in an isothermal manner. Products of pyrolysis are gases (H{sub 2}, CO, CO{sub 2}, and CH{sub 4}), liquids (methanol, acetone, furfurylic alcohol, phenol, furfural, naphthalene, and o-cresol), and solids (chars). Temperature is a significant variable, yielding increases of fixed carbon content, gases, and to a lesser extent, ash percentage. Catalyst presence also yields increases of solid phase content, but the amount of liquid components decrease. Among catalysts applied those of Fe andmore » Zn are the most advisable to obtain gases. Chemical treatment of bagasses with sulfuric or phosphoric acid washing leads to lower char yields, although fixed carbon content is higher and ash presence diminishes with respect to catalyst pyrolysis without chemical pretreatment. A pyrolysis kinetic study based on gas generation from thermal decomposition of residues has been carried out. From the model proposed, rate constants for the formation of each gas, reaction order of the catalyst, and activation energies were determined.« less

Effect of water vapor on NH3-NO/NO2 SCR performance of fresh and aged MnOx-NbOx-CeO2 catalysts.

PubMed

Chen, Lei; Si, Zhichun; Wu, Xiaodong; Weng, Duan; Wu, Zhenwei

2015-05-01

A MnOx-NbOx-CeO2 catalyst for low temperature selective catalytic reduction (SCR) of NOx with NH3 was prepared by a sol-gel method, and characterized by NH3-NO/NO2 SCR catalytic activity, NO/NH3 oxidation activity, NOx/NH3 TPD, XRD, BET, H2-TPR and in-situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS). The results indicate that the MnOx-NbOx-CeO2 catalyst shows excellent low temperature NH3-SCR activity in the temperature range of 150-300°C. Water vapor inhibits the low temperature activity of the catalyst in standard SCR due to the inhibition of NOx adsorption. As the NO2 content increases in the feed, water vapor does not affect the activity in NO2 SCR. Meanwhile, water vapor significantly enhances the N2 selectivity of the fresh and the aged catalysts due to its inhibition of the decomposition of NH4NO3 into N2O. Copyright © 2015. Published by Elsevier B.V.

A Tandem Catalyst with Multiple Metal Oxide Interfaces Produced by Atomic Layer Deposition.

PubMed

Ge, Huibin; Zhang, Bin; Gu, Xiaomin; Liang, Haojie; Yang, Huimin; Gao, Zhe; Wang, Jianguo; Qin, Yong

2016-06-13

Ideal heterogeneous tandem catalysts necessitate the rational design and integration of collaborative active sites. Herein, we report on the synthesis of a new tandem catalyst with multiple metal-oxide interfaces based on a tube-in-tube nanostructure using template-assisted atomic layer deposition, in which Ni nanoparticles are supported on the outer surface of the inner Al2 O3 nanotube (Ni/Al2 O3 interface) and Pt nanoparticles are attached to the inner surface of the outer TiO2 nanotube (Pt/TiO2 interface). The tandem catalyst shows remarkably high catalytic efficiency in nitrobenzene hydrogenation over Pt/TiO2 interface with hydrogen formed in situ by the decomposition of hydrazine hydrate over Ni/Al2 O3 interface. This can be ascribed to the synergy effect of the two interfaces and the confined nanospace favoring the instant transfer of intermediates. The tube-in-tube tandem catalyst with multiple metal-oxide interfaces represents a new concept for the design of highly efficient and multifunctional nanocatalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sol-Gel Synthesis, Electrochemical Characterization, and Stability Testing of Ti0.7W0.3O2 Nanoparticles for Catalyst Support Applications in Proton-Exchange Membrane Fuel Cells

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

Subban, Chinmayee V.; Zhou, Qin; Hu, Anthony

2010-11-19

The materials currently used in proton-exchange membrane fuel cells (PEMFCs) require complex control of operating conditions to make them sufficiently durable to permit commercial deployment. One of the major materials challenges to allow simplification of fuel cell operating strategies is the discovery of catalyst supports that are much more stable to oxidative decomposition than currently used carbon blacks. Here we report the synthesis and characterization of Ti 0.7W 0.3O 2 nanoparticles (approximately 50 nm diameter), a promising doped metal oxide that is a candidate for such a durable catalyst support. The synthesized nanoparticles were platinized, characterized by electrochemical testing, andmore » evaluated for stability under PEMFC and other oxidizing acidic conditions. Ti 0.7W 0.3O 2 nanoparticles show no evidence of decomposition when heated in a Nafion solution for 3 weeks at 80 °C. In contrast, when heated in sulfuric, nitric, perchloric, or hydrochloric acid, the oxide reacts to form salts such as titanylsulfatehydrate from sulfuric acid. Electrochemical tests show that rates of hydrogen oxidation and oxygen reduction by platinum nanoparticles supported on Ti 0.7W 0.3O 2 are comparable to those of commercial Pt on carbon black.« less

Photodecomposition of volatile organic compounds using TiO2 nanoparticles.

PubMed

Jwo, Ching-Song; Chang, Ho; Kao, Mu-Jnug; Lin, Chi-Hsiang

2007-06-01

This study examined the photodecomposition of volatile organic compounds (VOCs) using TiO2 catalyst fabricated by the Submerged Arc Nanoparticle Synthesis System (SANSS). TiO2 catalyst was employed to decompose volatile organic compounds and compare with Degussa-P25 TiO2 in terms of decomposition efficiency. In the electric discharge manufacturing process, a Ti bar, applied as the electrode, was melted and vaporized under high temperature. The vaporized Ti powders were then rapidly quenched under low-temperature and low-pressure conditions in deionized water, thus nucleating and forming nanocrystalline powders uniformly dispersed in the base solvent. The average diameter of the TiO2 nanoparticles was 20 nm. X-ray diffraction analysis confirmed that the nanoparticles in the deionized water were Anatase type TiO2. It was found that gaseous toluene exposed to UV irradiation produced intermediates that were even harder to decompose. After 60-min photocomposition, Degussa-P25 TiO2 reduced the concentration of gaseous toluene to 8.18% while the concentration after decomposition by SANSS TiO2 catalyst dropped to 0.35%. Under UV irradiation at 253.7 +/- 184.9 nm, TiO2 prepared by SANSS can produce strong chemical debonding energy, thus showing great efficiency, superior to that of Degussa-P25 TiO2, in decomposing gaseous toluene and its intermediates.

Photocatalytic ozonation of terephthalic acid: a by-product-oriented decomposition study.

PubMed

Fuentes, Iliana; Rodríguez, Julia L; Poznyak, Tatyana; Chairez, Isaac

2014-11-01

Terephthalic acid (TA) is considered as a refractory model compound. For this reason, the TA degradation usually requires a prolonged reaction time to achieve mineralization. In this study, vanadium oxide (VxOy) supported on titanium oxide (TiO2) served as a photocatalyst in the ozonation of the TA with light-emitting diodes (LEDs), having a bandwidth centered at 452 nm. The modified catalyst (VxOy/TiO2) in combination with ozone and LEDs improved the TA degradation and its by-products. The results obtained by this system were compared with photolysis, single ozonation, catalytic ozonation, and photocatalytic ozonation of VxOy/TiO2 with UV lamp. The LED-based photocatalytic ozonation showed almost the same decomposition efficiency of the TA, but it was better in comparison with the use of UV lamp. The oxalic acid accumulation, as the final product of the TA decomposition, was directly influenced by either the presence of VxOy or/and the LED irradiation. Several by-products formed during the TA degradation, such as muconic, fumaric, and oxalic acids, were identified. Besides, two unidentified by-products were completely removed during the observed time (60 min). It was proposed that the TA elimination in the presence of VxOy/TiO2 as catalyst was carried out by the combination of different mechanisms: molecular ozone reaction, indirect mechanism conducted by ·OH, and the surface complex formation.

Ammonia reactions with the stored oxygen in a commercial lean NO x trap catalyst

DOE PAGES

Bartova, Sarka; Mracek, David; Koci, Petr; ...

2014-10-12

Ammonia is an important intermediate of the NO x reduction in a NO x storage and reduction catalyst (aka lean NO x trap). NH 3 formed under rich conditions in the reduced front part of the catalyst is transported by convection downstream to the unregenerated (still oxidized) zone of the catalyst, where it further reacts with the stored oxygen and NO x. In this paper, the kinetics and selectivity of NH 3 reactions with the stored oxygen are studied in detail with a commercial Ba-based NO x storage catalyst containing platinum group metals (PGM), Ba and Ce oxides. Furthermore, steady-statemore » NH 3 decomposition, NH 3 oxidation by O 2 and NO, and N 2O decomposition are examined in light-off experiments. Periodic lean/rich cycling is measured first with O 2 and NH 3, and then with NO x + O 2 and NH 3 to discriminate between the NH 3 reactions with the stored oxygen and the stored NO x. The reaction of NH 3 with the stored O 2 is highly selective towards N 2, however a certain amount of NO x and N 2O is also formed. The formed NO x by-product is efficiently adsorbed on the NO x storage sites such that the NO x is not detected at the reactor outlet except at high temperatures. The stored NO x reacts with NH 3 feed in the next rich phase, contributing to the N 2O formation. Water inhibits the reactions of NH 3 with the stored oxygen. On the contrary, the presence of CO 2 increases the NH 3 consumption. Furthermore, CO 2 is able to provide additional oxygen for NH 3 oxidation, forming –CO in analogy to the reverse water gas shift reaction.« less

Micro-kinetic simulations of the catalytic decomposition of hydrazine on the Cu(111) surface.

PubMed

Tafreshi, Saeedeh S; Roldan, Alberto; de Leeuw, Nora H

2017-04-28

Hydrazine (N 2 H 4 ) is produced at industrial scale from the partial oxidation of ammonia or urea. The hydrogen content (12.5 wt%) and price of hydrazine make it a good source of hydrogen fuel, which is also easily transportable in the hydrate form, thus enabling the production of H 2 in situ. N 2 H 4 is currently used as a monopropellant thruster to control and adjust the orbits and altitudes of spacecrafts and satellites; with similar procedures applicable in new carbon-free technologies for power generators, e.g. proton-exchange membrane fuel cells. The N 2 H 4 decomposition is usually catalysed by the expensive Ir/Al 2 O 3 material, but a more affordable catalyst is needed to scale-up the process whilst retaining reaction control. Using a complementary range of computational tools, including newly developed micro-kinetic simulations, we have derived and analysed the N 2 H 4 decomposition mechanism on the Cu(111) surface, where the energetic terms of all states have been corrected by entropic terms. The simulated temperature-programmed reactions have shown how the pre-adsorbed N 2 H 4 coverage and heating rate affect the evolution of products, including NH 3 , N 2 and H 2 . The batch reactor simulations have revealed that for the scenario of an ideal Cu terrace, a slow but constant production of H 2 occurs, 5.4% at a temperature of 350 K, while the discharged NH 3 can be recycled into N 2 H 4 . These results show that Cu(111) is not suitable for hydrogen production from hydrazine. However, real catalysts are multi-faceted and present defects, where previous work has shown a more favourable N 2 H 4 decomposition mechanism, and, perhaps, the decomposition of NH 3 improves the production of hydrogen. As such, further investigation is needed to develop a general picture.

Direct evidence of atomic-scale structural fluctuations in catalyst nanoparticles.

PubMed

Lin, Pin Ann; Gomez-Ballesteros, Jose L; Burgos, Juan C; Balbuena, Perla B; Natarajan, Bharath; Sharma, Renu

2017-05-01

Rational catalyst design requires an atomic scale mechanistic understanding of the chemical pathways involved in the catalytic process. A heterogeneous catalyst typically works by adsorbing reactants onto its surface, where the energies for specific bonds to dissociate and/or combine with other species (to form desired intermediate or final products) are lower. Here, using the catalytic growth of single-walled carbon nanotubes (SWCNTs) as a prototype reaction, we show that the chemical pathway may in-fact involve the entire catalyst particle, and can proceed via the fluctuations in the formation and decomposition of metastable phases in the particle interior. We record in situ and at atomic resolution, the dynamic phase transformations occurring in a Cobalt catalyst nanoparticle during SWCNT growth, using a state-of-the-art environmental transmission electron microscope (ETEM). The fluctuations in catalyst carbon content are quantified by the automated, atomic-scale structural analysis of the time-resolved ETEM images and correlated with the SWCNT growth rate. We find the fluctuations in the carbon concentration in the catalyst nanoparticle and the fluctuations in nanotube growth rates to be of complementary character. These findings are successfully explained by reactive molecular dynamics (RMD) simulations that track the spatial and temporal evolution of the distribution of carbon atoms within and on the surface of the catalyst particle. We anticipate that our approach combining real-time, atomic-resolution image analysis and molecular dynamics simulations will facilitate catalyst design, improving reaction efficiencies and selectivity towards the growth of desired structure.

Synergistic effect of carbon nanofiber/nanotube composite catalyst on carbon felt electrode for high-performance all-vanadium redox flow battery.

PubMed

Park, Minjoon; Jung, Yang-jae; Kim, Jungyun; Lee, Ho il; Cho, Jeaphil

2013-10-09

Carbon nanofiber/nanotube (CNF/CNT) composite catalysts grown on carbon felt (CF), prepared from a simple way involving the thermal decomposition of acetylene gas over Ni catalysts, are studied as electrode materials in a vanadium redox flow battery. The electrode with the composite catalyst prepared at 700 °C (denoted as CNF/CNT-700) demonstrates the best electrocatalytic properties toward the V(2+)/V(3+) and VO(2+)/VO2(+) redox couples among the samples prepared at 500, 600, 700, and 800 °C. Moreover, this composite electrode in the full cell exhibits substantially improved discharge capacity and energy efficiency by ~64% and by ~25% at 40 mA·cm(-2) and 100 mA·cm(-2), respectively, compared to untreated CF electrode. This outstanding performance is due to the enhanced surface defect sites of exposed edge plane in CNF and a fast electron transfer rate of in-plane side wall of the CNT.

Photocatalytic carbon dioxide reduction with rhodium-based catalysts in solution and heterogenized within metal-organic frameworks.

PubMed

Chambers, Matthew B; Wang, Xia; Elgrishi, Noémie; Hendon, Christopher H; Walsh, Aron; Bonnefoy, Jonathan; Canivet, Jérôme; Quadrelli, Elsje Alessandra; Farrusseng, David; Mellot-Draznieks, Caroline; Fontecave, Marc

2015-02-01

The first photosensitization of a rhodium-based catalytic system for CO2 reduction is reported, with formate as the sole carbon-containing product. Formate has wide industrial applications and is seen as valuable within fuel cell technologies as well as an interesting H2 -storage compound. Heterogenization of molecular rhodium catalysts is accomplished via the synthesis, post-synthetic linker exchange, and characterization of a new metal-organic framework (MOF) Cp*Rh@UiO-67. While the catalytic activities of the homogeneous and heterogeneous systems are found to be comparable, the MOF-based system is more stable and selective. Furthermore it can be recycled without loss of activity. For formate production, an optimal catalyst loading of ∼10 % molar Rh incorporation is determined. Increased incorporation of rhodium catalyst favors thermal decomposition of formate into H2 . There is no precedent for a MOF catalyzing the latter reaction so far. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Demonstrating the Effect of Interphase Mass Transfer in a Transparent Fluidized Bed Reactor

ERIC Educational Resources Information Center

Saayman, Jean; Nicol, Willie

2011-01-01

A demonstration experiment is described that employs the ozone decomposition reaction at ambient conditions on Fe2O3 impregnated Fluidized Catalytic Cracking (FCC) catalyst. Using a two-dimensional see-through column the importance of interphase mass transfer is clearly illustrated by the significant difference in ozone conversion between the…

Synthesis of N-doped TiO2 Using Guanidine Nitrate: An Excellent Visible Light Photocatalyst

EPA Science Inventory

An excellent visible light active nitrogen-rich TiO2 photocatalyst have been synthesized by using guanidine nitrate as the doping material. The catalytic efficiency of the catalyst has been demonstrated by the decomposition of the dye, methyl orange (MO), and the pollutant, 2,4 d...

In Situ Studies of the Decomposition of Simulated Chemical Warfare Agents on Nanoparticle Catalysts

DTIC Science & Technology

2009-10-04

University of South Carolina NUMBER Office of Sponsored Programs & Research James F. Byrnes International Center Columbia, SC 29208 - 9...P.; Barrat , J. L. Phys. Rev. B 1997, 56, 2248. (28) Ercolessi, F.; Andreoni, W.; Tosatti, E. Phys. Rev. Lett. 1991, 66, 911. (29) Marks, L. D

Conversion of KCl into KBH4 by Mechano-Chemical Reaction and its Catalytic Decomposition

NASA Astrophysics Data System (ADS)

Bilen, Murat; Gürü, Metin; Çakanyildirim, Çetin

2017-07-01

Production of KBH4, in the presence of KCl, B2O3 and MgH2 by means of a mechanical reaction and a dehydrogenation kinetic, constitute the main parts of this study. Operating time and reactant ratio are considered as two parameters for the mechanical reaction to obtain the maximum yield. The production process was carried out in a ball milling reactor, and the product residue was purified with ethylene diamine (EDA) and subsequently characterized by Fourier Transform Infrared Spectroscopy (FT-IR) and x-ray Diffraction (XRD) analyses. Optimum time for mechano-chemical treatment and reactant ratio (MgH2/KCl) were obtained as 1000 min and 1.0, respectively. Synthesized and commercial KBH4 were compared by hydrolysis tests in the presence of Co1-xNix/Al2O3 heterogeneous catalyst. Hydrogen generation rates, activation energy and order of the KBH4 decomposition reaction were obtained as 1578 {mL}_{{{{H}}2 }} \\min^{ - 1} {g}_{{catalyst}}^{ - 1}, 39.2 kJ mol-1 and zero order, respectively.

Preparation and characterization of mesoporous ZnO-ZrO2 doped by Cr, Nd and Dy as a catalyst for conversion of coumarin using ultrasensitive fluorometric method

NASA Astrophysics Data System (ADS)

Ibrahim, M. M.

2017-04-01

Doping of mesoporous ZnO-ZrO2 nanoparticles with transition metal and lanthanides (Cr, Nd, Dy) were used as a catalyst to develop an ultrasensitive fluorometric method for the conversion of non fluorescent coumarin to highly fluorescent 7-hydroxycoumarin using H2O2 or light. It was found that doped- ZnO-ZrO2 mixed oxide can catalyze the decomposition of H2O2 to produce •OH radicals, which in turn convert coumarin to 7-hydroxycoumarin. At contrast, the doping has deleterious effect on conversion of coumarin by light due to high band gap and high concentrations of doping increase the recombination rate of electron and holes. Doped mixed oxides prepared by impregnation method and characterized by studying their structural, surface and optical properties. Chromium doped ZnO-ZrO2 had the highest rate of formation of hydroxyl radical due to decomposition of H2O2 and therefore 7-hydroxycoumarin due to surface area, small crystal size and high redox potential.

Ni@Fe2O3 heterodimers: controlled synthesis and magnetically recyclable catalytic application for dehalogenation reactions

NASA Astrophysics Data System (ADS)

Nakhjavan, Bahar; Tahir, Muhammad Nawaz; Natalio, Filipe; Panthöfer, Martin; Gao, Haitao; Dietzsch, Michael; Andre, Rute; Gasi, Teuta; Ksenofontov, Vadim; Branscheid, Robert; Kolb, Ute; Tremel, Wolfgang

2012-07-01

Ni@Fe2O3 heterodimer nanoparticles (NPs) were synthesized by thermal decomposition of organometallic reactants. After functionalization, these Ni@Fe2O3 heterodimers became water soluble. The pristine heterodimeric NPs were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Mössbauer spectroscopy and magnetic susceptibility measurements. A special advantage of the heterodimers lies in the fact that nanodomains of different composition can be used as catalysts for the removal of environmentally hazardous halogenated pollutants.Ni@Fe2O3 heterodimer nanoparticles (NPs) were synthesized by thermal decomposition of organometallic reactants. After functionalization, these Ni@Fe2O3 heterodimers became water soluble. The pristine heterodimeric NPs were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Mössbauer spectroscopy and magnetic susceptibility measurements. A special advantage of the heterodimers lies in the fact that nanodomains of different composition can be used as catalysts for the removal of environmentally hazardous halogenated pollutants. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr12121b

Nitrogen Chemistry and Coke Transformation of FCC Coked Catalyst during the Regeneration Process

NASA Astrophysics Data System (ADS)

Shi, Junjun; Guan, Jianyu; Guo, Dawei; Zhang, Jiushun; France, Liam John; Wang, Lefu; Li, Xuehui

2016-06-01

Regeneration of the coked catalyst is an important process of fluid catalytic cracking (FCC) in petroleum refining, however, this process will emit environmentally harmful gases such as nitrogen and carbon oxides. Transformation of N and C containing compounds in industrial FCC coke under thermal decomposition was investigated via TPD and TPO to examine the evolved gaseous species and TGA, NMR and XPS to analyse the residual coke fraction. Two distinct regions of gas evolution are observed during TPD for the first time, and they arise from decomposition of aliphatic carbons and aromatic carbons. Three types of N species, pyrrolic N, pyridinic N and quaternary N are identified in the FCC coke, the former one is unstable and tends to be decomposed into pyridinic and quaternary N. Mechanisms of NO, CO and CO2 evolution during TPD are proposed and lattice oxygen is suggested to be an important oxygen resource. Regeneration process indicates that coke-C tends to preferentially oxidise compared with coke-N. Hence, new technology for promoting nitrogen-containing compounds conversion will benefit the in-situ reduction of NO by CO during FCC regeneration.

Natural Magnetite: an efficient catalyst for the degradation of organic contaminant

NASA Astrophysics Data System (ADS)

He, Hongping; Zhong, Yuanhong; Liang, Xiaoliang; Tan, Wei; Zhu, Jianxi; Yan Wang, Christina

2015-05-01

Iron (hydr)oxides are ubiquitous earth materials that have high adsorption capacities for toxic elements and degradation ability towards organic contaminants. Many studies have investigated the reactivity of synthetic magnetite, while little is known about natural magnetite. Here, we first report the reactivity of natural magnetites with a variety of elemental impurities for catalyzing the decomposition of H2O2 to produce hydroxyl free radicals (•OH) and the consequent degradation of p-nitrophenol (p-NP). We observed that these natural magnetites show higher catalytic performance than that of the synthetic pure magnetite. The catalytic ability of natural magnetite with high phase purity depends on the surface site density while that for the magnetites with exsolutions relies on the mineralogical nature of the exsolved phases. The pleonaste exsolution can promote the generation of •OH and the consequent degradation of p-NP; the ilmenite exsolution has little effect on the decomposition of H2O2, but can increase the adsorption of p-NP on magnetite. Our results imply that natural magnetite is an efficient catalyst for the degradation of organic contaminants in nature.

Multifunctional Co₀.₈₅Se/graphene hybrid nanosheets: controlled synthesis and enhanced performances for the oxygen reduction reaction and decomposition of hydrazine hydrate.

PubMed

Zhang, Lin-fei; Zhang, Chun-yang

2014-01-01

Ultrathin nanosheets possess novel electronic structures and physical properties as compared with their corresponding bulk samples. However, the controlled synthesis of ultrathin monolayer nanosheets still remains a great challenge due to the lack of an intrinsic driving force for anisotropic growth of two-dimensional (2D) structures. Here we demonstrate, for the first time to our knowledge, the in situ synthesis of large-scale ultrathin single-crystalline Co₀.₈₅Se nanosheets on graphene oxide (GO) sheets, with a thickness of 3 nm. Owing to the synergetic chemical coupling effects between GO and Co₀.₈₅Se, the Co₀.₈₅Se/graphene hybrid nanosheets exhibit the highest catalytic performance among the available cobalt chalcogenide-based catalysts for the oxygen reduction reaction (ORR). Moreover, Co₀.₈₅Se/graphene hybrid nanosheets can catalyze the decomposition of hydrazine hydrate rapidly, with 97% of hydrazine hydrate being degraded in 12 min and the degradation rate remaining constant over 10 consecutive cycles, thus having great potential as long-term catalysts in wastewater treatment.

Enhanced protection of PDMS-embedded palladium catalysts by co-embedding of sulphide-scavengers.

PubMed

Comandella, Daniele; Ahn, Min Hyung; Kim, Hojeong; Mackenzie, Katrin

2017-12-01

For Pd-containing hydrodechlorination catalysts, coating with poly(dimethyl siloxane) (PDMS) was proposed earlier as promising protection scheme against poisoning. The PDMS coating can effectively repel non-permeating poisons (such as SO 3 2- ) retaining the hydrodechlorination Pd activity. In the present study, the previously achieved protection efficiency was enhanced by incorporation of sulphide scavengers into the polymer. The embedded scavengers were able to bind permeating non-ionic poisons (such as H 2 S) during their passage through PDMS prior to Pd contact which ensured an extended catalyst lifetime. Three scavenger types forming non-permeable sulphur species from H 2 S - alkaline, oxidative or iron-based compounds - were either incorporated into single-layer coats around individual Pd/Al 2 O 3 particles or into a second layer above Pd-containing PDMS films (Pd-PDMS). Hydrodechlorination and hydrogenation were chosen as model reactions, carried out in batch and continuous-flow reactors. Batch tests with all scavenger-containing catalysts showed extended Pd protection compared to scavenger-free catalysts. Solid alkaline compounds (Ca(OH) 2 , NaOH, CaO) and MnO 2 showed the highest instantaneous scavenger efficiencies (retained Pd activity=30-60%), while iron-based catalysts, such as nano zero-valent iron (nZVI) or ferrocene (FeCp 2 ), proved less efficient (1-10%). When stepwise poisoning was applied, the protection efficiency of iron-based and oxidizing compounds was higher in the long term than that of alkaline solids. Long-term experiments in mixed-flow reactors were performed with selected scavengers, revealing the following trend of protection efficiency: CaO 2 >Ca(OH) 2 >FeCp 2 . Under field-simulating conditions using a fixed-bed reactor, the combination of sulphide pre-oxidation in the water phase by H 2 O 2 and local scavenger-enhanced Pd protection was successful. The oxidizing agent H 2 O 2 does not disturb the Pd-catalysed reduction, while the PDMS-incorporated scavenger considerably extends the catalyst life in the presence of H 2 S. This work demonstrates that the scavenger-based protection strategy is an effective means to increase the resistance of PDMS-embedded Pd against permeating poisons. Copyright © 2017. Published by Elsevier B.V.

40 CFR 721.9665 - Organotin catalysts.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Organotin catalysts. 721.9665 Section... Substances § 721.9665 Organotin catalysts. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substances identified generically as organotin catalysts (PMNs P-93-853, P-93...

40 CFR 721.9665 - Organotin catalysts.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Organotin catalysts. 721.9665 Section... Substances § 721.9665 Organotin catalysts. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substances identified generically as organotin catalysts (PMNs P-93-853, P-93...

Liquid-phase hydrogenation of citral over Pt/SiO{sub 2} catalysts. 1. Temperature effects on activity and selectivity

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

Singh, U.K.; Vannice, M.A.

2000-04-01

Liquid-phase hydrogenation of citral (3,7-dimethyl-2,6-octadienal) over Pt/SiO{sub 2} catalysts was studied in the temperature and pressure ranges 298--423 K and 7--21 atm, respectively. The reaction kinetics were shown to be free of artifacts arising from transport limitations and poisoning effects. The reaction rate in hexane at the solvent exhibited an activity minimum at 373 K. The initial turnover frequency for citral disappearance over 1.44% Pt/SiO{sub 2} catalyst at 20 atm H{sub 2} pressure decreased from 0.19 s{sup {minus}1} at 298 K to 0.02 s{sup {minus}1} at 373 K, but exhibited normal Arrhenius behavior between 373 and 423 K with anmore » activation energy of 7 kcal/mol. Reaction at 298 K produced substantial deactivation, with the rate decreasing by more than an order of magnitude during the first 4 h of reaction; however, reaction at temperatures greater than 373 K exhibited negligible deactivation and a constant rate up to citral conversions greater than 70%. These unusual temperature effects were modeled using Langmuir-Hinshelwood kinetics invoking dissociative adsorption of hydrogen, competitive adsorption between hydrogen and the organic compounds, and addition of the second hydrogen atom to each reactant as the rate-determining step. Decomposition of the unsaturated alcohol (either geraniol or nerol) was proposed to occur concurrently with the hydrogenation steps to yield adsorbed CO and carbonaceous species which cause the deactivation, but at higher temperatures these species could be removed from the Pt surface by desorption or rapid hydrogenation, respectively. The activity minimum observed in the present study is attributed to the relative rates of the alcohol decomposition reaction and CO desorption, with the decomposition reaction having an activation barrier lower than that for CO desorption.« less

Manganese-cerium oxide catalysts prepared by non-thermal plasma for NO oxidation: Effect of O2 in discharge atmosphere

NASA Astrophysics Data System (ADS)

Liu, Lu; Zheng, Chenghang; Wu, Shenghao; Gao, Xiang; Ni, Mingjiang; Cen, Kefa

2017-09-01

Non-thermal plasma with different O2 concentration in discharge atmosphere was applied to synthesize manganese and cerium mixed-oxides catalysts, which were compared in NO oxidation activity. Discharge atmosphere displayed a crucial influence on the performance of the catalysts prepared by plasma. Relatively low O2 concentration in discharge atmosphere allows synthesizing manganese-cerium oxides catalysts in a moderate environment and therefore is favorable for better physicochemical properties which lead to superior catalytic behavior. The best catalyst was obtained by treatment with 10% O2/N2 plasma and presented over 80% NO conversion in the temperature range of 275-325 °C, whereas catalyst prepared in pure O2 discharge atmosphere had the same activity with a catalyst prepared by calcinations. A correlation between the surface properties of the plasma prepared catalysts and its catalytic activity in NO oxidation is proposed. The amount of the surface adsorbed oxygen has an obvious linear correlation with the amount of Ce3+, the H2 consumption at low temperatures and the catalytic performance. The superior catalytic performance is mainly attributed to the stronger interaction between manganese oxides and ceria, and the formation of poorly crystallized Mn-O-Ce phase in the catalyst which resulted from the slow decomposition of nitrates and organics during plasma treatment. Catalysts prepared in relatively low O2 concentration have large specific surface area and is abundant in Ce3+ species and active oxygen species. The study suggests that plasma treatment with proper discharge gas components is a promising method to prepare effective manganese- cerium oxides catalyst for NO oxidation.

Production of heavy water

DOEpatents

Spencer, Larry S.; Brown, Sam W.; Phillips, Michael R.

2017-06-06

Disclosed are methods and apparatuses for producing heavy water. In one embodiment, a catalyst is treated with high purity air or a mixture of gaseous nitrogen and oxygen with gaseous deuterium all together flowing over the catalyst to produce the heavy water. In an alternate embodiment, the deuterium is combusted to form the heavy water. In an alternate embodiment, gaseous deuterium and gaseous oxygen is flowed into a fuel cell to produce the heavy water. In various embodiments, the deuterium may be produced by a thermal decomposition and distillation process that involves heating solid lithium deuteride to form liquid lithium deuteride and then extracting the gaseous deuterium from the liquid lithium deuteride.

Supercritical Water Process for the Chemical Recycling of Waste Plastics

NASA Astrophysics Data System (ADS)

Goto, Motonobu

2010-11-01

The development of chemical recycling of waste plastics by decomposition reactions in sub- and supercritical water is reviewed. Decomposition reactions proceed rapidly and selectively using supercritical fluids compared to conventional processes. Condensation polymerization plastics such as PET, nylon, and polyurethane, are relatively easily depolymerized to their monomers in supercritical water. The monomer components are recovered in high yield. Addition polymerization plastics such as phenol resin, epoxy resin, and polyethylene, are also decomposed to monomer components with or without catalysts. Recycling process of fiber reinforced plastics has been studied. Pilot scale or commercial scale plants have been developed and are operating with sub- and supercritical fluids.

Autonomous movement of silica and glass micro-objects based on a catalytic molecular propulsion system.

PubMed

Stock, Christoph; Heureux, Nicolas; Browne, Wesley R; Feringa, Ben L

2008-01-01

A general approach for the easy functionalization of bare silica and glass surfaces with a synthetic manganese catalyst is reported. Decomposition of H(2)O(2) by this dinuclear metallic center into H(2)O and O(2) induced autonomous movement of silica microparticles and glass micro-sized fibers. Although several mechanisms have been proposed to rationalise movement of particles driven by H(2)O(2) decomposition to O(2) and water (recoil from O(2) bubbles, ([36,45]) interfacial tension gradient([37-42]), it is apparent in the present system that ballistic movement is due to the growth of O(2) bubbles.

Pyrolysis of polyethylene terephthalate containing real waste plastics using Ni loaded zeolite catalysts

NASA Astrophysics Data System (ADS)

Al-asadi, M.; Miskolczi, N.

2018-05-01

In this work the pyrolysis of polyethylene terephthalate (PET) containing real waste plastic was investigated using different Ni loaded catalysts: Ni/ZSM-5, Ni/y-zeolite, Ni/β-zeolite and Ni/natural zeolite (clinoptilolite). Raw materials were pyrolyzed in a horizontal tubular reactor between 600 and 900°C using 10% of catalysts. It was found, that both temperature increasing and catalysts presence can increase the gas yields, however owing to gasification reactions, the pyrolysis oil yield decreased with increasing temperature. Ni/y-zeolite catalyst had the most benefit in gas yield increasing at low temperature; however Ni/ZSM-5 showed advanced property in gas yield increasing at high temperature. Gases contained hydrogen, carbon oxides and hydrocarbons, which composition was significantly affected by catalysts. Ni loaded zeolites favoured to the formation of hydrogen and branched hydrocarbons; furthermore the concentrations of both CO and CO2 were also increased as function of elevated temperature. That phenomenon was attributed to the further decomposition of PET, especially to the side chain scission reactions. Owing to the Boudouard reaction, the ratio of CO2/CO can increased with temperature. Pyrolysis oils were the mixtures of n-saturated, n-unsaturated, branched, oxygen free aromatics and oxygenated hydrocarbons. Temperature increasing has a significant effect to the aromatization and isomerization reactions, while the catalysts can efficiently decreased the concentration of oxygen containing compounds.

Solid state gas sensors for detection of explosives and explosive precursors

NASA Astrophysics Data System (ADS)

Chu, Yun

The increased number of terrorist attacks using improvised explosive devices (IEDs) over the past few years has made the trace detection of explosives a priority for the Department of Homeland Security. Considerable advances in early detection of trace explosives employing spectroscopic detection systems and other sensing devices have been made and have demonstrated outstanding performance. However, modern IEDs are not easily detectable by conventional methods and terrorists have adapted to avoid using metallic or nitro groups in the manufacturing of IEDs. Instead, more powerful but smaller compounds, such as TATP are being more frequently used. In addition, conventional detection techniques usually require large capital investment, labor costs and energy input and are incapable of real-time identification, limiting their application. Thus, a low cost detection system which is capable of continuous online monitoring in a passive mode is needed for explosive detection. In this dissertation, a thermodynamic based thin film gas sensor which can reliably detect various explosive compounds was developed and demonstrated. The principle of the sensors is based on measuring the heat effect associated with the catalytic decomposition of explosive compounds present in the vapor phase. The decomposition mechanism is complicated and not well known, but it can be affected by many parameters including catalyst, reaction temperature and humidity. Explosives that have relatively high vapor pressure and readily sublime at room temperature, like TATP and 2, 6-DNT, are ideal candidate for vapor phase detection using the thermodynamic gas sensor. ZnO, W2O 3, V2O5 and SnO2 were employed as catalysts. This sensor exhibited promising sensitivity results for TATP, but poor selectivity among peroxide based compounds. In order to improve the sensitivity and selectivity of the thermodynamic sensor, a Pd:SnO2 nanocomposite was fabricated and tested as part of this dissertation. A combinatorial chemistry techniques were used for catalyst discovery. Specially, a series of tin oxide catalysts with continuous varying composition of palladium were fabricated to screen for the optimum Pd loading to maximize specificity. Experimental results suggested that sensors with a 12 wt.% palladium loading generated the highest sensitivity while a 8 wt.% palladium loading provided greatest selectivity. XPS and XRD were used to study how palladium doping level affects the oxidation state and crystal structure of the nanocomposite catalyst. As with any passive detection system, a necessary theme of this dissertation was the mitigation of false positive. Toward this end, an orthogonal detection system comprised of two independent sensing platforms sharing one catalyst was demonstrated using TATP, 2, 6-DNT and ammonium nitrate as target molecules. The orthogonal sensor incorporated a thermodynamic based sensing platform to measure the heat effect associated with the decomposition of explosive molecules, and a conductometric sensing platform that monitors the change in electrical conductivity of the same catalyst when exposed to the explosive substances. Results indicate that the orthogonal sensor generates an effective response to explosives presented at part per billion level. In addition, with two independent sensing platforms, a built-in redundancy of results could be expected to minimize false positive.

Cobalt nanoparticles encapsulated in nitrogen-rich carbon nanotubes as efficient catalysts for organic pollutants degradation via sulfite activation.

PubMed

Wu, Deming; Ye, Peng; Wang, Manye; Wei, Yi; Li, Xiaoxia; Xu, Aihua

2018-06-15

The activation of sulfite by heterogeneous catalysts displays a great potential in the development of new sulfate radials based technologies for wastewater treatment. Herein, cobalt nanoparticles embedded in N-doped carbon nanotubes (Co@NC) were prepared by a simple pyrolysis method. Due to the synergistic effects of the cobalt nanoparticles and N-doped carbon nanotubes, the Co@NC catalyst intrinsically shows an outstanding efficiency, excellent reusability and high stability in the catalytic oxidation of methyl orange (MO) in the presence of sulfite and dioxygen. The structure and efficiency of the catalyst was significantly affected by the content of cobalt and pyrolysis temperature. Several quenching experiments and electron paramagnetic resonance were carried out to investigate the catalytic mechanism. It is found that hydroxyl and sulfate radicals worked together to degrade MO in the system. The formation and decomposition of peroxymonosulfate may be an important route of these reactive radicals production. The effect of different anions, bicarbonate concentration, initial solution pH and dye types on the performance of the catalyst was also studied. This study can open a new approach for design and preparation of encapsulated cobalt in carbon materials as effective catalysts for pollutants degradation via sulfite activation. Copyright © 2018 Elsevier B.V. All rights reserved.

Dual properties of a hydrogen oxidation Ni-catalyst entrapped within a polymer promote self-defense against oxygen

DOE PAGES

Oughli, Alaa A.; Ruff, Adrian; Boralugodage, Nilusha Priyadarshani; ...

2018-02-28

A bio-inspired O 2 sensitive nickel catalyst dispersed in a hydrophobic and redox-silent polymer matrix shows enhanced stability for catalytic H 2 oxidation as well as O 2 tolerance. A simple but efficient electrode design separates the catalyst into two different reaction layers to promote different reactivity on the catalyst. (1) close to the electrode surface, the catalyst can directly exchange electrons with the electrode and generate current from H 2 oxidation; and (2) at the outer film boundary, the electrolyte exposed layer is electrically isolated from the electrode, which enables the H 2 reduced Ni-complex to convert O 2more » to H 2O and thus provides protection to the O 2-sensitive inner reaction layer. This strategy solves one of the biggest limitations of these otherwise outstanding catalysts and could be used to protect other similar catalysts whose wider application is currently limited by sensitivity towards oxygen.« less

Dual properties of a hydrogen oxidation Ni-catalyst entrapped within a polymer promote self-defense against oxygen

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

Oughli, Alaa A.; Ruff, Adrian; Boralugodage, Nilusha Priyadarshani

A bio-inspired O 2 sensitive nickel catalyst dispersed in a hydrophobic and redox-silent polymer matrix shows enhanced stability for catalytic H 2 oxidation as well as O 2 tolerance. A simple but efficient electrode design separates the catalyst into two different reaction layers to promote different reactivity on the catalyst. (1) close to the electrode surface, the catalyst can directly exchange electrons with the electrode and generate current from H 2 oxidation; and (2) at the outer film boundary, the electrolyte exposed layer is electrically isolated from the electrode, which enables the H 2 reduced Ni-complex to convert O 2more » to H 2O and thus provides protection to the O 2-sensitive inner reaction layer. This strategy solves one of the biggest limitations of these otherwise outstanding catalysts and could be used to protect other similar catalysts whose wider application is currently limited by sensitivity towards oxygen.« less

Micro–mesoporous iron oxides with record efficiency for the decomposition of hydrogen peroxide: morphology driven catalysis for the degradation of organic contaminants

EPA Science Inventory

A template-free solid-state synthesis of a morphologically controlled and highly organized iron(III)oxide micro–mesoporous Fenton catalyst has been engineered through a simple two-step synthetic procedure. The 3D nanoassembly of hematite nanoparticles (5–7 nm) organized into a ro...

Study of volatile contaminants in reclaimed water. [by distillation from urine

NASA Technical Reports Server (NTRS)

Mckee, H. C.; Millar, J. D.; Swynnerton, N. F.

1975-01-01

Different methods were evaluated for reducing the volatile contaminants found in water recovered from urine by distillation. The use of activated carbon, addition of potassium permanganate, and the use of oxidation catalyst are described along with laboratory tests. It is concluded that catalytic decomposition appears to be feasible, and further investigation is recommended.

Natural Catalysts for Molten Cellulose Pyrolysis to Targeted Bio-Oils

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

Dauenhauer, Paul J.

2017-06-02

Catalysis of biomass biopolymer cellulose by alkaline earth metals is a fundamental chemistry relevant to energy processes including combustion, pyrolysis and gasification. In this work, the catalytic decomposition of cellulose by calcium ions was evaluated at high temperature (400-500°C) to elucidate the chemical mechanisms leading to the formation of volatile organic compounds.

Heterogeneously Catalyzed Endothermic Fuel Cracking

DTIC Science & Technology

2016-08-28

Much of this literature is in the context of gas -to- liquids technology and industrial dehydrogenation processes. Based on the published measurements...certain zeolites. Comparisons of conversion, major product distributions and molecular weight growth processes in the gas -phase pyrolysis of model...thereby maximizing the extent of cooling, (b) increase catalyst activity for fuel decomposition, but inhibit gas -phase molecular weight growth

Analysis of the critical step in catalytic carbodiimide transformation: proton transfer from amines, phosphines, and alkynes to guanidinates, phosphaguanidinates, and propiolamidinates with Li and Al catalysts.

PubMed

Rowley, Christopher N; Ong, Tiow-Gan; Priem, Jessica; Richeson, Darrin S; Woo, Tom K

2008-12-15

While lithium amides supported by tetramethylethylenediamine (TMEDA) are efficient catalysts in the synthesis of substituted guanidines via the guanylation of an amine with carbodiimide, as well as the guanylation of phosphines and conversion of alkynes into propiolamidines, aluminum amides are only efficient catalysts for the guanylation of amides. Density functional theory (DFT) calculations were used to explain this difference in activity. The origin of this behavior is apparent in the critical step where a proton is transferred from the substrate to a metal guanidinate. The activation energies of these steps are modest for amines, phosphines, and alkynes when a lithium catalyst was used, but are prohibitively high for the analogous reactions with phosphines and alkynes for aluminum amide catalysts. Energy decomposition analysis (EDA) indicates that these high activations energies are due to the high energetic cost of the detachment of a chelating guanidinate nitrogen from the aluminum in the proton transfer transition state. Amines are able to adopt an ideal geometry for facile proton transfer to the aluminum guanidinate and concomitant Al-N bond formation, while phosphines and alkynes are not.

Impact of support calcination and competitive adsorbate in Fe/Mo-Al2O3 catalyst for synthesis of carbon nanotubes by V-flame

NASA Astrophysics Data System (ADS)

Sun, Ya-Ping; Sun, Bao-Min; Zhai, Gang; Guo, Yong-Hong; Jia, Xiao-Wei; Kang, Zhi-Zhong

2018-05-01

Carbon nanotubes (CNTs) were synthesized via carbon monoxide decomposition with aid of various Fe/Mo-Al2O3 catalysts by V-type flame method. The influences of support calcination and competitive adsorbates on the morphology and properties of CNTs were studied. SEM, HRTEM, TPO and Raman spectroscopy were applied to investigate the morphology and microstructure of CNT products. XRD, H2-TPR were employed to characterize catalysts. The obtained results indicate that calcinated support can increase production and promote the formation of CNTs with small diameter. Utilizing citric acid as a competitive adsorbate is successful in improving the quality of CNTs. Besides, the addition of citric acid and calcinated support in catalyst enhances the catalytic growth activity. The obtained CNTs have a diameter around 4–6 nm within a narrow diameter distribution range. Raman spectrum analysis also illustrates that highly graphitized CNTs are produced on the catalyst with calcinated support and citric acid. These results suggest that support calcination and competitive adsorbate have pronounced effect on the average diameter, diameter distribution, and graphitization of CNTs, which provides a simple and effective way to tune the properties of CNTs.

Enhancing Catalyzed Decomposition of Na2CO3 with Co2MnO x Nanowire-Decorated Carbon Fibers for Advanced Na-CO2 Batteries.

PubMed

Fang, Cong; Luo, Jianmin; Jin, Chengbin; Yuan, Huadong; Sheng, Ouwei; Huang, Hui; Gan, Yongping; Xia, Yang; Liang, Chu; Zhang, Jun; Zhang, Wenkui; Tao, Xinyong

2018-05-23

The metal-CO 2 batteries, especially Na-CO 2 , batteries come into sight owing to their high energy density, ability for CO 2 capture, and the abundance of sodium resource. Besides the sluggish electrochemical reactions at the gas cathodes and the instability of the electrolyte at a high voltage, the final discharge product Na 2 CO 3 is a solid and poor conductor of electricity, which may cause the high overpotential and poor cycle performance for the Na-CO 2 batteries. The promotion of decomposition of Na 2 CO 3 should be an efficient strategy to enhance the electrochemical performance. Here, we design a facile Na 2 CO 3 activation experiment to screen the efficient cathode catalyst for the Na-CO 2 batteries. It is found that the Co 2 MnO x nanowire-decorated carbon fibers (CMO@CF) can promote the Na 2 CO 3 decomposition at the lowest voltage among all these metal oxide-decorated carbon fiber structures. After assembling the Na-CO 2 batteries, the electrodes based on CMO@CF show lower overpotential and better cycling performance compared with the electrodes based on pristine carbon fibers and other metal oxide-modified carbon fibers. We believe this catalyst screening method and the freestanding structure of the CMO@CF electrode may provide an important reference for the development of advanced Na-CO 2 batteries.

Low temperature destruction of PCDD/Fs over V2O5-CeO2/TiO2 catalyst with ozone.

PubMed

Yu, Ming-Feng; Lin, Xiao-Qing; Yan, Mi; Li, Xiao-Dong; Chen, Tong; Yan, Jian-Hua

2016-09-01

Catalytic destruction of PCDD/Fs (polychlorinated dibenzo-p-dioxins and furans) over V2O5-CeO2/TiO2 catalyst was investigated at a low temperature range of 140-180 °C, in the absence and presence of ozone (200 ppm). Nano-TiO2 support was used to prepare the catalyst by step impregnation method. A stable PCDD/Fs-generating system was established to support the catalytic destruction tests. In the presence of ozone alone, destruction efficiencies of PCDD/Fs are between 32.2 and 43.1 % with temperature increasing from 140 to 180 °C. The activity of V2O5-CeO2/TiO2 catalyst alone on PCDD/Fs destruction is also studied. The increase of temperature from 140 to 180 °C enhances the activity of catalyst with destruction efficiencies increasing from 54.7 to 73.4 %. However, ozone addition greatly enhances the catalytic activity of V2O5-CeO2/TiO2 catalyst on PCDD/Fs decomposition. At 180 °C, the destruction efficiency of PCDD/Fs achieved with V2O5-CeO2/TiO2 catalyst and ozone is above 86.0 %. It indicates that the combined use of ozone and catalyst reduces the reaction temperature of PCDD/Fs oxidation and offers a new method to destroy PCDD/Fs with high destruction efficiency at a low temperature. Furthermore, the destruction efficiencies of 17 toxic PCDD/F congeners, achieved with ozone alone, catalyst alone, and catalyst/ozone are analyzed.

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

High Catalytic Efficiency of Nanostructured β-CoMoO₄ in the Reduction of the Ortho-, Meta- and Para-Nitrophenol Isomers.

PubMed

Al-Wadaani, Fahd; Omer, Ahmed; Abboudi, Mostafa; Oudghiri Hassani, Hicham; Rakass, Souad; Messali, Mouslim; Benaissa, Mohammed

2018-02-09

Nanostructured β-CoMoO₄ catalysts have been prepared via the thermal decomposition of an oxalate precursor. The catalyst was characterized by infrared spectroscopy (FTIR), X-ray diffraction (XRD), Brunauer-Emmett-Teller method (BET), energy dispersive X-ray spectroscopy (EDX), and transmission electron microscopy (TEM). The efficiency of these nanoparticles in the reduction of ortho - and meta -nitrophenol isomers (2-NP, 3-NP, and 4-NP) to their corresponding aminophenols was tested using UV-visible spectroscopy measurements. It was found that, with a β-CoMoO₄ catalyst, NaBH₄ reduces 3-NP instantaneously, whilst the reduction of 2-NP and 4-NP is slower at 8 min. This difference is thought to arise from the lower acidity of 3-NP, where the negative charge of the phenolate could not be delocalized onto the oxygen atoms of the meta-nitro group.

A Unique 3D Nitrogen-Doped Carbon Composite as High-Performance Oxygen Reduction Catalyst

PubMed Central

Karunagaran, Ramesh; Tung, Tran Thanh; Tran, Diana; Coghlan, Campbell; Doonan, Christian

2017-01-01

The synthesis and properties of an oxygen reduction catalyst based on a unique 3-dimensional (3D) nitrogen doped (N-doped) carbon composite are described. The composite material is synthesised via a two-step hydrothermal and pyrolysis method using bio-source low-cost materials of galactose and melamine. Firstly, the use of iron salts and galactose to hydrothermally produceiron oxide (Fe2O3) magnetic nanoparticle clusters embedded carbon spheres. Secondly, magnetic nanoparticles diffused out of the carbon sphere when pyrolysed in the presence of melamine as nitrogen precursor. Interestingly, many of these nanoparticles, as catalyst-grown carbon nanotubes (CNTs), resulted in the formation of N-doped CNTs and N-doped carbon spheres under the decomposition of carbon and a nitrogen environment. The composite material consists of integrated N-doped carbon microspheres and CNTs show high ORR activity through a predominantly four-electron pathway. PMID:28792432

Compatibility Studies of Hydrogen Peroxide and a New Hypergolic Fuel Blend

NASA Technical Reports Server (NTRS)

Baldridge, Jennifer; Villegas, Yvonne

2002-01-01

Several preliminary materials compatibility studies have been conducted to determine the practicality of a new hypergolic fuel system. Hypergolic fuel ignites spontaneously as the oxidizer decomposes and releases energy in the presence of the fuel. The bipropellant system tested consists of high-test hydrogen peroxide (HTP) and a liquid fuel blend consisting of a hydrocarbon fuel, an ignition enhancer and a transition metal catalyst. In order for further testing of the new fuel blend to take place, some basic materials compatibility and HTP decomposition studies must be accomplished. The thermal decomposition rate of HTP was tested using gas evolution and isothermal microcalorimetry (IMC). Materials were analyzed for compatibility with hydrogen peroxide including a study of the affect welding has on stainless steel elemental composition and its relation to HTP decomposition. Compatibility studies of valve materials in the fuel blend were performed to determine the corrosion resistance of the materials.

Organic hydrogen peroxide-driven low charge potentials for high-performance lithium-oxygen batteries with carbon cathodes

PubMed Central

Wu, Shichao; Qiao, Yu; Yang, Sixie; Ishida, Masayoshi; He, Ping; Zhou, Haoshen

2017-01-01

Reducing the high charge potential is a crucial concern in advancing the performance of lithium-oxygen batteries. Here, for water-containing lithium-oxygen batteries with lithium hydroxide products, we find that a hydrogen peroxide aqueous solution added in the electrolyte can effectively promote the decomposition of lithium hydroxide compounds at the ultralow charge potential on a catalyst-free Ketjen Black-based cathode. Furthermore, for non-aqueous lithium-oxygen batteries with lithium peroxide products, we introduce a urea hydrogen peroxide, chelating hydrogen peroxide without any water in the organic, as an electrolyte additive in lithium-oxygen batteries with a lithium metal anode and succeed in the realization of the low charge potential of ∼3.26 V, which is among the best levels reported. In addition, the undesired water generally accompanying hydrogen peroxide solutions is circumvented to protect the lithium metal anode and ensure good battery cycling stability. Our results should provide illuminating insights into approaches to enhancing lithium-oxygen batteries. PMID:28585527

Organic hydrogen peroxide-driven low charge potentials for high-performance lithium-oxygen batteries with carbon cathodes

NASA Astrophysics Data System (ADS)

Wu, Shichao; Qiao, Yu; Yang, Sixie; Ishida, Masayoshi; He, Ping; Zhou, Haoshen

2017-06-01

Reducing the high charge potential is a crucial concern in advancing the performance of lithium-oxygen batteries. Here, for water-containing lithium-oxygen batteries with lithium hydroxide products, we find that a hydrogen peroxide aqueous solution added in the electrolyte can effectively promote the decomposition of lithium hydroxide compounds at the ultralow charge potential on a catalyst-free Ketjen Black-based cathode. Furthermore, for non-aqueous lithium-oxygen batteries with lithium peroxide products, we introduce a urea hydrogen peroxide, chelating hydrogen peroxide without any water in the organic, as an electrolyte additive in lithium-oxygen batteries with a lithium metal anode and succeed in the realization of the low charge potential of ~3.26 V, which is among the best levels reported. In addition, the undesired water generally accompanying hydrogen peroxide solutions is circumvented to protect the lithium metal anode and ensure good battery cycling stability. Our results should provide illuminating insights into approaches to enhancing lithium-oxygen batteries.

Self-Protection Mechanism of Hexagonal WO3-Based DeNOx Catalysts against Alkali Poisoning.

PubMed

Zheng, Li; Zhou, Meijuan; Huang, Zhiwei; Chen, Yaxin; Gao, Jiayi; Ma, Zhen; Chen, Jianmin; Tang, Xingfu

2016-11-01

A good catalyst for efficiently controlling NO x emissions often demands strong resistance against alkali poisoning. Although the traditional ion-exchange model, based on acid-base reactions of alkalis with Brønsted acid sites, has been established over the past two decades, it is difficult to be used as a guideline to develop such an alkali-resistant catalyst. Here we establish a self-protection mechanism of deNO x catalysts against alkali poisoning by systematically studying the intrinsic nature of alkali resistance of V 2 O 5 /HWO (HWO = hexagonal WO 3 ) that shows excellent resistance to alkali poisoning in selective catalytic reduction of NO x with NH 3 (SCR). Synchrotron X-ray diffraction and absorption spectroscopies demonstrate that V 2 O 5 /HWO has spatially separated catalytically active sites (CASs) and alkali-trapping sites (ATSs). During the SCR process, ATSs spontaneously trap alkali ions such as K + , even if alkali ions initially block CASs, thus releasing CASs to realize the self-protection against alkali poisoning. X-ray photoelectron spectra coupled with theoretical calculations indicate that the electronic interaction between the alkali ions and ATSs with an energy saving is the driving force of the self-protection. This work provides a strategy to design alkali-resistant deNO x catalysts.

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.

Use of some oxides in radiolytical decomposition of water

NASA Astrophysics Data System (ADS)

Cecal, Al.; Goanta, M.; Palamaru, M.; Stoicescu, T.; Popa, K.; Paraschivescu, A.; Anita, V.

2001-10-01

This paper deals with a study on the radiolysis of water in the presence of certain oxides: BeO, SiO 2, TiO 2, ZrO 2 acting as catalysts for the hydrogen production. A radionuclide of 60Co with an activity of about 5×10 4 Ci was employed as an irradiation γ source. A considerable increase (up to ten times or more) of the amount of hydrogen resulting from the radiolysis of water in the presence of the above mentioned oxides was noticed in comparison with a reference sample, irradiated under the same experimental conditions, but without any catalyst. The radiolysis products have been identified by means of a method based on mass spectrometry.

Nanocrystal assembly for tandem catalysis

DOEpatents

Yang, Peidong; Somorjai, Gabor; Yamada, Yusuke; Tsung, Chia-Kuang; Huang, Wenyu

2014-10-14

The present invention provides a nanocrystal tandem catalyst comprising at least two metal-metal oxide interfaces for the catalysis of sequential reactions. One embodiment utilizes a nanocrystal bilayer structure formed by assembling sub-10 nm platinum and cerium oxide nanocube monolayers on a silica substrate. The two distinct metal-metal oxide interfaces, CeO.sub.2--Pt and Pt--SiO.sub.2, can be used to catalyze two distinct sequential reactions. The CeO.sub.2--Pt interface catalyzed methanol decomposition to produce CO and H.sub.2, which were then subsequently used for ethylene hydroformylation catalyzed by the nearby Pt--SiO.sub.2 interface. Consequently, propanal was selectively produced on this nanocrystal bilayer tandem catalyst.

In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks

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

Plonka, Anna M.; Wang, Qi; Gordon, Wesley O.

Recently, Zr-based metal organic frameworks (MOFs) were shown to be among the fastest catalysts of nerve-agent hydrolysis in solution. Here, we report a detailed study of the adsorption and decomposition of a nerve-agent simulant, dimethyl methylphosphonate (DMMP), on UiO-66, UiO-67, MOF-808, and NU-1000 using synchrotron-based X-ray powder diffraction, X-ray absorption, and infrared spectroscopy, which reveals key aspects of the reaction mechanism. The diffraction measurements indicate that all four MOFs adsorb DMMP (introduced at atmospheric pressures through a flow of helium or air) within the pore space. In addition, the combination of X-ray absorption and infrared spectra suggests direct coordination ofmore » DMMP to the Zr6 cores of all MOFs, which ultimately leads to decomposition to phosphonate products. Our experimental probes into the mechanism of adsorption and decomposition of chemical warfare agent simulants on Zr-based MOFs open new opportunities in rational design of new and superior decontamination materials.« less

In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks

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

Plonka, Anna M.; Wang, Qi; Gordon, Wesley O.

Zr-based metal organic frameworks (MOFs) have been recently shown to be among the fastest catalysts of nerve-agent hydrolysis in solution. We report a detailed study of the adsorption and decomposition of a nerve-agent simulant, dimethyl methylphosphonate (DMMP), on UiO-66, UiO-67, MOF-808, and NU-1000 using synchrotron-based X-ray powder diffraction, X-ray absorption, and infrared spectroscopy, which reveals key aspects of the reaction mechanism. The diffraction measurements indicate that all four MOFs adsorb DMMP (introduced at atmospheric pressures through a flow of helium or air) within the pore space. In addition, the combination of X-ray absorption and infrared spectra suggests direct coordination ofmore » DMMP to the Zr6 cores of all MOFs, which ultimately leads to decomposition to phosphonate products. These experimental probes into the mechanism of adsorption and decomposition of chemical warfare agent simulants on Zr-based MOFs open new opportunities in rational design of new and superior decontamination materials.« less

In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks

DOE PAGES

Plonka, Anna M.; Wang, Qi; Gordon, Wesley O.; ...

2016-12-30

Recently, Zr-based metal organic frameworks (MOFs) were shown to be among the fastest catalysts of nerve-agent hydrolysis in solution. Here, we report a detailed study of the adsorption and decomposition of a nerve-agent simulant, dimethyl methylphosphonate (DMMP), on UiO-66, UiO-67, MOF-808, and NU-1000 using synchrotron-based X-ray powder diffraction, X-ray absorption, and infrared spectroscopy, which reveals key aspects of the reaction mechanism. The diffraction measurements indicate that all four MOFs adsorb DMMP (introduced at atmospheric pressures through a flow of helium or air) within the pore space. In addition, the combination of X-ray absorption and infrared spectra suggests direct coordination ofmore » DMMP to the Zr6 cores of all MOFs, which ultimately leads to decomposition to phosphonate products. Our experimental probes into the mechanism of adsorption and decomposition of chemical warfare agent simulants on Zr-based MOFs open new opportunities in rational design of new and superior decontamination materials.« less

Hydrogen peroxide as sustainable fuel: electrocatalysts for production with a solar cell and decomposition with a fuel cell.

PubMed

Yamada, Yusuke; Fukunishi, Yurie; Yamazaki, Shin-ichi; Fukuzumi, Shunichi

2010-10-21

Hydrogen peroxide was electrochemically produced by reducing oxygen in an aqueous solution with [Co(TCPP)] as a catalyst and photovoltaic solar cell operating at 0.5 V. Hydrogen peroxide thus produced is utilized as a fuel for a one-compartment fuel cell with Ag-Pb alloy nanoparticles as the cathode.

Three-Dimensional Ordered Macroporous FePO4 as High-Efficiency Catalyst for Rechargeable Li-O2 Batteries.

PubMed

Li, Chao; Guo, Ziyang; Pang, Ying; Sun, Yunhe; Su, Xiuli; Wang, Yonggang; Xia, Yongyao

2016-11-23

The Li-O 2 battery is receiving much recent attention because of its superhigh theoretical energy density. However, its performance is limited by the irreversible formation/decomposition of Li 2 O 2 on the cathode and the undesired electrolyte decomposition. In this work, low-cost three-dimensional ordered macroporous (3DOM) FePO 4 is synthesized by using polystyrene (PS) spheres template in a facile experimental condition and applied as a high-efficiency catalyst for rechargeable Li-O 2 batteries, including good rate performance, high specific capacity, and perfect cycling stability. The superior performances can be attributed to the unique structure of 3DOM FePO 4 cathodes, which can provide an efficient buffer space for O 2 /Li 2 O 2 conversion. In addition, it is demonstrated that the Li + intercalation/deintercalation behavior of 3DOM FePO 4 in ether-based electrolyte can contribute to capacity for Li-O 2 batteries over cycling. As a result, when there is no O 2 in the environment, the Li-O 2 cell can also be operated as a rechargeable Li-FePO 4 cell with a perfect cycle capability.

Nitrogen Chemistry and Coke Transformation of FCC Coked Catalyst during the Regeneration Process

PubMed Central

Shi, Junjun; Guan, Jianyu; Guo, Dawei; Zhang, Jiushun; France, Liam John; Wang, Lefu; Li, Xuehui

2016-01-01

Regeneration of the coked catalyst is an important process of fluid catalytic cracking (FCC) in petroleum refining, however, this process will emit environmentally harmful gases such as nitrogen and carbon oxides. Transformation of N and C containing compounds in industrial FCC coke under thermal decomposition was investigated via TPD and TPO to examine the evolved gaseous species and TGA, NMR and XPS to analyse the residual coke fraction. Two distinct regions of gas evolution are observed during TPD for the first time, and they arise from decomposition of aliphatic carbons and aromatic carbons. Three types of N species, pyrrolic N, pyridinic N and quaternary N are identified in the FCC coke, the former one is unstable and tends to be decomposed into pyridinic and quaternary N. Mechanisms of NO, CO and CO2 evolution during TPD are proposed and lattice oxygen is suggested to be an important oxygen resource. Regeneration process indicates that coke-C tends to preferentially oxidise compared with coke-N. Hence, new technology for promoting nitrogen-containing compounds conversion will benefit the in-situ reduction of NO by CO during FCC regeneration. PMID:27270486

Probing properties of the interfacial perimeter sites in TiO x /Au/SiO 2 with 2-propanol decomposition

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

Wu, Yi Y.; Kung, Harold H.

The decomposition of 2-propanol was studied over SiO2, SiO2 with an overlayer of TiO2 (Ti/SiO2), Au/SiO2, and Au/SiO2 with an overlayer of TiO2 (Ti/[Au/SiO2]) at 170–190 °C. There was no reaction on SiO2. Propene was the only product on Ti/SiO2, and its rate of formation increased proportionally with the Ti content. Acetone was the major product (selectivity 65–99%) on all Au-containing catalysts. Its rate of formation also increased with Ti loading. In addition, small amounts of propene were also formed on Ti/[Au/SiO2] the rate of which increased with Ti loading. Characterization of the catalysts with N2 adsorption, STEM, DR-UV-vis spectroscopy,more » XPS, XANES and EXAFS suggested that the Ti formed an amorphous TiO2 overlayer on the catalyst. At high Ti loadings (4–5 wt.%), there were patches of thick porous TiO2 layer, and some microdomains of crystalline TiO2 could be detected. Au was present as 1–3 nm nanoparticles on all catalysts, before and after used in reaction. Only Lewis acid sites were detected based on results from pyridine adsorption, and their quantities increased with Ti loading. Based on the comparison of reaction rates, the dependence of the kinetics on 2-propanol partial pressure, the apparent activation energies, and the effect of co-feeding O2 among different catalysts, it was concluded that propene was formed on the TiO2 overlayer, acetone was formed primarily at the Au-TiO2 interfacial perimeter sites, and α-C-H bond breaking preceding acetone formation was more facile on Au at the interfacial site than other surface Au atoms. Implication of these results to the selective acetone formation in the oxidation of propane in the presence of a O2/H2 mixture was discussed.« less

Carbon-embedded Ni nanocatalysts derived from MOFs by a sacrificial template method for efficient hydrogenation of furfural to tetrahydrofurfuryl alcohol.

PubMed

Su, Yanping; Chen, Chun; Zhu, Xiaoguang; Zhang, Yong; Gong, Wanbing; Zhang, Haimin; Zhao, Huijun; Wang, Guozhong

2017-05-16

We report a fast and simple method for the synthesis of Ni-based metal-organic-frameworks (Ni-MOFs). Due to the existence of nickel ions and an organic ligand, the MOFs are employed as a sacrificial template for the facile preparation of carbon-embedded Ni (Ni/C) catalysts by a direct thermal decomposition method. The obtained Ni/C catalysts exhibit excellent catalytic activity for selectively transforming furfural (FAL) to tetrahydrofurfuryl alcohol (THFOL) due to the Ni nanoparticles (NPs) embedded uniformly in the ligand-derived carbon. The exemplified results illustrate that the catalytic performance of the Ni/C catalyst is greatly affected by the calcination conditions (temperature and time), composition of the Ni-MOF precursor and the catalysis conditions. The conversion of FAL and selectivity of THFOL both reached 100% under the conditions of 120 °C, 1 MPa H 2 pressure and 120 min of hydrogenation over the Ni/C-500 catalyst, derived from the pyrolysis of Ni-MOFs (Ni : BTC mole ratio of 1.0) at 500 °C for 120 min, which exhibits an average nanoparticle size of ∼14 nm and uniform dispersion, and the highest BET surface area (∼92 m 2 g -1 ) among all investigated Ni/C catalysts. This facilely prepared heterogeneous catalyst would be very promising for the replacement of noble metal catalysts for the efficient catalytic conversion of biomass-derived feedstocks into value-added chemicals.

Evaluation of Silica-Supported Metal and Metal Phosphide Nanoparticle Catalysts for the Hydrodeoxygenation of Guaiacol Under Ex Situ Catalytic Fast Pyrolysis Conditions

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

Griffin, Michael B.; Baddour, Frederick G.; Habas, Susan E.

A series of metal and metal phosphide catalysts were investigated for the hydrodeoxygenation of guaiacol under ex situ catalytic fast pyrolysis (CFP) conditions (350 °C, 0.5 MPa, 12 H 2:1 guaiacol, weight hourly space velocity 5 h $-$1). Ligand-capped Ni, Pt, Rh, Ni 2P, and Rh 2P nanoparticles (NPs) were prepared using solution-phase synthesis techniques and dispersed on a silica support. For the metal phosphide NP-catalysts, a synthetic route that relies on the decomposition of a single molecular precursor was employed. The reactivity of the NP-catalysts was compared to a series of reference materials including Ni/SiO 2 and Pt/SiO 2more » prepared using incipient wetness (IW) impregnation and a commercial (com) Pt/SiO 2 catalyst. The NP-Ni/SiO 2 catalyst exhibited the largest reduction in the oxygen mol% of the organic phase and outperformed the IW-Ni/SiO 2 material. Although it was less active for guaiacol conversion than NP-Ni/SiO 2, NP-Rh2P/SiO 2 demonstrated the largest production of completely deoxygenated products and the highest selectivity to anisole, benzene, and cyclohexane, suggesting that it is a promising catalyst for deoxygenation of aryl-OH bonds. Finally, the com-Pt/SiO 2 and IW-Pt/SiO 2 catalyst exhibited the highest normalized rate of guaiacol conversion per m 2 and per gram of active phase, respectively, but did not produce any completely deoxygenated products.« less

Evaluation of Silica-Supported Metal and Metal Phosphide Nanoparticle Catalysts for the Hydrodeoxygenation of Guaiacol Under Ex Situ Catalytic Fast Pyrolysis Conditions

DOE PAGES

Griffin, Michael B.; Baddour, Frederick G.; Habas, Susan E.; ...

2015-09-30

A series of metal and metal phosphide catalysts were investigated for the hydrodeoxygenation of guaiacol under ex situ catalytic fast pyrolysis (CFP) conditions (350 °C, 0.5 MPa, 12 H 2:1 guaiacol, weight hourly space velocity 5 h $-$1). Ligand-capped Ni, Pt, Rh, Ni 2P, and Rh 2P nanoparticles (NPs) were prepared using solution-phase synthesis techniques and dispersed on a silica support. For the metal phosphide NP-catalysts, a synthetic route that relies on the decomposition of a single molecular precursor was employed. The reactivity of the NP-catalysts was compared to a series of reference materials including Ni/SiO 2 and Pt/SiO 2more » prepared using incipient wetness (IW) impregnation and a commercial (com) Pt/SiO 2 catalyst. The NP-Ni/SiO 2 catalyst exhibited the largest reduction in the oxygen mol% of the organic phase and outperformed the IW-Ni/SiO 2 material. Although it was less active for guaiacol conversion than NP-Ni/SiO 2, NP-Rh2P/SiO 2 demonstrated the largest production of completely deoxygenated products and the highest selectivity to anisole, benzene, and cyclohexane, suggesting that it is a promising catalyst for deoxygenation of aryl-OH bonds. Finally, the com-Pt/SiO 2 and IW-Pt/SiO 2 catalyst exhibited the highest normalized rate of guaiacol conversion per m 2 and per gram of active phase, respectively, but did not produce any completely deoxygenated products.« less

Rational approach to polymer-supported catalysts: synergy between catalytic reaction mechanism and polymer design.

PubMed

Madhavan, Nandita; Jones, Christopher W; Weck, Marcus

2008-09-01

Supported catalysis is emerging as a cornerstone of transition metal catalysis, as environmental awareness necessitates "green" methodologies and transition metal resources become scarcer and more expensive. Although these supported systems are quite useful, especially in their capacity for transition metal catalyst recycling and recovery, higher activity and selectivity have been elusive compared with nonsupported catalysts. This Account describes recent developments in polymer-supported metal-salen complexes, which often surpass nonsupported analogues in catalytic activity and selectivity, demonstrating the effectiveness of a systematic, logical approach to designing supported catalysts from a detailed understanding of the catalytic reaction mechanism. Over the past few decades, a large number of transition metal complex catalysts have been supported on a variety of materials ranging from polymers to mesoporous silica. In particular, soluble polymer supports are advantageous because of the development of controlled and living polymerization methods that are tolerant to a wide variety of functional groups, including controlled radical polymerizations and ring-opening metathesis polymerization. These methods allow for tuning the density and structure of the catalyst sites along the polymer chain, thereby enabling the development of structure-property relationships between a catalyst and its polymer support. The fine-tuning of the catalyst-support interface, in combination with a detailed understanding of catalytic reaction mechanisms, not only permits the generation of reusable and recyclable polymer-supported catalysts but also facilitates the design and realization of supported catalysts that are significantly more active and selective than their nonsupported counterparts. These superior supported catalysts are accessible through the optimization of four basic variables in their design: (i) polymer backbone rigidity, (ii) the nature of the linker, (iii) catalyst site density, and (iv) the nature of the catalyst attachment. Herein, we describe the design of polymer supports tuned to enhance the catalytic activity or decrease, or even eliminate, decomposition pathways of salen-based transition metal catalysts that follow either a monometallic or a bimetallic reaction mechanism. These findings result in the creation of some of the most active and selective salen catalysts in the literature.

Permanganate oxidation of sulfur compounds to prevent poisoning of Pd catalysts in water treatment processes.

PubMed

Angeles-Wedler, Dalia; Mackenzie, Katrin; Kopinke, Frank-Dieter

2008-08-01

The practical application of Pd-catalyzed water treatment processes is impeded by catalyst poisoning by reduced sulfur compounds (RSCs). In this study, the potential of permanganate as a selective oxidant for the removal of microbially generated RSCs in water and as a regeneration agent for S-poisoned catalysts was evaluated. Hydrodechlorination using Pd/Al2O3 was carried out as a probe reaction in permanganate-pretreated water. The activity of the Pd catalysts in the successfully pretreated reaction medium was similar to that in deionized water. The catalyst showed no deactivation behavior in the presence of permanganate at a concentration level < or = 0.07 mM. With a residual oxidant concentration of > or = 0.08 mM, a significant but temporary inhibition of the catalytic dechlorination was observed. Unprotected Pd/Al2O3, which had been completely poisoned by sulfide, was reactivated by a combined treatment with permanganate and hydrazine. However, the anthropogenic water pollutants thiophene and carbon disulfide were resistant against permanganate. Together with the preoxidation of catalyst poisons, hydrophobic protection of the catalysts was studied. Pd/zeolite and various hydrophobically coated catalysts showed a higher stability against ionic poisons and permanganate than the uncoated catalyst. By means of a combination of oxidative water pretreatment and hydrophobic catalyst protection, we provide a new tool to harness the potential of Pd-catalyzed hydrodehalogenation for the treatment of real waters.

Decomposition of toluene in a steady-state atmospheric-pressure glow discharge

NASA Astrophysics Data System (ADS)

Trushkin, A. N.; Grushin, M. E.; Kochetov, I. V.; Trushkin, N. I.; Akishev, Yu. S.

2013-02-01

Results are presented from experimental studies of decomposition of toluene (C6H5CH3) in a polluted air flow by means of a steady-state atmospheric pressure glow discharge at different water vapor contents in the working gas. The experimental results on the degree of C6H5CH3 removal are compared with the results of computer simulations conducted in the framework of the developed kinetic model of plasma chemical decomposition of toluene in the N2: O2: H2O gas mixture. A substantial influence of the gas flow humidity on toluene decomposition in the atmospheric pressure glow discharge is demonstrated. The main mechanisms of the influence of humidity on C6H5CH3 decomposition are determined. The existence of two stages in the process of toluene removal, which differ in their duration and the intensity of plasma chemical decomposition of C6H5CH3 is established. Based on the results of computer simulations, the composition of the products of plasma chemical reactions at the output of the reactor is analyzed as a function of the specific energy deposition and gas flow humidity. The existence of a catalytic cycle in which hydroxyl radical OH acts a catalyst and which substantially accelerates the recombination of oxygen atoms and suppression of ozone generation when the plasma-forming gas contains water vapor is established.

FTIR study of methanol decomposition on gold catalyst for fuel cells

NASA Astrophysics Data System (ADS)

Boccuzzi, F.; Chiorino, A.; Manzoli, M.

The interaction of methanol (m), methanol-water (mw) and methanol-water-oxygen (mwo) on Au/TiO 2 catalyst has been investigated by in situ infrared spectroscopy (FTIR) and quadrupole mass spectrometry (QMS) at different temperatures. The aim of the work is to elucidate the nature and the abundance of the surface intermediates formed in different experimental conditions and to understand the mechanisms of methanol decomposition, of steam reforming and of combined reforming reactions. FTIR spectra run at room temperature in the different reaction mixtures show that differently coordinated methoxy species, that is on top species adsorbed on oxygen vacancy sites, on top species on uncoordinated Ti 4+ sites and bridged species on two Ti 4+ ions, are produced in all the mixtures. Quite strong formaldehyde and formate species adsorbed on gold are produced already at 403 K only in the combined reforming reaction mixture. At 473 K, on top species on uncoordinated Ti 4+ sites and methoxy species adsorbed on oxygen vacancy sites reduce their intensity and, at the same time, some formate species adsorbed on the support are produced in the steam reforming and combined reforming mixtures. At 523 K, on both methanol and methanol-water reaction mixtures, no more definite surface species are evidenced by FTIR on the catalysts, while in the methanol-water-oxygen mixture some residual methoxy and formate species are still present. Moreover, methanol is no more detected by QMS in the gas phase. A role of oxygen adsorbed on gold particles near oxygen vacancies of the support in the oxidative dehydrogenation of methanol is proposed.

Synthesis of 5'-O-DMT-2'-O-TBS Mononucleosides Using an Organic Catalyst.

PubMed

Lee, Sunggi; Blaisdell, Thomas P; Kasaplar, Pinar; Sun, Xixi; Tan, Kian L

2014-06-24

This unit describes a highly effective method to produce 5'-O-DMT-2'-O-TBS mononucleosides selectively using a small organic catalyst. This methodology avoids the tedious protection/deprotection strategy necessary to differentiate the 2'- and 3'-hydroxyl groups in a ribonucleoside. The catalyst was synthesized in two steps, starting from the condensation of valinol and cyclopentyl aldehyde, followed by anionic addition of N-methylimidazole. Ring closure of the amino alcohol with N,N-dimethylformamide dimethyl acetal in methanol furnishes the catalyst. All four 2'-O-TBS protected mono-nucleosides, U, A(Bz), G(Ib), and C(Ac), were produced in a single step using 10 to 20 mol% of the catalyst at room temperature with excellent yields and selectivity. Further transformation to phosphoramidite demonstrates the utility of this protocol in the preparation of monomers useful for automated synthesis of RNA. Copyright © 2014 John Wiley & Sons, Inc.

On the surface chemistry of molybdena-alumina catalysts prepared from Mo(CO) sub 6

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

Goldwasser, J.; Fang, S.M.; Houalla, M.

1989-01-01

Catalysts were prepared by subliming Mo(CO){sub 6} onto partially dehydroxylated (PDA) and exhaustively dehydroxylated (DA) alumina made from the same parent preparation (American Cyanamid Aero 100PHF). The chemisorption of NO and Co on these materials was studied using volumetric, chromatographic, and spectroscopic techniques. ESCA data indicated that metallic Mo crystals formed on Mo(CO){sub 6}/DA whereas on PDA both Mo{sup 4+} and some lower valence state, Mo{sup 2+} or Mo{sup 0}, were present. NO chemisorbed on both preparations at 195 K without releasing either N{sub 2}O or N{sub 2}. The chemisorption on the PDA preparations was over tenfold higher than thatmore » on the DA-supported catalysts under these conditions, but at 300 K the difference was reduced to a factor of 2. Moreover, redox chemistry occurred at this higher temperature as evidenced by the release of N{sub 2}O and N{sub 2}. The amounts of NO actually chemisorbed correlated well with the integrated IR band intensities. These data suggest that lower valence states are oxidized to Mo{sup 4+} at 300 K and that the observed IR bands stem from Mo{sup 4+}(NO){sub 2}, irrespective of the initial catalyst. Infrared spectra from residual CO remaining on decomposition of Mo(CO){sub 6} on DA and PDA showed bands which could be attributed to residual Mo(CO){sub 6} and/or to subcarbonyl species formed during decomposition. By 573 K, no residual bands could be observed. On adding-back CO at 300 K to the PDA preparation, bands at 1989 and 2170 cm{sup {minus}1} appeared, suggesting the presence of Mo{sup 4+} and residual Mo{sup 0}. Spectra from similar experiments with the DA preparation demonstrated that chemisorbed Mo(CO){sub 6} was reforming and possibly some subcarbonyl species.« less

Traits drive global wood decomposition rates more than climate.

PubMed

Hu, Zhenhong; Michaletz, Sean T; Johnson, Daniel J; McDowell, Nate G; Huang, Zhiqun; Zhou, Xuhui; Xu, Chonggang

2018-06-14

Wood decomposition is a major component of the global carbon cycle. Decomposition rates vary across climate gradients, which is thought to reflect the effects of temperature and moisture on the metabolic kinetics of decomposers. However, decomposition rates also vary with wood traits, which may reflect the influence of stoichiometry on decomposer metabolism as well as geometry relating the surface areas that decomposers colonize with the volumes they consume. In this paper, we combined metabolic and geometric scaling theories to formalize hypotheses regarding the drivers of wood decomposition rates, and assessed these hypotheses using a global compilation of data on climate, wood traits, and wood decomposition rates. Our results are consistent with predictions from both metabolic and geometric scaling theories. Approximately half of the global variation in decomposition rates was explained by wood traits (nitrogen content and diameter), while only a fifth was explained by climate variables (air temperature, precipitation, and relative humidity). These results indicate that global variation in wood decomposition rates is best explained by stoichiometric and geometric wood traits. Our findings suggest that inclusion of wood traits in global carbon cycle models can improve predictions of carbon fluxes from wood decomposition. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Stable Fe/ZSM-5 Nanosheet Zeolite Catalysts for the Oxidation of Benzene to Phenol

PubMed Central

2017-01-01

Fe/ZSM-5 nanosheet zeolites of varying thickness were synthesized with di- and tetraquaternary ammonium structure directing agents and extensively characterized for their textural, structural, and catalytic properties. Introduction of Fe3+ ions in the framework of nanosheet zeolites was slightly less effective than in bulk ZSM-5 zeolite. Steaming was necessary to activate all catalysts for N2O decomposition and benzene oxidation. The higher the Fe content, the higher the degree of Fe aggregation was after catalyst activation. The degree of Fe aggregation was lower when the crystal domain size of the zeolite or the Fe content was decreased. These two parameters had a substantial influence on the catalytic performance. Decreasing the number of Fe sites along the b-direction strongly suppressed secondary reactions of phenol and, accordingly, catalyst deactivation. This together with the absence of diffusional limitations in nanosheet zeolites explains the much higher phenol productivity obtainable with nanostructured Fe/ZSM-5. Steamed Fe/ZSM-5 zeolite nanosheet synthesized using C22-6-3·Br2 (domain size in b-direction ∼3 nm) and containing 0.24 wt % Fe exhibited the highest catalytic performance. During the first 24 h on stream, this catalyst produced 185 mmolphenol g–1. Calcination to remove the coke deposits completely restored the initial activity. PMID:28413693

40 CFR 90.427 - Catalyst thermal stress resistance evaluation.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Catalyst thermal stress resistance... Gaseous Exhaust Test Procedures § 90.427 Catalyst thermal stress resistance evaluation. (a) The purpose of the evaluation procedure specified in this section is to determine the effect of thermal stress on...

40 CFR 90.427 - Catalyst thermal stress resistance evaluation.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 21 2012-07-01 2012-07-01 false Catalyst thermal stress resistance... Gaseous Exhaust Test Procedures § 90.427 Catalyst thermal stress resistance evaluation. (a) The purpose of the evaluation procedure specified in this section is to determine the effect of thermal stress on...

40 CFR 90.427 - Catalyst thermal stress resistance evaluation.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 20 2014-07-01 2013-07-01 true Catalyst thermal stress resistance... Gaseous Exhaust Test Procedures § 90.427 Catalyst thermal stress resistance evaluation. (a) The purpose of the evaluation procedure specified in this section is to determine the effect of thermal stress on...

40 CFR 90.427 - Catalyst thermal stress resistance evaluation.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 21 2013-07-01 2013-07-01 false Catalyst thermal stress resistance... Gaseous Exhaust Test Procedures § 90.427 Catalyst thermal stress resistance evaluation. (a) The purpose of the evaluation procedure specified in this section is to determine the effect of thermal stress on...

40 CFR 90.427 - Catalyst thermal stress resistance evaluation.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 20 2011-07-01 2011-07-01 false Catalyst thermal stress resistance... Gaseous Exhaust Test Procedures § 90.427 Catalyst thermal stress resistance evaluation. (a) The purpose of the evaluation procedure specified in this section is to determine the effect of thermal stress on...

MICROWAVE-ASSISTED PREPARATION OF DIALKYLIMIDAZOLIUM TETRACHLOROALUMINATES AND THEIR USE AS CATALYSTS IN THE SOLVENT-FREE TETRAHYDROPYRANYLATION OF ALCOHOLS AND PHENOLS

EPA Science Inventory

Microwave-assisted preparation of dialkylimidazolium tetrachloroaluminates and their application as recyclable catalysts for the efficient and eco-friendly protection of alcohols as tetrahydropyranyl (THP) ethers are described; the same catalyst can also be utilized for the depro...

Thermal Decomposition of Calcium Perchlorate/Iron-Mineral Mixtures: Implications of the Evolved Oxygen from the Rocknest Eolian Deposit in Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Bruck, A. M.; Sutter, B.; Ming, D. W.; Mahaffy, P.

2014-01-01

A major oxygen release between 300 and 500 C was detected by the Mars Curiosity Rover Sample Analysis at Mars (SAM) instrument at the Rocknest eolian deposit. Thermal decomposition of perchlorate (ClO4-) salts in the Rocknest samples are a possible explanation for this evolved oxygen release. Releative to Na-, K-, Mg-, and Fe-perchlorate, the thermal decomposition of Ca-perchlorate in laboratory experiments released O2 in the temperature range (400-500degC) closest to the O2 release temperatures observed for the Rocknest material. Furthermore, calcium perchlorate could have been the source of Cl in the chlorinated-hydrocarbons species that were detected by SAM. Different components in the Martian soil could affect the decomposition temperature of calcium per-chlorate or another oxychlorine species. This interaction of the two components in the soil could result in O2 release temperatures consistent with those detected by SAM in the Rocknest materials. The decomposition temperatures of various alkali metal perchlorates are known to decrease in the presence of a catalyst. The objective of this work is to investigate catalytic interactions on calcium perchlorate from various iron-bearing minerals known to be present in the Rocknest material

Catalyst Complexed Carbon Slurry Fuel Development.

DTIC Science & Technology

1981-01-01

materials of fine particle size made by procedures denoted as furnace, channel , thermal, and lamp. Car- bon black materials are composed essentially of...far the largest group of commercially available materials, and are prepared by partial combustion of heavy hydrocarbon liquids. Channel blacks are...manufactured by impingement of natural gas flames on cold channel irons. Thermal blacks are produced by thermal decomposition of natural gas, while

The effect of peroxynitrite decomposition catalyst MnTBAP on aldehyde dehydrogenase-2 nitration by organic nitrates: role in nitrate tolerance.

PubMed

Mollace, Vincenzo; Muscoli, Carolina; Dagostino, Concetta; Giancotti, Luigino Antonio; Gliozzi, Micaela; Sacco, Iolanda; Visalli, Valeria; Gratteri, Santo; Palma, Ernesto; Malara, Natalia; Musolino, Vincenzo; Carresi, Cristina; Muscoli, Saverio; Vitale, Cristiana; Salvemini, Daniela; Romeo, Francesco

2014-11-01

Bioconversion of glyceryl trinitrate (GTN) into nitric oxide (NO) by aldehyde dehydrogenase-2 (ALDH-2) is a crucial mechanism which drives vasodilatory and antiplatelet effect of organic nitrates in vitro and in vivo. Oxidative stress generated by overproduction of free radical species, mostly superoxide anions and NO-derived peroxynitrite, has been suggested to play a pivotal role in the development of nitrate tolerance, though the mechanism still remains unclear. Here we studied the free radical-dependent impairment of ALDH-2 in platelets as well as vascular tissues undergoing organic nitrate ester tolerance and potential benefit when using the selective peroxynitrite decomposition catalyst Mn(III) tetrakis (4-Benzoic acid) porphyrin (MnTBAP). Washed human platelets were made tolerant to nitrates via incubation with GTN for 4h. This was expressed by attenuation of platelet aggregation induced by thrombin (40U/mL), an effect accompanied by GTN-related induction of cGMP levels in platelets undergoing thrombin-induced aggregation. Both effects were associated to attenuated GTN-induced nitrite formation in platelets supernatants and to prominent nitration of ALDH-2, the GTN to NO metabolizing enzyme, suggesting that GTN tolerance was associated to reduced NO formation via impairment of ALDH-2. These effects were all antagonized by co-incubation of platelets with MnTBAP, which restored GTN-induced responses in tolerant platelets. Comparable effect was found under in in vivo settings. Indeed, MnTBAP (10mg/kg, i.p.) significantly restored the hypotensive effect of bolus injection of GTN in rats made tolerants to organic nitrates via chronic administration of isosorbide-5-mononitrate (IS-5-MN), thus confirming the role of peroxynitrite overproduction in the development of tolerance to vascular responses induced by organic nitrates. In conclusion, oxidative stress subsequent to prolonged use of organic nitrates, which occurs via nitration of ALDH-2, represents a key event in GTN tolerance, an effect counteracted both in vitro and in vivo by novel peroxynitrite decomposition catalyst. Copyright © 2014 Elsevier Ltd. All rights reserved.

Biogas as a fuel for solid oxide fuel cells and synthesis gas production: effects of ceria-doping and hydrogen sulfide on the performance of nickel-based anode materials.

PubMed

Laycock, Christian J; Staniforth, John Z; Ormerod, R Mark

2011-05-28

Numerous investigations have been carried out into the conversion of biogas into synthesis gas (a mixture of H(2) + CO) over Ni/YSZ anode cermet catalysts. Biogas is a variable mixture of gases consisting predominantly of methane and carbon dioxide (usually in a 2 : 1 ratio, but variable with source), with other constituents including sulfur-containing gases such as hydrogen sulfide, which can cause sulfur poisoning of nickel catalysts. The effect of temperature on carbon deposition and sulfur poisoning of 90 : 10 mol% Ni/YSZ under biogas conversion conditions has been investigated by carrying out a series of catalytic reactions of methane-rich (2 : 1) CH(4)/CO(2) mixtures in the absence and presence of H(2)S over the temperature range 750-1000 °C. The effect of ceria-doping on carbon dioxide reforming, carbon deposition and sulfur tolerance has also been investigated by carrying out a similar series of reactions over ceria-doped Ni/YSZ. Ceria was doped at 5 mol% of the nickel content to give an anode catalyst composition of 85.5 : 4.5 : 10 mol% Ni/CeO(2)/YSZ. Reactions were followed using quadrupolar mass spectrometry (QMS) and the amount of carbon deposition was analysed by subjecting the reacted catalyst samples to a post-reaction temperature programmed oxidation (TPO). On undoped Ni/YSZ, carbon deposition occurred predominantly through thermal decomposition of methane. Ceria-doping significantly suppressed methane decomposition and at high temperatures simultaneously promoted the reverse Boudouard reaction, significantly lowering carbon deposition. Sulfur poisoning of Ni/YSZ occurred in two phases, the first of which caused the most activity loss and was accelerated on increasing the reaction temperature, while the second phase had greater stability and became more favourable with increasing reaction temperature. Adding H(2)S significantly inhibited methane decomposition, resulting in much less carbon deposition. Ceria-doping significantly increased the sulfur tolerance of Ni/YSZ, however, in the presence of H(2)S ceria did not promote the reverse Boudouard reaction and at high temperatures carbon deposition was greater over ceria-doped Ni/YSZ. In order to further study the effects of ceria-doping, a solid oxide fuel cell (SOFC) was constructed with a ceria-doped anode cermet and its electrical performance on simulated biogas compared to hydrogen was tested. This fuel cell was subsequently ran for 1000 h on simulated biogas with no degradation in its overall electrical performance.

Surface chemistry and catalytic properties of VOX/Ti-MCM-41 catalysts for dibenzothiophene oxidation in a biphasic system

NASA Astrophysics Data System (ADS)

González, J.; Chen, L. F.; Wang, J. A.; Manríquez, Ma.; Limas, R.; Schachat, P.; Navarrete, J.; Contreras, J. L.

2016-08-01

A series of vanadium oxide supported on Ti-MCM-41 catalysts was synthesized via the incipient impregnation method by varying the vanadia loading from 5 wt% to 10, 15, 20 and 25 wt%. These catalysts were characterized by a variety of advanced techniques for investigating their crystalline structure, textural properties, and surface chemistry information including surface acidity, reducibility, vanadium oxidation states, and morphological features. The catalytic activities of the catalysts were evaluated in a biphasic reaction system for oxidative desulfurization (ODS) of a model diesel containing 300 ppm of dibenzothiophene (DBT) where acetonitrile was used as extraction solvent and H2O2 as oxidant. ODS activity was found to be proportional to the V5+/(V4+ + V5+) values of the catalysts, indicating that the surface vanadium pentoxide (V2O5) was the active phase. Reaction temperature would influence significantly the ODS efficiency; high temperature, i.e., 80 °C, would lead to low ODS reaction due to the partial decomposition of oxidant. All the catalysts contained both Lewis and Brønsted acid sites but the former was predominant. The catalysts with low vanadia loading (5 or 10 wt%V2O5) had many Lewis acid sites and could strongly adsorb DBT molecule via the electron donation/acceptance action which resulted in an inhibition for the reaction of DBT with the surface peroxometallic species. The catalyst with high vanadia loading (25wt%V2O5/Ti-MCM-41) showed the highest catalytic activity and could remove 99.9% of DBT at 60 °C within 60 min.

Degradation reaction of Diazo reactive black 5 dye with copper (II) sulfate catalyst in thermolysis treatment.

PubMed

Lau, Yen-Yie; Wong, Yee-Shian; Ang, Tze-Zhang; Ong, Soon-An; Lutpi, Nabilah Aminah; Ho, Li-Ngee

2018-03-01

The theme of present research demonstrates performance of copper (II) sulfate (CuSO 4 ) as catalyst in thermolysis process to treat reactive black 5 (RB 5) dye. During thermolysis without presence of catalyst, heat was converted to thermal energy to break the enthalpy of chemical structure bonding and only 31.62% of color removal. With CuSO 4 support as auxiliary agent, the thermally cleaved molecular structure was further destabilized and reacted with CuSO 4 . Copper ions functioned to delocalize the coordination of π of the lone paired electron in azo bond, C=C bond of the sp 2 carbon to form C-C of the sp 3 amorphous carbon in benzene and naphthalene. Further, the radicals of unpaired electrons were stabilized and RB 5 was thermally decomposed to methyl group. Zeta potential measurement was carried out to analyze the mechanism of RB 5 degradation and measurement at 0 mV verified the critical chemical concentration (CCC) (0.7 g/L copper (II) sulfate), as the maximum 92.30% color removal. The presence of copper (II) sulfate catalyst has remarkably increase the RB 5 dye degradation as the degradation rate constant without catalyst, k 1 is 6.5224 whereas the degradation rate constant with catalyst, k 2 is 25.6810. This revealed the correlation of conversion of thermal energy from heat to break the chemical bond strength, subsequent fragmentation of RB 5 dye molecular mediated by copper (II) sulfate catalyst. The novel framework on thermolysis degradation of molecular structure of RB 5 with respect to the bond enthalpy and interfacial intermediates decomposition with catalyst reaction were determined.

N-Heterocycle-Fused Pentalenes by a Gold-Catalyzed Annulation of Diethynyl-Quinoxalines and -Phenazines.

PubMed

Sekine, Kohei; Stuck, Fabian; Schulmeister, Jürgen; Wurm, Thomas; Zetschok, Dominik; Rominger, Frank; Rudolph, Matthias; Hashmi, A Stephen K

2018-06-19

The gold-catalyzed annulation of diethynyl N-heterocycles for the synthesis of quinoxaline-/phenazine-based pentalenes, and the study of their optoelectronic properties is described. The inhibition of the gold catalyst by the nitrogen centers in the substrate and the product could be overcome by increasing the reaction temperature to 130 °C, which in gold catalysis usually leads to catalyst decomposition. At 130 °C 6,7-di(arylethynyl)quinoxalines in chlorobenzene at afford the corresponding pentalenes. The annulation of 2,3-di(arylethynyl)quinoxalines requires an even higher temperature under microwave irradiation. The quinoxaline-based pentalenes showed lower LUMO levels compared to the corresponding naphthalene-based pentalenes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fundamentals of Hydrocarbon Upgrading to Liquid Fuels and Commodity Chemicals over Catalytic Metallic Nanoparticles

NASA Astrophysics Data System (ADS)

Chen, Tao

Promising new technologies for biomass conversion into fuels and chemical feedstocks rely on the production of bio-oils, which need to be upgraded in order to remove oxygen-containing hydrocarbons and water. A high oxygen concentration makes bio-oils acidic and corrosive, unstable during storage, and less energetically valuable per unit weight than petroleum-derived hydrocarbons. Although there are efficient processes for the production of bio-oils, there are no efficient technologies for their upgrading. Current technologies utilize traditional petroleum refining catalysts, which are not optimized for biomass processing. New upgrading technologies are, therefore, urgently needed for development of sustainable energy resources. Development of such new technologies, however, is severely hindered by a lack of fundamental understanding of how oxygen and oxygen-containing hydrocarbons derived from biomass interact with promising noble-metal catalysts. In this study, kinetic reaction measurements, catalyst characterization and quantum chemical calculations using density functional theory were combined for determining adsorption modes and reaction mechanisms of hydrocarbons in the presence of oxygen on surfaces of catalytic noble-metal nanoparticles. The results were used for developing improved catalyst formulations and optimization of reaction conditions. The addition of molybdenum to platinum catalysts was shown to improve catalytic activity, stability, and selectivity in hydrodeoxygenation of acetic acid, which served as a model biomass compound. The fundamental results that describe interactions of oxygen and hydrocarbons with noble-metal catalysts were extended to other reactions and fields of study: evaluation of the reaction mechanism for hydrogen peroxide decomposition, development of improved hydrogenation catalysts and determination of adsorption modes of a spectroscopic probe molecule.

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.

Porous Nanocrystalline Silicon Supported Bimetallic Pd-Au Catalysts: Preparation, Characterization, and Direct Hydrogen Peroxide Synthesis

PubMed Central

Potemkin, Dmitriy I.; Maslov, Dmitry K.; Loponov, Konstantin; Snytnikov, Pavel V.; Shubin, Yuri V.; Plyusnin, Pavel E.; Svintsitskiy, Dmitry A.; Sobyanin, Vladimir A.; Lapkin, Alexei A.

2018-01-01

Bimetallic Pd-Au catalysts were prepared on the porous nanocrystalline silicon (PSi) for the first time. The catalysts were tested in the reaction of direct hydrogen peroxide synthesis and characterized by standard structural and chemical techniques. It was shown that the Pd-Au/PSi catalyst prepared from conventional H2[PdCl4] and H[AuCl4] precursors contains monometallic Pd and a range of different Pd-Au alloy nanoparticles over the oxidized PSi surface. The PdAu2/PSi catalyst prepared from the [Pd(NH3)4][AuCl4]2 double complex salt (DCS) single-source precursor predominantly contains bimetallic Pd-Au alloy nanoparticles. For both catalysts the surface of bimetallic nanoparticles is Pd-enriched and contains palladium in Pd0 and Pd2+ states. Among the catalysts studied, the PdAu2/PSi catalyst was the most active and selective in the direct H2O2 synthesis with H2O2 productivity of 0.5 mol gPd-1 h-1 at selectivity of 50% and H2O2 concentration of 0.023 M in 0.03 M H2SO4-methanol solution after 5 h on stream at −10°C and atmospheric pressure. This performance is due to high activity in the H2O2 synthesis reaction and low activities in the undesirable H2O2 decomposition and hydrogenation reactions. Good performance of the PdAu2/PSi catalyst was associated with the major part of Pd in the catalyst being in the form of the bimetallic Pd-Au nanoparticles. Porous silicon was concluded to be a promising catalytic support for direct hydrogen peroxide synthesis due to its inertness with respect to undesirable side reactions, high thermal stability, and conductivity, possibility of safe operation at high temperatures and pressures and a well-established manufacturing process. PMID:29637068

Porous nanocrystalline silicon supported bimetallic Pd-Au catalysts: preparation, characterization and direct hydrogen peroxide synthesis

NASA Astrophysics Data System (ADS)

Potemkin, Dmitriy I.; Maslov, Dmitry K.; Loponov, Konstantin; Snytnikov, Pavel V.; Shubin, Yuri V.; Plyusnin, Pavel E.; Svintsitskiy, Dmitry A.; Sobyanin, Vladimir A.; Lapkin, Alexei A.

2018-03-01

Bimetallic Pd-Au catalysts were prepared on the porous nanocrystalline silicon (PSi) for the first time. The catalysts were tested in the reaction of direct hydrogen peroxide synthesis and characterised by standard structural and chemical techniques. It was shown that the Pd-Au/PSi catalyst prepared from conventional H2[PdCl4] and H[AuCl4] precursors contains monometallic Pd and a range of different Pd-Au alloy nanoparticles over the oxidized PSi surface. The PdAu2/PSi catalyst prepared from the [Pd(NH3)4][AuCl4]2 double complex salt single-source precursor predominantly contains bimetallic Pd-Au alloy nanoparticles. For both catalysts the surface of bimetallic nanoparticles is Pd-enriched and contains palladium in Pd0 and Pd2+ states. Among the catalysts studied, the PdAu2/PSi catalyst was the most active and selective in the direct H2O2 synthesis with H2O2 productivity of 0.5 at selectivity of 50 % and H2O2 concentration of 0.023 M in 0.03 M H2SO4-methanol solution after 5 h on stream at -10 °C and atmospheric pressure. This performance is due to high activity in the H2O2 synthesis reaction and low activities in the undesirable H2O2 decomposition and hydrogenation reactions. Good performance of the PdAu2/PSi catalyst was associated with the major part of Pd in the catalyst being in the form of the bimetallic Pd-Au nanoparticles. Porous silicon was concluded to be a promising catalytic support for direct hydrogen peroxide synthesis due to its inertness with respect to undesirable side reactions, high thermal stability and conductivity, possibility of safe operation at high temperatures and pressures and a well-established manufacturing process.

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.

The role of carbon solubility in Fe-C nano-clusters on the growth of small single-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Curtarolo, Stefano; Awasthy, Neha; Setyawan, Wahyu; Mora, Elena; Tokune, Toshio; Bolton, Kim; Harutyunyan, Avetik

2008-03-01

Various diameters of alumina-supported Fe catalysts are used to grow single-walled carbon nanotubes (SWCNTs) with chemical vapor decomposition. We find that the reduction of the catalyst size requires an increase of the minimum temperature necessary for the growth. We address this phenomenon in terms of solubility of C in Fe nanoclusters and, by using first principles calculations, we devise a simple model to predict the behavior of the phases competing for stability in Fe-C nanoclusters at low temperature. We show that, as a function particles size, there are three scenarios compatible with steady state-, limited- and no-growth of SWCNTs, corresponding to unaffected, reduced and no solubility of C in the particles. The result raises previously unknown concerns about the growth feasibility of small and very-long SWCNTs within the current Fe CVD technology, and suggests new strategies in the search of better catalysts. Research supported by Honda R.I. and NSF.

Cuboid Ni2 P as a Bifunctional Catalyst for Efficient Hydrogen Generation from Hydrolysis of Ammonia Borane and Electrocatalytic Hydrogen Evolution.

PubMed

Du, Yeshuang; Liu, Chao; Cheng, Gongzhen; Luo, Wei

2017-11-16

The design of high-performance catalysts for hydrogen generation is highly desirable for the upcoming hydrogen economy. Herein, we report the colloidal synthesis of nanocuboid Ni 2 P by the thermal decomposition of nickel chloride hexahydrate (NiCl 2 ⋅6 H 2 O) and trioctylphosphine. The obtained nanocuboid Ni 2 P was characterized by using powder X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and inductively coupled plasma atomic emission spectroscopy. For the first time, the as-synthesized nanocuboid Ni 2 P is used as a bifunctional catalyst for hydrogen generation from the hydrolysis of ammonia borane and electrocatalytic hydrogen evolution. Owing to the strong synergistic electronic effect between Ni and P, the as-synthesized Ni 2 P exhibits catalytic performance that is superior to its counterpart without P doping. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Atomic-Level Structural Dynamics of Polyoxoniobates during DMMP Decomposition

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

Wang, Qi; Chapleski, Robert C.; Plonka, Anna M.

Ambient pressure in situ synchrotron-based spectroscopic techniques have been correlated to illuminate atomic-level details of bond breaking and formation during the hydrolysis of a chemical warfare nerve agent simulant over a polyoxometalate catalyst. Specifically, a Cs 8[Nb 6O 19] polyoxoniobate catalyst has been shown to react readily with dimethyl methylphosphonate (DMMP). The atomic-level transformations of all reactant moieties, the [Nb 6O 19] 8- polyanion, its Cs + counterions, and the DMMP substrate, were tracked under ambient conditions by a combination of X-ray absorption fine structure spectroscopy, Raman spectroscopy, and X-ray diffraction. Results reveal that the reaction mechanism follows general basemore » (in contrast to specific base) hydrolysis. Together with computational results, the work demonstrates that the ultimate fate of DMMP hydrolysis at the Cs 8[Nb 6O 19] catalyst is strong binding of the (methyl) methylphosphonic acid ((M)MPA) product to the polyanions, which ultimately inhibits catalytic turnover.« less

Modeling of the HiPco process for carbon nanotube production. I. Chemical kinetics

NASA Technical Reports Server (NTRS)

Dateo, Christopher E.; Gokcen, Tahir; Meyyappan, M.

2002-01-01

A chemical kinetic model is developed to help understand and optimize the production of single-walled carbon nanotubes via the high-pressure carbon monoxide (HiPco) process, which employs iron pentacarbonyl as the catalyst precursor and carbon monoxide as the carbon feedstock. The model separates the HiPco process into three steps, precursor decomposition, catalyst growth and evaporation, and carbon nanotube production resulting from the catalyst-enhanced disproportionation of carbon monoxide, known as the Boudouard reaction: 2 CO(g)-->C(s) + CO2(g). The resulting detailed model contains 971 species and 1948 chemical reactions. A second model with a reduced reaction set containing 14 species and 22 chemical reactions is developed on the basis of the detailed model and reproduces the chemistry of the major species. Results showing the parametric dependence of temperature, total pressure, and initial precursor partial pressures are presented, with comparison between the two models. The reduced model is more amenable to coupled reacting flow-field simulations, presented in the following article.

Atomic-Level Structural Dynamics of Polyoxoniobates during DMMP Decomposition

DOE PAGES

Wang, Qi; Chapleski, Robert C.; Plonka, Anna M.; ...

2017-04-10

Ambient pressure in situ synchrotron-based spectroscopic techniques have been correlated to illuminate atomic-level details of bond breaking and formation during the hydrolysis of a chemical warfare nerve agent simulant over a polyoxometalate catalyst. Specifically, a Cs 8[Nb 6O 19] polyoxoniobate catalyst has been shown to react readily with dimethyl methylphosphonate (DMMP). The atomic-level transformations of all reactant moieties, the [Nb 6O 19] 8- polyanion, its Cs + counterions, and the DMMP substrate, were tracked under ambient conditions by a combination of X-ray absorption fine structure spectroscopy, Raman spectroscopy, and X-ray diffraction. Results reveal that the reaction mechanism follows general basemore » (in contrast to specific base) hydrolysis. Together with computational results, the work demonstrates that the ultimate fate of DMMP hydrolysis at the Cs 8[Nb 6O 19] catalyst is strong binding of the (methyl) methylphosphonic acid ((M)MPA) product to the polyanions, which ultimately inhibits catalytic turnover.« less

Biochemical Control of Fungal Biomass and Enzyme Production During Native Hawaiian Litter Degradation

NASA Astrophysics Data System (ADS)

Amatangelo, K. L.; Cordova, T. P.; Vitousek, P. M.

2007-12-01

Microbial growth and enzyme production during decomposition is controlled by the availability of carbon substrates, essential elements, and the ratios of these (such as lignin:N). We manipulated carbon:nutrient stoichiometry during decomposition using a natural fertility gradient in Hawaii and litter of varying initial biochemistry. We collected freshly senesced litter of seven biochemically distinct species from three sites offering differing levels of N, P, cations, and 15N , but similar yearly rainfall and temperature patterns. Litter types were decomposed at both the sites they were collected, and at the other site(s) that species was found. Litter was collected at multiple time points, and after one year of decomposition, calculated K constants varied an order of magnitude, from 0.276 to 2.76. Decomposition rates varied significantly with both litter site of origin and deployment, except at the oldest, P-limited site, where litter site of origin was not significantly correlated with decomposition within species. As microbial exocellular enzymes provide the catalyst for the breakdown of organic molecules including phenols, cellulose, and cutin, we assayed polyphenol oxidase, cellobiohydrolase, cutinase, chitinase, and lignin peroxidase to evaluate the breakdown sequence of different litter types. To measure the fungal biomass accumulating during decomposition, we extracted (22E)-Ergosta-5,7,22-trien-3beta- ol (ergosterol) on a subset of samples. The production of particular exocellular enzymes on litter species responded distinctly to origin and decomposition sites: after six months, chitinase and cellobiohydrolase were significantly affected by origin site, whereas polyphenol oxidase activity was controlled by deployment site. We conclude that site characteristics can alter the interaction between litter carbon:nutrient ratios and decomposition rate, mediated through microbial biomass and enzyme production.

First-principles study on the initial decomposition process of CH3NH3PbI3

NASA Astrophysics Data System (ADS)

Xue, Yuanbin; Shan, Yueyue; Xu, Hu

2017-09-01

Hybrid perovskites are promising materials for high-performance photovoltaics. Unfortunately, hybrid perovskites readily decompose in particular under humid conditions, and the mechanisms of this phenomenon have not yet been fully understood. In this work, we systematically studied the possible mechanisms and the structural properties during the initial decomposition process of MAPbI3 (MA = CH3NH3+) using first-principles calculations. The theoretical results show that it is energetically favorable for PbI2 to nucleate and crystalize from the MAPbI3 matrix ahead of other decomposition products. Additionally, the structural instability is an intrinsic property of MAPbI3, regardless of whether the system is exposed to humidity. We find that H2O could facilitate the desorption of gaseous components, acting as a catalyst to transfer the H+ ion. These results provide insight into the cause of the instability of MAPbI3 and may improve our understanding of the properties of hybrid perovskites.

Preparation and catalytic activities of LaFeO3 and Fe2O3 for HMX thermal decomposition.

PubMed

Wei, Zhi-Xian; Xu, Yan-Qing; Liu, Hai-Yan; Hu, Chang-Wen

2009-06-15

Perovskite-type LaFeO(3) and alpha-Fe(2)O(3) with high specific surface areas were directly prepared with appropriate stearic acid-nitrates ratios by a novel stearic acid solution combustion method. The obtained powders were characterized by XRD, FT-IR and XPS techniques. The catalytic activities of perovskite-type LaFeO(3) and alpha-Fe(2)O(3) for the thermal decomposition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) were investigated by TG and TG-EGA techniques. The experimental results show that the catalytic activity of perovskite-type LaFeO(3) was much higher than that of alpha-Fe(2)O(3) because of higher concentration of surface-adsorbed oxygen (O(ad)) and hydroxyl of LaFeO(3). The study points out a potential way to develop new and more active perovskite-type catalysts for the HMX thermal decomposition.

Lattice Matched Carbide–Phosphide Composites with Superior Electrocatalytic Activity and Stability

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

Regmi, Yagya N.; Roy, Asa; King, Laurie A.

Composites of electrocatalytically active transition-metal compounds present an intriguing opportunity toward enhanced activity and stability. Here, to identify potentially scalable pairs of a catalytically active family of compounds, we demonstrate that phosphides of iron, nickel, and cobalt can be deposited on molybdenum carbide to generate nanocrystalline heterostructures. Composites synthesized via solvothermal decomposition of metal acetylacetonate salts in the presence of highly dispersed carbide nanoparticles show hydrogen evolution activities comparable to those of state-of-the-art non-noble metal catalysts. Investigation of the spent catalyst using high resolution microscopy and elemental analysis reveals that formation of carbide–phosphide composite prevents catalyst dissolution in acid electrolyte.more » Lattice mismatch between the two constituent electrocatalysts can be used to rationally improve electrochemical stability. Among the composites of iron, nickel, and cobalt phosphide, iron phosphide displays the lowest degree of lattice mismatch with molybdenum carbide and shows optimal electrochemical stability. Turnover rates of the composites are higher than that of the carbide substrate and compare favorably to other electrocatalysts based on earth-abundant elements. Lastly, our findings will inspire further investigation into composite nanocrystalline electrocatalysts that use molybdenum carbide as a stable catalyst support.« less

Sol-gel (template) synthesis of macroporous Mo-based catalysts for hydrothermal oxidation of radionuclide-organic complexes

NASA Astrophysics Data System (ADS)

Papynov, E. K.; Palamarchuk, M. S.; Mayorov, V. Yu; Modin, E. B.; Portnyagin, A. S.; Sokol'nitskaya, T. A.; Belov, A. A.; Tananaev, I. G.; Avramenko, V. A.

2017-07-01

Molybdenum compounds are industrially demanding as heterogeneous catalysts for oxidation of various organic substances. Highly porous structure of molybdenum-containing catalysts avoids surface's colmatation and prevents blocking catalytic sites that makes these materials play a key role in processes of hydrothermal oxidation of radionuclide organic complexes. The study presents an original way of sol-gel synthesis of new macroporous molybdenum compounds using ;core-shell; colloid template (polymer latex) as poreforming agent. We have described three individual routs of template removal via thermal decomposition to obtain porous materials based on molybdenum compounds. Thermal treatment conditions (temperature, gaseous atmosphere) have been studied with respect to their influence on composition, structure and catalytic properties of synthesized molybdenum systems. The optimal way to synthesis of crystal molybdenum (VI) oxide with ordered porous structure (mean pore size 100-160 nm) has been suggested. Catalytic properties of macroporous molybdenum materials have been investigated in the process of liquid phase and hydrothermal oxidation of such organic substances thiazine and stable Co-EDTA complex. It was shown that macroporous molybdenum oxides could be applied as prospective catalysts for hydrothermal oxidation of organic radionuclide complexes during the processing of radioactive waste.

pH-insusceptible cobalt-manganese immobilizing mesoporous siliceous MCM-41 catalyst for ozonation of dimethyl phthalate.

PubMed

Tang, Yiming; Pan, Zhaoqi; Li, Laisheng

2017-12-15

Mesoporous siliceous MCM-41 immobilized with Co and Mn metal ions (Co-Mn-MCM-41) was synthesized using a hydrothermal method. The structural regularity and the valence states of the metal species were measured by X-ray diffractometer and X-ray photoelectron spectrometer. The resultant bimetallic Co-Mn-MCM-41 catalyst was tested for the degradation of dimethyl phthalate (DMP) via a catalytic ozonation mechanism, demonstrating that the catalytic properties of Co-Mn-MCM-41 catalyst significantly accelerated the ozonation process. Total organic carbon (TOC) and DMP removal efficiency reached 94% and 99.7% at 15min under the optimal conditions. The oxidation pathways were proposed after identifying the intermediate products from ozonation using a gas chromatography-mass spectrometer. The enhanced catalytic reactivity was attributed to the highly-dispersive cobalt and manganese species in MCM-41 scaffolds, which promoted the ozone decomposition and hydroxyl radicals' generation in catalytic ozonation and accelerated the degradation of DMP. Bimetallic Co-Mn-MCM-41 catalyst remained stable in mild acidic conditions and continued to show high activity after repeated runs. Copyright © 2017 Elsevier Inc. All rights reserved.

Lattice Matched Carbide–Phosphide Composites with Superior Electrocatalytic Activity and Stability

DOE PAGES

Regmi, Yagya N.; Roy, Asa; King, Laurie A.; ...

2017-10-19

Composites of electrocatalytically active transition-metal compounds present an intriguing opportunity toward enhanced activity and stability. Here, to identify potentially scalable pairs of a catalytically active family of compounds, we demonstrate that phosphides of iron, nickel, and cobalt can be deposited on molybdenum carbide to generate nanocrystalline heterostructures. Composites synthesized via solvothermal decomposition of metal acetylacetonate salts in the presence of highly dispersed carbide nanoparticles show hydrogen evolution activities comparable to those of state-of-the-art non-noble metal catalysts. Investigation of the spent catalyst using high resolution microscopy and elemental analysis reveals that formation of carbide–phosphide composite prevents catalyst dissolution in acid electrolyte.more » Lattice mismatch between the two constituent electrocatalysts can be used to rationally improve electrochemical stability. Among the composites of iron, nickel, and cobalt phosphide, iron phosphide displays the lowest degree of lattice mismatch with molybdenum carbide and shows optimal electrochemical stability. Turnover rates of the composites are higher than that of the carbide substrate and compare favorably to other electrocatalysts based on earth-abundant elements. Lastly, our findings will inspire further investigation into composite nanocrystalline electrocatalysts that use molybdenum carbide as a stable catalyst support.« less

Catalysts for long-life closed-cycle CO2 lasers

NASA Technical Reports Server (NTRS)

Schryer, David R.; Sidney, Barry D.; Miller, Irvin M.; Hess, Robert V.; Wood, George M.; Batten, Carmen E.; Burney, Lewis G.; Hoyt, Ronald F.; Paulin, Patricia A.; Brown, Kenneth G.

1987-01-01

Long-life, closed-cycle operation of pulsed CO2 lasers requires catalytic CO-O2 recombination both to remove O2, which is formed by discharge-induced CO2 decomposition, and to regenerate CO2. Platinum metal on a tin (IV) oxide substrate (Pt/SnO2) has been found to be an effective catalyst for such recombination in the desired temperature range of 25 to 100 C. This paper presents a description of ongoing research at NASA-LaRC on Pt/SnO2 catalyzed CO-O2 recombination. Included are studies with rare-isotope gases since rare-isotope CO2 is desirable as a laser gas for enhanced atmospheric transmission. Results presented include: (1) achievement of 98% to 100% conversion of a stoichiometric mixture of CO and O2 to CO2 for 318 hours (greater than 1 x 10 to the 6th power seconds), continuous, at a catalyst temperature of 60 C, and (2) development of a technique verified in a 30-hour test, to prevent isotopic scrambling when CO-18 and O-18(2) are reacted in the presence of a common-isotope Pt/Sn O-16(2) catalyst.

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.

Catalytic decomposition of nitrous oxide monopropellant for hybrid motor ignition

NASA Astrophysics Data System (ADS)

Wilson, Matthew

Nitrous oxide (N2O) is an inexpensive and readily available non-toxic rocket motor oxidizer. It is the most commonly used oxidizer for hybrid bipropellant rocket systems, and several bipropellant liquid rocket designs have also used nitrous oxide. In liquid form, N2O is highly stable, but in vapor form it has the potential to decompose exothermically, releasing up to 1865 Joules per gram of vapor as it dissociates into nitrogen and oxygen. Consequently, it has long been considered as a potential "green" replacement for existing highly toxic and dangerous monopropellants. This project investigates the feasibility of using the nitrous oxide decomposition reaction as a monopropellant energy source for igniting liquid bipropellant and hybrid rockets that already use nitrous oxide as the primary oxidizer. Because nitrous oxide is such a stable propellant, the energy barrier to dissociation is quite high; normal thermal decomposition of the vapor phase does not occur until temperatures are above 800 C. The use of a ruthenium catalyst decreases the activation energy for this reaction to allow rapid decomposition below 400 C. This research investigates the design for a prototype device that channels the energy of dissociation to ignite a laboratory scale hybrid rocket motor.

Fabrication of porous MgCo2O4 with rod-like morphology and its superb catalytic activity towards ammonium perchlorate thermal decomposition

NASA Astrophysics Data System (ADS)

Li, Gang; Liu, Xiaoli; Bai, Weiyang

2018-03-01

In this paper, porous MgCo2O4 with rod-like morphology was successfully synthesized through the thermal treatment of metal oxalates precursor originated by the reaction of metal sulfates and oxalic acid, without the addition of other additives. The porous rod-like MgCo2O4, with a diameter of several hundred nanometers and a length of several micrometers, was formed through the agglomeration of numerous crystalline grains sized in 10–25 nm. Its catalytic effect on ammonium perchlorate (AP) thermal decomposition was evaluated using differential scanning calorimetry (DSC) techniques. It was found that the pyrolysis temperature of AP reduced by 129 °C and the heat release increased more than 3.19-fold with a 2 wt% addition of MgCo2O4. Meanwhile, the addition of MgCo2O4 resulted in an AP decomposition activation energy reduction from 216 kJ mol‑1 to 155 kJ mol‑1, calculated using the Kissinger correlation. This study provides new insights into the design and development of high performance catalysts for AP thermal decomposition.

Boron Nitride-supported Sub-nanometer Pd 6 Clusters for Formic Acid Decomposition: A DFT Study

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

Schimmenti, Roberto; Cortese, Remedios; Duca, Dario

A periodic, self-consistent planewave DFT study was carried out to explore the potential use of Pd 6 clusters supported on a boron nitride sheet as a catalyst for the selective decomposition of formic acid (HCOOH) to CO 2 and H 2. The competition between formate (HCOO) and carboxyl (COOH) paths on catalytic sites, with different proximities to the support, was studied. Based on energetics alone, the reaction may mainly follow the HCOO route. Slightly lower activation energies were found at the lateral sites of the cluster as compared to top face sites. This is particularly true for the bidentate tomore » monodentate HCOO conversion. Through comparison of results with similar studies on HCOOH decomposition on extended Pd surfaces, it was demonstrated that the existence of undercoordinated sites in the sub-nanometer cluster could play a key role in preferentially stabilizing HCOO over COOH, which is a common CO precursor in this reaction. A hydrogen spillover mechanism was also investigated; migration toward the boron nitride support is not favorable, at least in the early stages of the reaction. However, hydrogen diffusion on the cluster has low barriers compared to those involved in formic acid decomposition.« less

Boron Nitride-supported Sub-nanometer Pd 6 Clusters for Formic Acid Decomposition: A DFT Study

DOE PAGES

Schimmenti, Roberto; Cortese, Remedios; Duca, Dario; ...

2017-04-25

A periodic, self-consistent planewave DFT study was carried out to explore the potential use of Pd 6 clusters supported on a boron nitride sheet as a catalyst for the selective decomposition of formic acid (HCOOH) to CO 2 and H 2. The competition between formate (HCOO) and carboxyl (COOH) paths on catalytic sites, with different proximities to the support, was studied. Based on energetics alone, the reaction may mainly follow the HCOO route. Slightly lower activation energies were found at the lateral sites of the cluster as compared to top face sites. This is particularly true for the bidentate tomore » monodentate HCOO conversion. Through comparison of results with similar studies on HCOOH decomposition on extended Pd surfaces, it was demonstrated that the existence of undercoordinated sites in the sub-nanometer cluster could play a key role in preferentially stabilizing HCOO over COOH, which is a common CO precursor in this reaction. A hydrogen spillover mechanism was also investigated; migration toward the boron nitride support is not favorable, at least in the early stages of the reaction. However, hydrogen diffusion on the cluster has low barriers compared to those involved in formic acid decomposition.« less

Decomposition of toluene in a steady-state atmospheric-pressure glow discharge

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

Trushkin, A. N.; Grushin, M. E.; Kochetov, I. V.

Results are presented from experimental studies of decomposition of toluene (C{sub 6}H{sub 5}CH{sub 3}) in a polluted air flow by means of a steady-state atmospheric pressure glow discharge at different water vapor contents in the working gas. The experimental results on the degree of C{sub 6}H{sub 5}CH{sub 3} removal are compared with the results of computer simulations conducted in the framework of the developed kinetic model of plasma chemical decomposition of toluene in the N{sub 2}: O{sub 2}: H{sub 2}O gas mixture. A substantial influence of the gas flow humidity on toluene decomposition in the atmospheric pressure glow discharge ismore » demonstrated. The main mechanisms of the influence of humidity on C{sub 6}H{sub 5}CH{sub 3} decomposition are determined. The existence of two stages in the process of toluene removal, which differ in their duration and the intensity of plasma chemical decomposition of C{sub 6}H{sub 5}CH{sub 3} is established. Based on the results of computer simulations, the composition of the products of plasma chemical reactions at the output of the reactor is analyzed as a function of the specific energy deposition and gas flow humidity. The existence of a catalytic cycle in which hydroxyl radical OH acts a catalyst and which substantially accelerates the recombination of oxygen atoms and suppression of ozone generation when the plasma-forming gas contains water vapor is established.« less

Molybdenum-based additives to mixed-metal oxides for use in hot gas cleanup sorbents for the catalytic decomposition of ammonia in coal gases

DOEpatents

Ayala, Raul E.

1993-01-01

This invention relates to additives to mixed-metal oxides that act simultaneously as sorbents and catalysts in cleanup systems for hot coal gases. Such additives of this type, generally, act as a sorbent to remove sulfur from the coal gases while substantially simultaneously, catalytically decomposing appreciable amounts of ammonia from the coal gases.

Concepts in Heterogeneous Catalysis

DTIC Science & Technology

1974-06-01

silvetrcrystals. LEEI)invistigations showed that the (100) face of tungsten is active in ammonia chemiisorption and decomposition whilet the! (110...CThem, Rep., Tokyo, 29,233 (1936). 21A. Sherman and 11, Kyring, J. Am. Chcm, Sot., L4,2661 (1932). 220 . breekl, Rev, of Mod. Picyplte, 17 ’ 61( 1945 ...differewnt eations (!an oectur, such am for instanci’ dehydration or dehy’drogenation of alcohols, the- relative activity of the catalyst for dehydration

The Use of Spray-Dried Mn₃O₄/C Composites as Electrocatalysts for Li-O₂ Batteries.

PubMed

Yang, Hong-Kai; Chin, Chih-Chun; Chen, Jenn-Shing

2016-11-07

The electrocatalytic activities of Mn₃O₄/C composites are studied in lithium-oxygen (Li-O₂) batteries as cathode catalysts. The Mn₃O₄/C composites are fabricated using ultrasonic spray pyrolysis (USP) with organic surfactants as the carbon sources. The physical and electrochemical performance of the composites is characterized by X-ray diffraction, scanning electron microscopy, particle size analysis, Brunauer-Emmett-Teller (BET) measurements, elemental analysis, galvanostatic charge-discharge methods and rotating ring-disk electrode (RRDE) measurements. The electrochemical tests demonstrate that the Mn₃O₄/C composite that is prepared using Trition X-114 (TX114) surfactant has higher activity as a bi-functional catalyst and delivers better oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalytic performance in Li-O₂ batteries because there is a larger surface area and particles are homogeneous with a meso/macro porous structure. The rate constant ( k f ) for the production of superoxide radical (O₂ • - ) and the propylene carbonate (PC)-electrolyte decomposition rate constant ( k ) for M₃O₄/C and Super P electrodes are measured using RRDE experiments and analysis in the 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF₆)/PC electrolyte. The results show that TX114 has higher electrocatalytic activity for the first step of ORR to generate O₂ • - and produces a faster PC-electrolyte decomposition rate.

Method of fabrication of anchored nanostructure materials

DOEpatents

Seals, Roland D; Menchhofer, Paul A; Howe, Jane Y; Wang, Wei

2013-11-26

Methods for fabricating anchored nanostructure materials are described. The methods include heating a nano-catalyst under a protective atmosphere to a temperature ranging from about 450.degree. C. to about 1500.degree. C. and contacting the heated nano-catalysts with an organic vapor to affix carbon nanostructures to the nano-catalysts and form the anchored nanostructure material.

Characterization of Co and Fe-MCM-56 catalysts for NH3-SCR and N2O decomposition: An in situ FTIR study

NASA Astrophysics Data System (ADS)

Grzybek, Justyna; Gil, Barbara; Roth, Wieslaw J.; Skoczek, Monika; Kowalczyk, Andrzej; Chmielarz, Lucjan

2018-05-01

Two-step preparation of iron and cobalt-containing MCM-56 zeolites has been undertaken to evaluate the influence of their physicochemical properties in the selective catalytic reduction (NH3-SCR or DeNOx) of NO using NH3 as a reductant. Zeolites were prepared by the selective leaching of the framework cations by concentrated HNO3 solution and NH4F/HF mixture and consecutively, introduction of Co and Fe heteroatoms, in quantities below 1 wt%. Further calcination allowed to obtain highly dispersed active species. Their evaluation and speciation was realized by adsorption of pyridine and NO, followed by FTIR spectroscopy. Both Fe-MCM-56 zeolites showed excellent activities (maximum NO conversion 92%) with high selectivity to dinitrogen (above 99%) in the high temperature NH3-SCR process. High catalytic activity of Fe-MCM-56 zeolites was assigned to the formation of stable nitrates, delivering NO to react with NH3 at higher temperatures and suppressing the direct NO oxidation. It was found that more nitrates was formed in Fe-MCM-56 (HNO3) than in Fe-MCM-56 (HF/NH4F) and that could compensate for the lower Fe loading, resulting in very similar catalytic activity of both catalysts. At the same time both Co-and Fe-MCM-56 zeolites were moderately active in direct N2O decomposition, with maximum N2O conversion not higher than 80% and activity window starting at 500 °C. This phenomenon was expected since both types of catalysts contained well dispersed active centers, not beneficial for this reaction.

Characterization of Co and Fe-MCM-56 catalysts for NH3-SCR and N2O decomposition: An in situ FTIR study.

PubMed

Grzybek, Justyna; Gil, Barbara; Roth, Wieslaw J; Skoczek, Monika; Kowalczyk, Andrzej; Chmielarz, Lucjan

2018-05-05

Two-step preparation of iron and cobalt-containing MCM-56 zeolites has been undertaken to evaluate the influence of their physicochemical properties in the selective catalytic reduction (NH 3 -SCR or DeNOx) of NO using NH 3 as a reductant. Zeolites were prepared by the selective leaching of the framework cations by concentrated HNO 3 solution and NH 4 F/HF mixture and consecutively, introduction of Co and Fe heteroatoms, in quantities below 1wt%. Further calcination allowed to obtain highly dispersed active species. Their evaluation and speciation was realized by adsorption of pyridine and NO, followed by FTIR spectroscopy. Both Fe-MCM-56 zeolites showed excellent activities (maximum NO conversion 92%) with high selectivity to dinitrogen (above 99%) in the high temperature NH 3 -SCR process. High catalytic activity of Fe-MCM-56 zeolites was assigned to the formation of stable nitrates, delivering NO to react with NH 3 at higher temperatures and suppressing the direct NO oxidation. It was found that more nitrates was formed in Fe-MCM-56 (HNO 3 ) than in Fe-MCM-56 (HF/NH 4 F) and that could compensate for the lower Fe loading, resulting in very similar catalytic activity of both catalysts. At the same time both Co-and Fe-MCM-56 zeolites were moderately active in direct N 2 O decomposition, with maximum N 2 O conversion not higher than 80% and activity window starting at 500°C. This phenomenon was expected since both types of catalysts contained well dispersed active centers, not beneficial for this reaction. Copyright © 2018 Elsevier B.V. All rights reserved.

Experimental study on removals of SO2 and NO(x) using adsorption of activated carbon/microwave desorption.

PubMed

Ma, Shuang-Chen; Yao, Juan-Juan; Gao, Li; Ma, Xiao-Ying; Zhao, Yi

2012-09-01

Experimental studies on desulfurization and denitrification were carried out using activated carbon irradiated by microwave. The influences of the concentrations of nitric oxide (NO) and sulfur dioxide (SO2), the flue gas coexisting compositions, on adsorption properties of activated carbon and efficiencies of desulfurization and denitrification were investigated. The results show that adsorption capacity and removal efficiency of NO decrease with the increasing of SO2 concentrations in flue gas; adsorption capacity of NO increases slightly first and drops to 12.79 mg/g, and desulfurization efficiency descends with the increasing SO2 concentrations. Adsorption capacity of SO2 declines with the increasing of O2 content in flue gas, but adsorption capacity of NO increases, and removal efficiencies of NO and SO2 could be larger than 99%. Adsorption capacity of NO declines with the increase of moisture in the flue gas, but adsorption capacity of SO2 increases and removal efficiencies of NO and SO2 would be relatively stable. Adsorption capacities of both NO and SO2 decrease with the increasing of CO2 content; efficiencies of desulfurization and denitrification augment at the beginning stage, then start to fall when CO2 content exceeds 12.4%. The mechanisms of this process are also discussed. The prominent SO2 and NOx treatment techniques in power plants are wet flue gas desulfurization (FGD) and the catalytic decomposition method like selective catalytic reduction (SCR) or nonselective catalytic reduction (NSCR). However, these processes would have some difficulties in commercial application due to their high investment, requirement of expensive catalysts and large-scale equipment, and so on. A simple SO2 and NOx reduction utilizing decomposition by microwave energy method can be used. The pollutants control of flue gas in the power plants by the method of microwave-induced decomposition using adsorption of activated carbon/microwave desorption can meet the requirements of environmental protection, which will be stricter in the future.

Ultrasound (US), Ultraviolet light (UV) and combination (US+UV) assisted semiconductor catalysed degradation of organic pollutants in water: oscillation in the concentration of hydrogen peroxide formed in situ.

PubMed

Jyothi, K P; Yesodharan, Suguna; Yesodharan, E P

2014-09-01

Application of Advanced Oxidation Processes (AOP) such as sono, photo and sonophoto catalysis in the purification of polluted water under ambient conditions involve the formation and participation of Reactive Oxygen Species (ROS) like ·OH, HO2·, O2(-), H2O2 etc. Among these, H2O2 is the most stable and is also a precursor for the reactive free radicals. Current investigations on the ZnO mediated sono, photo and sonophoto catalytic degradation of phenol pollutant in water reveal that H2O2 formed in situ cannot be quantitatively correlated with the degradation of the pollutant. The concentration of H2O2 formed does not increase corresponding to phenol degradation and reaches a plateau or varies in a wave-like fashion (oscillation) with well defined crests and troughs, indicating concurrent formation and decomposition. The concentration at which decomposition overtakes formation or formation overtakes decomposition is sensitive to the reaction conditions. Direct photolysis of H2O2 in the absence of catalyst or the presence of pre-equilibrated (with the adsorption of H2O2) catalyst in the absence of light does not lead to the oscillation. The phenomenon is more pronounced in sonocatalysis, the intensity of oscillation being in the order sonocatalysis>photocatalysis⩾sonophotocatalysis while the degradation of phenol follows the order sonophotocatalysis>photocatalysis>sonocatalysis>sonolysis>photolysis. In the case of sonocatalysis, the oscillation continues for some more time after discontinuing the US irradiation indicating that the reactive free radicals as well as the trapped electrons and holes which interact with H2O2 have longer life time (memory effect). Copyright © 2014 Elsevier B.V. All rights reserved.

Protection from wintertime rainfall reduces nutrient losses and greenhouse gas emissions during the decomposition of poultry and horse manure-based amendments.

PubMed

Maltais-Landry, Gabriel; Neufeld, Katarina; Poon, David; Grant, Nicholas; Nesic, Zoran; Smukler, Sean

2018-04-01

Manure-based soil amendments (herein "amendments") are important fertility sources, but differences among amendment types and management can significantly affect their nutrient value and environmental impacts. A 6-month in situ decomposition experiment was conducted to determine how protection from wintertime rainfall affected nutrient losses and greenhouse gas (GHG) emissions in poultry (broiler chicken and turkey) and horse amendments. Changes in total nutrient concentration were measured every 3 months, changes in ammonium (NH 4 + ) and nitrate (NO 3 - ) concentrations every month, and GHG emissions of carbon dioxide (CO 2 ), methane (CH 4 ), and nitrous oxide (N 2 O) every 7-14 days. Poultry amendments maintained higher nutrient concentrations (except for K), higher emissions of CO 2 and N 2 O, and lower CH 4 emissions than horse amendments. Exposing amendments to rainfall increased total N and NH 4 + losses in poultry amendments, P losses in turkey and horse amendments, and K losses and cumulative N 2 O emissions for all amendments. However, it did not affect CO 2 or CH 4 emissions. Overall, rainfall exposure would decrease total N inputs by 37% (horse), 59% (broiler chicken), or 74% (turkey) for a given application rate (wet weight basis) after 6 months of decomposition, with similar losses for NH 4 + (69-96%), P (41-73%), and K (91-97%). This study confirms the benefits of facilities protected from rainfall to reduce nutrient losses and GHG emissions during amendment decomposition. The impact of rainfall protection on nutrient losses and GHG emissions was monitored during the decomposition of broiler chicken, turkey, and horse manure-based soil amendments. Amendments exposed to rainfall had large ammonium and potassium losses, resulting in a 37-74% decrease in N inputs when compared with amendments protected from rainfall. Nitrous oxide emissions were also higher with rainfall exposure, although it had no effect on carbon dioxide and methane emissions. Overall, this work highlights the benefits of rainfall protection during amendment decomposition to reduce nutrient losses and GHG emissions.

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

Jarvis, Jacqueline M.; Sudasinghe, Nilusha M.; Albrecht, Karl O.

We apply Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) for direct characterization of iron-porphyrins in hydrothermal liquefaction (HTL) biocrude oils derived from two algae: Tetraselmis sp. and cyanobacteria. The ironporphyrin compounds are shown to cause catalyst bed plugging during hydroprocessing due to iron deposition. Inductively-coupled plasma optical emission spectrometry (ICPOES) was utilized for iron quantitation in the plugged catalyst beds formed through hydroprocessing of the two HTL biocrudes and identifies an enrichment of iron in the upper five centimeters of the catalyst bed for Tetraselmis sp. (Fe=100,728 ppm) and cyanobacteria (Fe=115,450 ppm). Direct infusion FT-ICR MS analysis ofmore » the two HTL biocrudes with optimized instrument conditions facilitates rapid screening and identification of iron-porphyrins without prior chromatographic separation. With FT-ICR MS we identify 138 unique iron-porphyrin compounds in the two HTL biocrudes that are structurally similar to metal-porphyrins (e.g. Ni and V) observed in petroleum. No ironporphyrins are observed in the cyanobacteria HTL biocrude after hydroprocessing, which indicates that iron-porphyrin structures in the HTL biocrude are degraded during hydroprocessing. Hydrodemetallization reactions that occur through hydroprocessing of HTL biocrudes could be responsible for the decomposition of iron-porphyrin structures leading to metal deposition in the catalyst bed that result in catalyst deactivation and bed plugging, and must be addressed for effective upgrading of algal HTL biocrudes.« less

Controlled synthesis of carbon-encapsulated copper nanostructures by using smectite clays as nanotemplates.

PubMed

Tsoufis, Theodoros; Colomer, Jean-François; Maccallini, Enrico; Jankovič, Lubos; Rudolf, Petra; Gournis, Dimitrios

2012-07-23

Rhomboidal and spherical metallic-copper nanostructures were encapsulated within well-formed graphitic shells by using a simple chemical method that involved the catalytic decomposition of acetylene over a copper catalyst that was supported on different smectite clays surfaces by ion-exchange. These metallic-copper nanostructures could be separated from the inorganic support and remained stable for months. The choice of the clay support influenced both the shape and the size of the synthesized Cu nanostructures. The synthesized materials and the supported catalysts from which they were produced were studied in detail by TEM and SEM, powder X-ray diffraction, thermal analysis, as well as by Raman and X-ray photoelectron spectroscopy. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Comparative Study of N2O Formation during the Selective Catalytic Reduction of NOx with NH3 on Zeolite Supported Cu Catalysts

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

Chen, Hai-Ying; Wei, Zhehao; Kollar, Marton

A comparative study was carried out on a small-pore CHA.Cu and a large-pore BEA.Cu zeolite catalyst to understand the lower N2O formation on small-pore zeolite supported Cu catalysts in the selective catalytic reduction (SCR) of NOx with NH3. On both catalysts, the N2O yield increases with an increase in the NO2/NOx ratios of the feed gas, suggesting N2O formation via the decomposition of NH4NO3. Temperature-programmed desorption experiments reveal that NH4NO3 is more stable on CHA.Cu than on BEA.Cu. In situ FTIR spectra following stepwise (NO2 + O2) and (15NO + NH3 + O2) adsorption and reaction, and product distribution analysismore » using isotope-labelled reactants, unambiguously prove that surface nitrate groups are essential for the formation of NH4NO3. Furthermore, CHA.Cu is shown to be considerably less active than BEA.Cu in catalyzing NO oxidation and the subsequent formation of surface nitrate groups. Both factors, i.e., (1) the higher thermal stability of NH4NO3 on CHA.Cu, and (2) the lower activity for this catalyst to catalyze NO oxidation and the subsequent formation of surface nitrates, likely contribute to the higher SCR selectivity with less N2O formation on this catalyst as compared to BEA.Cu. The latter is determined as the primary reason since surface nitrates are the source that leads to the formation of NH4NO3 on the catalysts.« less

Metal Doping Effect of the M-Co2P/Nitrogen-Doped Carbon Nanotubes (M = Fe, Ni, Cu) Hydrogen Evolution Hybrid Catalysts.

PubMed

Pan, Yuan; Liu, Yunqi; Lin, Yan; Liu, Chenguang

2016-06-08

The enhancement of catalytic performance of cobalt phosphide-based catalysts for the hydrogen evolution reaction (HER) is still challenging. In this work, the doping effect of some transition metal (M = Fe, Ni, Cu) on the electrocatalytic performance of the M-Co2P/NCNTs (NCNTs, nitrogen-doped carbon nanotubes) hybrid catalysts for the HER was studied systematically. The M-Co2P/NCNTs hybrid catalysts were synthesized via a simple in situ thermal decomposition process. A series of techniques, including X-ray diffraction, X-ray photoelectron spectroscopy, inductively coupled plasma-optical emission spectrometry, transmission electron microscopy, and N2 sorption were used to characterize the as-synthesized M-Co2P/NCNTs hybrid catalysts. Electrochemical measurements showed the catalytic performance according to the following order of Fe-Co2P/NCNTs > Ni-Co2P/NCNTs > Cu-Co2P/NCNTs, which can be ascribed to the difference of structure, morphology, and electronic property after doping. The doping of Fe atoms promote the growth of the [111] crystal plane, resulting in a large specific area and exposing more catalytic active sites. Meanwhile, the Fe(δ+) has the highest positive charge among all the M-Co2P/NCNTs hybrid catalysts after doping. All these changes can be used to contribute the highest electrocatalytic activity of the Fe-Co2P/NCNTs hybrid catalyst for HER. Furthermore, an optimal HER electrocatalytic activity was obtained by adjusting the doping ratio of Fe atoms. Our current research indicates that the doping of metal is also an important strategy to improve the electrocatalytic activity for the HER.

The influence of desilication on high-silica MFI and its catalytic performance for N2O decomposition

NASA Astrophysics Data System (ADS)

Shen, Qun; Wu, Minfang; Wang, Hui; Sun, Nannan; He, Chi; Wei, Wei

2018-05-01

A series of MFI zeolites with different Si/Al ratios were pretreated by a basic solution and their catalytic activity was evaluated in N2O decomposition after iron exchange. The performance of Fe-ZSM-5 catalysts could be improved by alkaline pretreatment. Among these samples, the activity curve of Fe-Z5-250-S sample could move to low temperature by >100 °C with a good preservation of hydrothermal stability. It is found that with the meso-microporous hybrid structure, the content of iron as active metal is significantly increased. Additionally, well preservation of the chemical environment around the tetrahedral aluminum and the site accessibility probably may be the other important factors to influence the catalytic activity.

Carbon Allotrope Dependence on Temperature and Pressure During Thermal Decomposition of Silicon Carbide

DTIC Science & Technology

2014-03-27

temperature, to its electrical conductivity, while considering its dopant concentration ( or ) [2]. (1-2) As previously stated, temperature effects...electrons [2]. Equations (1-3) and (1-4) are used to calculate electron (or hole) mobility in Si based on total dopant concentration (N) at a given...nickel, or cobalt . The metal catalyst breaks down the carbon feedstock to produce CNTs. As shown in Figure 53 below, 83 gaseous carbon feedstock

Synthesis and characterization of catalysts for the selective transformation of biomass-derived materials

NASA Astrophysics Data System (ADS)

Ghampson, Isaac Tyrone

The experimental work in this thesis focuses on generating catalysts for two intermediate processes related to the thermal conversion of lignocellulosic biomass: the synthesis and characterization of mesoporous silica supported cobalt catalysts for the Fischer-Tropsch reaction, and an exploration of the reactivity of bulk and supported molybdenum-based nitride catalysts for the hydrodeoxygenation (HDO) of guaiacol, a lignin model compound. The first section of the work details the synthesis of a series of silica-supported cobalt Fischer-Tropsch catalysts with pore diameters ranging from 2-23 nm. Detailed X-ray diffraction measurements were used to determine the composition and particle diameters of the metal fraction, analyzed as a three-phase system containing Cofcc, Cohcp and CoO particles. Catalyst properties were determined at three stages in catalyst history: (1) after the initial calcination step to thermally decompose the catalyst precursor into Co3O4, (2) after the hydrogen reduction step to activate the catalyst to Co and (3) after the FT reaction. From the study, it was observed that larger pore diameters supported higher turnover frequency; smaller pore diameters yielded larger mole fraction of CoO; XRD on post-reduction and post-FTS catalyst samples indicated significant changes in dispersivity after reduction. In the next section, the catalytic behaviors of unsupported, activated carbon-, alumina-, and SBA-15 mesoporous silica-supported molybdenum nitride catalysts were evaluated for the hydrodeoxygenation of guaiacol (2-methoxy phenol) at 300°C and 5 MPa. The nitride catalysts were prepared by thermal decomposition of bulk and supported ammonium heptamolybdate to form MoO 3 followed by nitridation in either flowing ammonia or a nitrogen/hydrogen mixture. The catalytic properties were strongly affected by the nitriding and purging treatment as well as the physical and chemical properties of support. The overall reaction was influenced by the crystalline phase present in the catalyst, dispersion of molybdenum nitride/oxynitride, and the porosity of the support. The hydrodeoxygenation of guaiacol followed two proposed reaction pathways: demethylation (DME) of guaiacol to form catechol, followed by dehydroxylation to form phenol; or a direct demethoxylation (DMO) to form phenol. The selectivity of the reaction was expressed in terms of the phenol/catechol ratio. Phenol was the predominant product for all the catalysts studied, except for the alumina-supported catalysts (an effect of the alumina support). The results from this thesis are encouraging for the application of Mo nitride based catalysts for hydrodeoxygenation of whole pyrolysis oil.

Introducing Network Analysis into Science Education: Methodological Research Examining Secondary School Students' Understanding of "Decomposition"

ERIC Educational Resources Information Center

Schizas, Dimitrios; Katrana, Evagelia; Stamou, George

2013-01-01

In the present study we used the technique of word association tests to assess students' cognitive structures during the learning period. In particular, we tried to investigate what students living near a protected area in Greece (Dadia forest) knew about the phenomenon of decomposition. Decomposition was chosen as a stimulus word because it…

40 CFR 85.1512 - Admission of catalyst and O2 sensor-equipped vehicles.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 18 2010-07-01 2010-07-01 false Admission of catalyst and O2 sensor... Vehicles and Motor Vehicle Engines § 85.1512 Admission of catalyst and O2 sensor-equipped vehicles. (a)(1... system and/or O2 sensor; (iii) Is labeled in accordance with 40 CFR part 86, subpart A or subpart S, or...

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

Catalytic Conversion of Short-Chain Alcohols on Atomically Dispersed Au and Pd Supported on Nanoscale Metal Oxides

NASA Astrophysics Data System (ADS)

Wang, Chongyang

With the development of technologies for cellulosic biomass conversion to fuels and chemicals, bio-alcohols are among the main alternative feedstocks to fossil fuels. The research pursued in my thesis was the investigation of gold and palladium as catalysts for the application of short aliphatic alcohols to hydrogen generation and value-added chemicals production. Specifically, selective methanol steam reforming and non-oxidative ethanol dehydrogenation to hydrogen and acetaldehyde were investigated in this thesis work. A major aim of the thesis was to develop atomically efficient catalysts with tuned surface chemistry for the desired reactions, using suitable synthesis methods. Methanol steam reforming (SRM) for hydrogen production has recently been investigated on gold catalysts to overcome the drawbacks of copper catalysts (deactivation, pyrophoricity). Previous work at Tufts University has shown that both CeO2 and ZnO are suitable supports for gold. In this thesis, nanoscale composite oxides ZnZrOx were prepared by a carbon hard-template method, which resulted in homogeneous distribution of Zn species in the matrix of ZrO2. Tunable surface chemistry of ZnZrO x was demonstrated by varying the Zn/Zr ratio to suppress the strong Lewis acidity of ZrO2, which leads to undesired production of CO through methanol decomposition. With atomic dispersion of gold, Au/ZnZrO x catalyzes the SRM reaction exclusively via the methanol self-coupling pathway up to 375°C. The activity of Au/ZnZrOx catalysts was compared to Au/TiO2, which is another catalyst system demonstrating atomic dispersion of gold. Similarity in the apparent activation energy of SRM on all the supported gold catalysts studied in this thesis and in the literature further confirms the same single-site Au-Ox-MO centers as active sites for SRM with indirect effects of the supports exploited. With this fundamental understanding of gold-catalyzed C1 alcohol reforming, the Au/ZnZrOx catalyst was evaluated for the dehydrogenation of ethanol. Bare ZnZrOx activate ethanol conversion in the range of 280-300°C and produce undesired ethylene as product of ethanol dehydration, whereas, addition of small amount of gold (<1wt.%) was found to significantly change the product distribution in the low-temperature range (200°C-350°C). As gold passivates the strong Bronsted acid sites of ZrO2 and selectively facilitates the dehydrogenation of ethanol at low-temperature, a wide temperature range was found between the production of acetaldehyde (dehydrogenation products) and ethylene (dehydration product), which can be harnessed for the industrial application. Interestingly, the steam reforming of ethanol did not take place in the low-temperature region, thus the selectivity to acetaldehyde and hydrogen was 100% even in the presence of water. In addition to gold, palladium was also studied in this thesis work on the ZnZrOx composite oxides, and its activity and selectivity were compared to Au/ZnZrOx. Monometallic Pd catalyzes the decomposition of methanol and ethanol, resulting in different product distribution for C 1-C2 alcohol reactions. With ZnZrOx employed as the catalyst support in this thesis work, the finely dispersed ZnO species in ZrO2 were found to alloy with the supported palladium under reduction treatment. Alloying with Zn tunes the chemistry of Pd to catalyze the SRM reaction through the methanol coupling mechanism, shutting off the undesired methanol decomposition pathway. A preliminary study of the Pd/ZnZrO x system for ethanol dehydrogenation also demonstrated the modification of Pd when in the PdZn alloy form. Different from the monometallic Pd catalyst, which primarily catalyzes the C-C bond scission of ethanol, high selectivity to ethanol dehydrogenation products was found on PdZn, over the temperature range of 200-400°C. Formation of the PdZn alloy broadens the application of Pd and potentially other Group VIII metals for selective alcohol conversion reactions. In summary, this thesis work has investigated two noble metals Au and Pd from Group IB and Group VIII, respectively, for methanol and ethanol alcohol reforming reactions employing a novel ZnZrOx composite oxide as a platform catalyst support. Comprehensive study of Au catalyst has deepened our understanding of atomically dispersed Au anchored on various supports through oxygen bonds as the active sites for alcohol reforming reactions, and showed the support effect to be indirect, serving as the carrier and stabilizer of the gold species. For Pd, the Zn species of the composite oxide is necessary to modify the Pd catalyst and the PdZn alloy gives it the desired Au-like properties. Full characterization of the catalysts used here by ICP, XPS, XRD, FTIR and STEM imaging was conducted throughout the thesis to identify the stable species and correlate the catalyst performance with its composition and morphology. Surface acidity titration by isopropanol temperature-programmed desorption/mass spectrometry (IPA-TPD/MS) and pyridine-IR adsorption/desorption was conducted in parallel to temperature-programmed surface reaction (TPSR) studies and products from isothermal steady-state reactions were monitored online by mass spectrometry.

Fe1-xZnxS ternary solid solution as an efficient Fenton-like catalyst for ultrafast degradation of phenol.

PubMed

Gao, Jing; Liu, Yutang; Xia, Xinnian; Wang, Longlu; Dong, Wanyue

2018-07-05

Heterogeneous Fenton-like system has been proved to be an promising alternative to Fenton system due to its easy separation. However, it's a challenge to design heterogeneous Fenton-like catalysts with high activity and great durability. Here, ternary solid solution Fe 1-x Zn x S were prepared via hydrothermal synthesis as heterogeneous Fenton-like catalysts. The Fe 0.7 Zn 0.3 S sample exhibited state of the art activity for yielding OH by H 2 O 2 decomposition, and the ultrafast degradation of phenol was achieved in 4 min at initial acidic condition under room temperature. The phenol degradation rate constant of Fe 0.7 Zn 0.3 S was 99 and 70 times of ZnS and FeS, respectively. Further, we show that the unique structural configuration of iron atoms, the formation of FeS 2 -pyrite with (200) plane, are responsible for the excellent activity. The intermediate products were identified by LC-MS and a possible pathway was accordingly proposed to elucidate the mechanism of phenol degradation by OH. Overall, this work provides an idea for the rational design of the relevant heterogeneous Fenton-like catalysts. Copyright © 2018 Elsevier B.V. All rights reserved.

Exploring the activity of a novel Au/TiC(001) model catalyst towards CO and CO 2 hydrogenation

DOE PAGES

Asara, Gian Giacomo; Ricart, Josep M.; Rodriguez, Jose A.; ...

2015-02-02

Small metallic nanoparticles supported on transition metal carbides exhibit an unexpected high activity towards a series of chemical reactions. In particular, the Au/TiC system has proven to be an excellent catalyst for SO 2 decomposition, thiophene hydrodesulfurization, O 2 and H 2 dissociation and the water gas shift reaction. Recent studies have shown that Au/TiC is a very good catalyst for the reverse water–gas shift (CO 2 + H 2 → CO + H 2O) and CO 2 hydrogenation to methanol. The present work further expands the range of applicability of this novel type of systems by exploring the catalyticmore » activity of Au/TiC towards the hydrogenation of CO or CO 2 with periodic density functional theory (DFT) calculations on model systems. Hydrogen dissociates easily on Au/TiC but direct hydrogenation of CO to methanol is hindered by very high activation barriers implying that, on this model catalyst, methanol production from CO 2 involves the hydrogenation of a HOCO-like intermediate. Thus, when dealing with mixtures of syngas (CO/CO 2/H 2/H 2O), CO could be transformed into CO 2 through the water gas shift reaction with subsequent hydrogenation of CO 2 to methanol.« less

Synthesis, Decomposition and Characterization of Fe and Ni Sulfides and Fe and CO Nanoparticles for Aerospace Applications

NASA Technical Reports Server (NTRS)

Cowen, Jonathan E.; Hepp, Aloysius F.; Duffy, Norman V.; Jose, Melanie J.; Choi, D. B.; Brothers, Scott M.; Baird, Michael F.; Tomsik, Thomas M.; Duraj, Stan A.; Williams, Jennifer N.;

Identifying Different Types of Catalysts for CO2 Reduction by Ethane through Dry Reforming and Oxidative Dehydrogenation.

PubMed

Porosoff, Marc D; Myint, Myat Noe Zin; Kattel, Shyam; Xie, Zhenhua; Gomez, Elaine; Liu, Ping; Chen, Jingguang G

2015-12-14

The recent shale gas boom combined with the requirement to reduce atmospheric CO2 have created an opportunity for using both raw materials (shale gas and CO2 ) in a single process. Shale gas is primarily made up of methane, but ethane comprises about 10 % and reserves are underutilized. Two routes have been investigated by combining ethane decomposition with CO2 reduction to produce products of higher value. The first reaction is ethane dry reforming which produces synthesis gas (CO+H2 ). The second route is oxidative dehydrogenation which produces ethylene using CO2 as a soft oxidant. The results of this study indicate that the Pt/CeO2 catalyst shows promise for the production of synthesis gas, while Mo2 C-based materials preserve the CC bond of ethane to produce ethylene. These findings are supported by density functional theory (DFT) calculations and X-ray absorption near-edge spectroscopy (XANES) characterization of the catalysts under in situ reaction conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and thermal characterization of xylan-graft-polyacrylonitrile.

PubMed

Ünlü, Cüneyt H; Öztekin, N Simge; Atıcı, Oya Galioğlu

2012-10-01

In this study emulsion polymerization of acrylonitrile using xylan from agricultural waste material (corn cob) and cerium ammonium nitrate was investigated in terms of catalyst acid. Stock ceric solutions were prepared using either nitric or perchloric acid as catalyst. Optimum conditions were determined using different parameters such as reaction time, temperature, and component concentrations. Nitric acid catalyzed reactions resulted in maximum conversion ratio (96%) at 50°C, 1 h where ceric ion, acrylonitrile, xylan, and catalyst concentrations were 21.7 mmol l(-1), 0.5 mol l(-1), 0.2% (w/v), and 0.1 mol l(-1), respectively. However, 83% conversion was obtained with perchloric acid catalysis at 27 °C, 1 h where concentrations were 5.4 mmol l(-1), 0.8 mol l(-1), 0.5% (w/v), and 0.2 mol l(-1), respectively. Copolymer synthesis using perchloric acid was realized at milder conditions than using nitric acid. Thermal analyses of obtained polymers were conducted to characterize copolymers. Results showed that calculated activation energy, maximum degradation temperature, and heat of thermal decomposition changed relying mainly on molecular weight. Copyright © 2012 Elsevier Ltd. All rights reserved.

Catalytic decomposition of methanol for onboard hydrogen generation

NASA Technical Reports Server (NTRS)

Brabbs, T.

1978-01-01

The steam reformation of an equimolar mixture of methanol and water on a copper chromite catalyst was studied at three furnace temperatures and at feed space velocities from 800 to 2600 per hour. The hydrogen space velocity could be related to the reactor temperature by the equation Sv = A exp (-omega T), where A and omega are constants determined for each value of alpha and T is temperature. At a methanol conversion of 0.87 and a reactor temperature of 589 K, the extrapolated value of the hydrogen space velocity was 9400 per hour. This velocity was used to estimate the size of an onboard hydrogen reactor for automotive applications. Such a reactor would need only about 0.8 liter of catalyst to produce 7630 STP liters (1.5 lb) of hydrogen per hour. This quantity of catalyst would fit into nine tubes 17.8 centimeters along and 2.54 centimeters in inside diameter, which is smaller than most mufflers. The reactor products would contain 12 to 13 percent more chemical energy than the incoming methanol and water.

Identifying different types of catalysts for CO 2 reduction by ethane through dry reforming and oxidative dehydrogenation

DOE PAGES

Marc D. Porosoff; Chen, Jingguang G.; Myint, Myat Noe Zin; ...

2015-11-10

In this study, the recent shale gas boom combined with the requirement to reduce atmospheric CO 2 have created an opportunity for using both raw materials (shale gas and CO 2) in a single process. Shale gas is primarily made up of methane, but ethane comprises about 10 % and reserves are underutilized. Two routes have been investigated by combining ethane decomposition with CO 2 reduction to produce products of higher value. The first reaction is ethane dry reforming which produces synthesis gas (CO+H 2). The second route is oxidative dehydrogenation which produces ethylene using CO 2 as a softmore » oxidant. The results of this study indicate that the Pt/CeO 2 catalyst shows promise for the production of synthesis gas, while Mo 2C-based materials preserve the C—C bond of ethane to produce ethylene. These findings are supported by density functional theory (DFT) calculations and X-ray absorption near-edge spectroscopy (XANES) characterization of the catalysts under in situ reaction conditions.« less

In-situ analysis of hydrazine decomposition products

NASA Technical Reports Server (NTRS)

Curran, Francis M.; Whalen, Margaret V.

1987-01-01

A gas analyzer utilizing a nondispersive infrared (NDIR) detection system was used to monitor the ammonia and water vapor content of the products of a previously unused hydrazine gas generator. This provided an in-situ measurement of the generator's efficiency difficult to obtain by other means. The analyzer was easily installed in both the calibration and hydrazine systems, required no maintenance other than periodic zero adjustments, and performed well for extended periods in the operating range tested. The catalyst bed operated smoothly and repeatably during the 28 hr of testing. No major transients were observed on startup or during steady state operation. The amount of ammonia in the output stream of the gas generator was found to be a strong function of temperature at catalyst bed temperatures below 450 C. At temperatures above this, the efficiency remained nearly constant. On startup the gas generator efficiency was found to decrease with time until a steady state value was attained. Elevated catalyst bed temperatures in the periods before steady state operation was found to be responsible for this phenomenon.

Dynamic investigation of the role of the surface sulfates in NO{sub x} reduction and SO{sub 2} oxidation over V{sub 2}O{sub 5}-WO{sub 3}/TiO{sub 2} catalysts

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

Orsenigo, C.; Lietti, L.; Tronconi, E.

1998-06-01

Transient experiments performed over synthesized and commercial V{sub 2}O{sub 5}-WO{sub 3}/TiO{sub 2} catalysts during catalyst conditioning and during step changes of the operating variables (SO{sub 2} inlet concentration and temperature) show that conditioning of the catalyst is required to attain significant and reproducible steady-state data in both the reduction of NO{sub x} and the oxidation of SO{sub 2}. The response time of conditioning for NO{sub x} reduction is of a few hours and that for SO{sub 2} oxidation is of several hours. Fourier transform infrared spectroscopy temperature programmed decomposition, and thermogravimetric measurements showed that catalyst conditioning is associated with amore » slow process of buildup of sulfates: the different characteristic conditioning times observed in the reduction of NO{sub x} and in the oxidation of SO{sub 2} suggest that the buildup of sulfates occurs first at the vanadyl sites and later on at the exposed titania surface. Formation of sulfates at or near the vanadyl sites increases the reactivity in the de-NO{sub x} reaction, possibly due to the increase in the Broensted and Lewis acidity of the catalyst, whereas the titania surface acts as SO{sub 3} acceptor and affects the outlet SO{sub 3} concentration during catalyst conditioning for the SO{sub 2} oxidation reaction. The response time to step changes in SO{sub 2} concentration and temperature is of a few hours in the case of SO{sub 2} oxidation and much shorter in the case of NO{sub x} reduction. The different time responses associated with conditioning and with step changes in the settings of the operating variables have been rationalized in terms of the different extent of perturbation of the sulfate coverage experienced by the catalyst.« less

Effect of fly ash on catalytic removal of gaseous dioxins over V{sub 2}O{sub 5}-WO{sub 3} catalyst of a sinter plant

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

Shu Hao Chang; Kai Hsien Chi; Chi Wei Young

2009-10-01

A PCDD/F (polychlorinated dibenzo-p-dioxin and dibenzofuran)-containing gas stream generating system was developed to investigate the efficiency and effectiveness of V{sub 2}O{sub 5}-WO{sub 3} catalyst for PCDD/F destruction. Catalytic decomposition of PCDD/Fs (simulated gas streams) was evaluated with lab-scale pelletized and plate-type catalyst based on V{sub 2}O{sub 5}-WO{sub 3}/TiO{sub 2} at controlled temperature, space velocity, and inlet PCDD/F concentration. Due to the lower porosity of the pelletized catalyst, PCDD/F destruction efficiencies reach 72.9-83.2% for different levels of inlet PCDD/F concentrations (1.08-3.04 ng-TEQ/Nm{sup 3}) of the gas stream (space velocity: 5000 h-1). As the surface area is increased from 287 m{sup 2}/m{supmore » 3} (plate-type A) to 550 m{sup 2}/m{sup 3} (plate-type B), the PCDD/F destruction achieved with plate-type catalyst increases from 76.0% to 85.3% at 320{sup o}C (space velocity: 5000 h{sup -1}). In addition, the results of pilot-scale experiment (real flue gases of a sinter plant) indicate that relatively lower PCDD/F destruction efficiencies (62.1-65.7%) were achieved with the plate-type B catalyst as the solid-phase PCDD/F and fly ash passed through the reactor (space velocity: 5000 h{sup -1}). Overall, the lab-scale and pilot-scale experiments indicate that PCDD/F destructions achieved with pelletized and plate-type catalysts strongly depend on the operating temperature of the catalyst. The results also indicate that the presence of fly ash lowers PCDD/F destruction due to significant PCDD/F formation via de novo synthesis at 320{sup o}C. 20 refs., 5 figs., 3 tabs.« less

Low Catalyst Loadings in Olefin Metathesis: Synthesis of Nitrogen Heterocycles by Ring Closing Metathesis

PubMed Central

Kuhn, Kevin M.; Champagne, Timothy M.; Hong, Soon Hyeok; Wei, Wen-Hao; Nickel, Andrew; Lee, Choon Woo; Virgil, Scott C.; Grubbs, Robert H.; Pederson, Richard L.

2010-01-01

(eq 1) A series of ruthenium catalysts have been screened under ring closing metathesis (RCM) conditions to produce five-, six-, and seven-membered carbamate-protected cyclic amines. Many of these catalysts demonstrated excellent RCM activity and yields with as low as 500 ppm catalyst loadings. RCM of the five-membered carbamate-series could be run neat, the six-membered carbamate-series could be run at 1.0 M concentrations and the seven-membered carbamate-series worked best at 0.2 M to 0.05 M concentrations. PMID:20141172

ADVANCED OXIDATION: OXALATE DECOMPOSITION TESTING WITH OZONE

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

Ketusky, E.; Subramanian, K.

At the Savannah River Site (SRS), oxalic acid is currently considered the preferred agent for chemically cleaning the large underground Liquid Radioactive Waste Tanks. It is applied only in the final stages of emptying a tank when generally less than 5,000 kg of waste solids remain, and slurrying based removal methods are no-longer effective. The use of oxalic acid is preferred because of its combined dissolution and chelating properties, as well as the fact that corrosion to the carbon steel tank walls can be controlled. Although oxalic acid is the preferred agent, there are significant potential downstream impacts. Impacts include:more » (1) Degraded evaporator operation; (2) Resultant oxalate precipitates taking away critically needed operating volume; and (3) Eventual creation of significant volumes of additional feed to salt processing. As an alternative to dealing with the downstream impacts, oxalate decomposition using variations of ozone based Advanced Oxidation Process (AOP) were investigated. In general AOPs use ozone or peroxide and a catalyst to create hydroxyl radicals. Hydroxyl radicals have among the highest oxidation potentials, and are commonly used to decompose organics. Although oxalate is considered among the most difficult organic to decompose, the ability of hydroxyl radicals to decompose oxalate is considered to be well demonstrated. In addition, as AOPs are considered to be 'green' their use enables any net chemical additions to the waste to be minimized. In order to test the ability to decompose the oxalate and determine the decomposition rates, a test rig was designed, where 10 vol% ozone would be educted into a spent oxalic acid decomposition loop, with the loop maintained at 70 C and recirculated at 40L/min. Each of the spent oxalic acid streams would be created from three oxalic acid strikes of an F-area simulant (i.e., Purex = high Fe/Al concentration) and H-area simulant (i.e., H area modified Purex = high Al/Fe concentration) after nearing dissolution equilibrium, and then decomposed to {le} 100 Parts per Million (ppm) oxalate. Since AOP technology largely originated on using ultraviolet (UV) light as a primary catalyst, decomposition of the spent oxalic acid, well exposed to a medium pressure mercury vapor light was considered the benchmark. However, with multi-valent metals already contained in the feed, and maintenance of the UV light a concern; testing was conducted to evaluate the impact from removing the UV light. Using current AOP terminology, the test without the UV light would likely be considered an ozone based, dark, ferrioxalate type, decomposition process. Specifically, as part of the testing, the impacts from the following were investigated: (1) Importance of the UV light on the decomposition rates when decomposing 1 wt% spent oxalic acid; (2) Impact of increasing the oxalic acid strength from 1 to 2.5 wt% on the decomposition rates; and (3) For F-area testing, the advantage of increasing the spent oxalic acid flowrate from 40 L/min (liters/minute) to 50 L/min during decomposition of the 2.5 wt% spent oxalic acid. The results showed that removal of the UV light (from 1 wt% testing) slowed the decomposition rates in both the F & H testing. Specifically, for F-Area Strike 1, the time increased from about 6 hours to 8 hours. In H-Area, the impact was not as significant, with the time required for Strike 1 to be decomposed to less than 100 ppm increasing slightly, from 5.4 to 6.4 hours. For the spent 2.5 wt% oxalic acid decomposition tests (all) without the UV light, the F-area decompositions required approx. 10 to 13 hours, while the corresponding required H-Area decompositions times ranged from 10 to 21 hours. For the 2.5 wt% F-Area sludge, the increased availability of iron likely caused the increased decomposition rates compared to the 1 wt% oxalic acid based tests. In addition, for the F-testing, increasing the recirculation flow rates from 40 liter/minute to 50 liter/minute resulted in an increased decomposition rate, suggesting a better use of ozone.« less

GREENING OF OXIDATION CATALYSIS THROUGH IMPROVED CATALYST AND PROCESS DESIGN

EPA Science Inventory

Greening of Oxidation Catalysis Through Improved Catalysts and Process Design
Michael A. Gonzalez*, Thomas Becker, and Raymond Smith

United State Environmental Protection Agency, Office of Research and Development, National Risk Management Research Laboratory, 26 W...

Catalytic decomposition of gaseous 1,2-dichlorobenzene over CuOx/TiO₂ and CuOx/TiO₂-CNTs catalysts: Mechanism and PCDD/Fs formation.

PubMed

Wang, Qiu-lin; Huang, Qun-xing; Wu, Hui-fan; Lu, Sheng-yong; Wu, Hai-long; Li, Xiao-dong; Yan, Jian-hua

2016-02-01

Gaseous 1,2-dichlorobenzene (1,2-DCBz) was catalytically decomposed in a fixed-bed catalytic reactor using composite copper-based titanium oxide (CuOx/TiO2) catalysts with different copper ratios. Carbon nanotubes (CNTs) were introduced to produce novel CuOx/TiO2-CNTs catalysts by the sol-gel method. The catalytic performances of CuOx/TiO2 and CuOx/TiO2-CNTs on 1,2-DCBz oxidative destruction under different temperatures (150-350 °C) were experimentally examined and the correlation between catalyst structure and catalytic activity was characterized and the role of oxygen in catalytic reaction was discussed. Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) generation during 1,2-DCBz catalytic oxidation by CuOx/TiO2-CNTs composite catalyst was also examined. Results indicate that the 1,2-DCBz destruction/removal efficiencies of CuOx (4 wt%)/TiO2 catalyst at 150 °C and 350 °C with a GHSV of 3400 h(-1) are 59% and 94% respectively and low-temperature (150 °C) catalytic activity of CuOx/TiO2 on 1,2-DCBz oxidation can be improved from 59 to 77% when CNTs are introduced. Furthermore, oxygen either in catalyst or from reaction atmosphere is indispensible in reaction. The former is offered to activate and oxidize the 1,2-DCBz adsorbed on catalyst, thus can be generally consumed during reaction and the oxygen content in catalyst is observed lost from 39.9 to 35.0 wt% after reacting under inert atmosphere; the latter may replenish the vacancy in catalyst created by the consumed oxygen thus extends the catalyst life and raises the destruction/removal efficiency. The introduction of CNTs also increases the Cu(2+)/Cu(+) ratio, chemisorbed oxygen concentration and surface lattice oxygen binding energy which are closely related with catalytic activity. PCDD/Fs is confirmed to be formed when 1,2-DCBz catalytically oxidized by CuOx/TiO2-CNTs composite catalyst with sufficient oxygen (21%), proper temperature (350 °C) and high concentration of 1,2-DCBz feed (120 ppm). Copyright © 2015 Elsevier Ltd. All rights reserved.

Ambient-temperature NO oxidation over amorphous CrOx-ZrO 2 mixed oxide catalysts: Significant promoting effect of ZrO 2

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

Wang, Aiyong; Guo, Yanglong; Gao, Feng

2017-03-01

Three series of Cr-based mixed oxides (Cr-Co, Cr-Fe, and Cr-Ni oxides) with high specific surface areas and amorphous textures are synthesized using a novel sol-gel method. These mixed oxides, in comparison to their pure metal oxide (CrOx, Co3O4, FeOx and NiO) counterparts, display enhanced performance for catalytic oxidation of low-concentration NO at room temperature. Over best performing catalysts, 100% NO conversion can be maintained up to 30 h of operation at a high space velocity of 45,000 ml g-1 h-1. The amorphous structure is found to be critical for these catalysts to maintain high activity and durability. Cr/M (M=Co, Femore » and Ni) molar ratio, nitrate precursor decomposition temperature and catalyst calcination temperature are important criteria for the synthesis of the highly active catalysts. This work was supported by National Basic Research Program of China (2013CB933200), National Natural Science Foundation of China (21577035, 21577034), Commission of Science and Technology of Shanghai Municipality (15DZ1205305) and 111 Project (B08021). Aiyong Wang gratefully acknowledges the China Scholarship Council for the Joint-Training Scholarship Program with the Pacific Northwest National Laboratory (PNNL). PNNL is operated for the U.S. Department of Energy (DOE) by Battelle. FG and CHFP are supported by the U.S. DOE/Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office.« less

Laboratory-scale photoredox catalysis using hydrated electrons sustainably generated with a single green laser.

PubMed

Naumann, Robert; Kerzig, Christoph; Goez, Martin

2017-11-01

The ruthenium-tris-bipyridyl dication as catalyst combined with the ascorbate dianion as bioavailable sacrificial donor provides the first regenerative source of hydrated electrons for chemical syntheses on millimolar scales. This electron generator is operated simply by illumination with a frequency-doubled Nd:YAG laser (532 nm) running at its normal repetition rate. Much more detailed information than by product studies alone was obtained by photokinetical characterization from submicroseconds (time-resolved laser flash photolysis) up to one hour (preparative photolysis). The experiments on short timescales established a reaction mechanism more complex than previously thought, and proved the catalytic action by unchanged concentration traces of the key transients over a number of flashes so large that the accumulated electron total surpassed the catalyst concentration many times. Preparative photolyses revealed that the sacrificial donor greatly enhances the catalyst stability through quenching the initial metal-to-ligand charge-transfer state before destructive dd states can be populated from it, such that the efficiency of this electron generator is no longer limited by catalyst decomposition but by electron scavenging by the accumulating oxidation products of the ascorbate. Applications covered dechlorinations of selected aliphatic and aromatic chlorides and the reduction of a model ketone. All these substrates are impervious to photoredox catalysts exhibiting lower reducing power than the hydrated electron, but the combination of an extremely negative standard potential and a long unquenched life allowed turnover numbers up to 1400 with our method.

Catalytic destruction of perchlorate in ferric chloride and hydrochloric acid solution with control of temperature, pressure and chemical reagents

DOEpatents

Gu, Baohua; Cole, David R.; Brown, Gilbert M.

2004-10-05

A method is described to decompose perchlorate in a FeCl.sub.3 /HCl aqueous solution such as would be used to regenerate an anion exchange resin used to remove perchlorate. The solution is mixed with a reducing agent, preferably an organic alcohol and/or ferrous chloride, and can be heated to accelerate the decomposition of perchlorate. Lower temperatures may be employed if a catalyst is added.

Functionalized white graphene - Copper oxide nanocomposite: Synthesis, characterization and application as catalyst for thermal decomposition of ammonium perchlorate.

PubMed

Paulose, Sanoop; Raghavan, Rajeev; George, Benny K

2017-05-15

Reactivity is of great importance for metal oxide nanoparticles (MONP) used as catalysts and advanced materials, but seeking for higher reactivity seems to be conflict with high chemical stability required for MONP. There is direct balance between reactivity and stability of these MONP. This could be acheived for metal oxide by dispersing them in a substrate. Here, we report a simple, efficient and high-yield process for the production of copper oxide (CuO) nanoparticles dispersed on a chemically inert material, few-layer hexagonal boron nitride (h-BN) with a thickness around 1.7nm and lateral dimensions mostly below 200nm. The mechano-chemical reaction which take place at atmospheric pressure and room temperature involves a urea assisted exfoliation of pristine boron nitride. Copper oxide nanoparticles dispersed on the surface of these few layered h-BN reduced its tendency for aggregation. The optimum concentration of CuO:h-BN was found to be 2:1 which shows highest catalytic activity for the thermal decomposition of ammonium perchlorate. The high catalytic activity of the in situ synthesized CuO-h-BN composite may be attributed to uniform distribution of CuO nanoparticles on the few layered h-BN which in turn provide a number of active sites on the surface due to non aggregation. Copyright © 2017 Elsevier Inc. All rights reserved.

CARBON NANOTUBES AND NANO-Ce-Zr OXIDES SUPPORTED H3PW12O40 FOR EFFECTIVE ADSORPTION-DECOMPOSITION OF NOx

NASA Astrophysics Data System (ADS)

Cheng, Lin; Wang, Rui

2012-01-01

Surface-modified carbon nanotubes (CNTs) and nano-Ce-Zr mixed oxides (CZO) were prepared and employed initially as supports of H3PW12O40 (HPW) for NOx adsorption-decomposition. Both CNTs and nano-CZO are favorable supports for HPW. After loading with HPW, the NOx adsorption efficiency increases, especially for HPW/CZO in which the highest adsorption efficiency can achieve 98% at the HPW loading of 70%, much higher than that of single HPW. NOx adsorption efficiency can be influenced considerably by catalyst preparing conditions, in particularly, ethyl alcohol is superior to water as solvent for HPW loading onto CNTs; the -OH containing CNTs shows better promotion effect on the adsorption of NOx than that containing -COOH when using absolute ethyl alcohol as solvent; mechanical grinding method is superior to incipient impregnation method in loading HPW onto the support of CZO. For both catalysts of HPW/CNTs and HPW/CZO, with the increase of HPW loading, the NOx adsorption efficiency tends to reach a peak value before dropping down. Heated from 150°C to 450°C at a rate of 50°C/min, the adsorbed NO was found to decompose into N2, O2 and N2O, and yields of N2 being 21.8% and 27.3%, respectively for HPW/CNTs and HPW/CZO were obtained.

Simultaneous sonosynthesis and sonofabrication of N-doped ZnO/TiO2 core-shell nanocomposite on wool fabric: Introducing various properties specially nano photo bleaching.

PubMed

Behzadnia, Amir; Montazer, Majid; Rad, Mahnaz Mahmoudi

2015-11-01

In this study, N-doped ZnO/TiO2 core-shell nanocomposite was successfully sonosynthesized and sonofabricated on wool fabric through a facile one-step method under ambient pressure and low temperature (75-80°C) as a novel photo-catalyst nanocomposite on textile material. The differences between crystalline phase transformation of conventional and ultrasound synthesized N-ZnO/TiO2 has been compared. The influence of different zinc acetate and titanium isopropoxide precursors in the formation of nanocomposite was studied and optimized through response surface methodology. The photocatalytic activity of the sonofabricated catalyst on the wool fabric surface was evaluated through decomposition of Methylene Blue as a model compound under sunlight irradiation. Also, N-doped ZnO/TiO2 nanocomposite sonosynthesized on wool fabric led to photo bleaching of wool fabric due to decomposition of the naturally occurred pigments under daylight irradiation. Further, yellowness index, antibacterial and antifungal activity against Escherichia coli, Staphylococcus aureus and Candida albicans, cell viability, char residual, alkali solubility, mechanical properties and water drop absorption time on the treated wool fabrics were evaluated. Also, the acid solubility of the synthesized nanopowder obtained from sonobath after treatment was characterized in acetic acid indicating higher acid resistance on N-doped ZnO/TiO2 nanocomposite. Copyright © 2015 Elsevier B.V. All rights reserved.

Investigation of Methods of Inspired Gas Heating.

DTIC Science & Technology

1981-10-30

inhaled gas. Good for one hour at 1 percent CO, the apparatus is a simple Hopcalite catalyst bed mounted on a mouthpiece. Hopcalite , a mixture of...Respirator pro- The Self-Rescuer uses the oxidation also expeiled through the expiratory vides emergency respiratory protection catalyst Hopcalites to...tection against carbon monoxide in the Hopcalite catalyst, and a drying life; it can be carried by personnel or otherwise respirable air; it should not

Novel Nano-Composite Catalysts for Renewable Energy Storage Applications

NASA Astrophysics Data System (ADS)

Devaguptapu, Surya Vamsi

Spinel NiCo2O4 catalysts are considered the promising precious metal-free catalyst for oxygen reactions. Significant efforts are mainly explore optimal chemical doping and substituent to tune its electronic structures for enhanced performance. Here, we focuses on morphology control and determine the morphology-dependent activity for bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). In particular, three types of spinel NiCo2O4 were prepared using temple-free, SiO 2 hard template, and Pluronic-123 soft template hydrothermal methods, showing significantly different morphologies, respectively. In particular, template-free method yield dense structures. Sold-template method assists the formation of porous and hollow structures. Importantly, the soft template is effective to prepare a unique nanoflower morphology containing abundant rose petal (needle) like structures. The effect of the utilization of templates, both soft and hard as well as a template free synthesis on the morphology as well as the activity and stability of the final catalyst is investigated. Compared to others, the nanoflower-like NiCo2O4 exhibited the highest bifunctional catalytic activity simultaneously for ORR and OER, likely due to the facile absorption of oxygen molecules on increased surface areas with efficient mass transfer. The nanoflower NiCo2O 4 also exhibited an onset and half-wave potentials of 0.94 and 0.82 V for the ORR in alkaline media. Although it is still inferior to state of the art Pt, the new type of spinel NiCo2O4 catalyst represents the best activity compared to reported carbon-free oxides. Meanwhile, OER activity and stability were achieved with an onset potential of 1.48 V generating a current density of 14 mA/cm2 at 1.6 V. The OER activity does not declined after 10,000 potential cycles demonstrating excellent stability, which is superior to the benchmark of Ir for the OER. This work provides an effective solution to enhance catalytic activity and stability of oxides by engineering their morphology and nanostructures. The high performance bifunctional oxide catalyst is carbon free and can eventually overcome the stability issue for reversible fuel cell and metal-air battery applications. In addition, we have synthesized highly active transition metal doped Carbon Nano Tubes of very small thickness called Graphene Tubes which when integrated with metal oxides can lead to enhanced activity and durability for ORR and OER with current density as high as 25mAcm-2 at 1.6V vs RHE for OER and an onset potential of 1.0V vs RHE during ORR. Finally, we conclude by giving a brief description of the Hydrogen Economy and the role that ammonia decomposition can play in achieving the potential of hydrogen economy. We detail the synthesis procedures of some highly active transition metal nitride- alkali metal imide composites and study their activity for ammonia decomposition. The catalysts show conversion efficiencies as high as 95%.

Coaxial electrospinning of WO3 nanotubes functionalized with bio-inspired Pd catalysts and their superior hydrogen sensing performance

NASA Astrophysics Data System (ADS)

Choi, Seon-Jin; Chattopadhyay, Saptarshi; Kim, Jae Jin; Kim, Sang-Joon; Tuller, Harry L.; Rutledge, Gregory C.; Kim, Il-Doo

2016-04-01

Macroporous WO3 nanotubes (NTs) functionalized with nanoscale catalysts were fabricated using coaxial electrospinning combined with sacrificial templating and protein-encapsulated catalysts. The macroporous thin-walled nanotubular structures were obtained by introducing colloidal polystyrene (PS) particles to a shell solution of W precursor and poly(vinylpyrrolidone). After coaxial electrospinning with a core liquid of mineral oil and subsequent calcination, open pores with an average diameter of 173 nm were formed on the surface of WO3 NTs due to decomposition of the PS colloids. In addition, catalytic Pd nanoparticles (NPs) were synthesized using bio-inspired protein cages, i.e., apoferritin, and uniformly dispersed within the shell solution and subsequently on the WO3 NTs. The resulting Pd functionalized macroporous WO3 NTs were demonstrated to be high performance hydrogen (H2) sensors. In particular, Pd-functionalized macroporous WO3 NTs exhibited a very high H2 response (Rair/Rgas) of 17.6 at 500 ppm with a short response time. Furthermore, the NTs were shown to be highly selective for H2 compared to other gases such as carbon monoxide (CO), ammonia (NH3), and methane (CH4). The results demonstrate a new synthetic method to prepare highly porous nanotubular structures with well-dispersed nanoscale catalysts, which can provide improved microstructures for chemical sensing.Macroporous WO3 nanotubes (NTs) functionalized with nanoscale catalysts were fabricated using coaxial electrospinning combined with sacrificial templating and protein-encapsulated catalysts. The macroporous thin-walled nanotubular structures were obtained by introducing colloidal polystyrene (PS) particles to a shell solution of W precursor and poly(vinylpyrrolidone). After coaxial electrospinning with a core liquid of mineral oil and subsequent calcination, open pores with an average diameter of 173 nm were formed on the surface of WO3 NTs due to decomposition of the PS colloids. In addition, catalytic Pd nanoparticles (NPs) were synthesized using bio-inspired protein cages, i.e., apoferritin, and uniformly dispersed within the shell solution and subsequently on the WO3 NTs. The resulting Pd functionalized macroporous WO3 NTs were demonstrated to be high performance hydrogen (H2) sensors. In particular, Pd-functionalized macroporous WO3 NTs exhibited a very high H2 response (Rair/Rgas) of 17.6 at 500 ppm with a short response time. Furthermore, the NTs were shown to be highly selective for H2 compared to other gases such as carbon monoxide (CO), ammonia (NH3), and methane (CH4). The results demonstrate a new synthetic method to prepare highly porous nanotubular structures with well-dispersed nanoscale catalysts, which can provide improved microstructures for chemical sensing. Electronic supplementary information (ESI) available: Coaxial electrospinning with different feeding rates, additional TEM analysis for pore size analysis, XPS analysis of Pd-loaded macroporous WO3 NTs, and dynamic response transition properties of sensors. See DOI: 10.1039/c5nr06611e

Functionalized polymer nanofibre membranes for protection from chemical warfare stimulants

NASA Astrophysics Data System (ADS)

Ramaseshan, Ramakrishnan; Sundarrajan, Subramanian; Liu, Yingjun; Barhate, R. S.; Lala, Neeta L.; Ramakrishna, S.

2006-06-01

A catalyst for the detoxification of nerve agents is synthesized from β-cyclodextrin (β-CD) and o-iodosobenzoic acid (IBA). Functionalized polymer nanofibre membranes from PVC polymer are fabricated with β-CD, IBA, a blend of β-CD+IBA, and the synthesized catalyst. These functionalized nanofibres are then tested for the decontamination of paraoxon, a nerve agent stimulant, and it is observed that the stimulant gets hydrolysed. The kinetics of hydrolysis is investigated using UV spectroscopy. The rates of hydrolysis for different organophosphate hydrolyzing agents are compared. The reactivity and amount of adsorption of these catalysts are of higher capacity than the conventionally used activated charcoal. A new design for protective wear is proposed based on the functionalized nanofibre membrane.

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

Ulvestad, Andrew; Sasikumar, Kiran; Kim, Jong Woo

Multielectron transfer processes are crucially important in energy and biological science but require favorable catalysts to achieve fast kinetics. Nanostructuring catalysts can dramatically improve their properties, which can be difficult to understand due to strain- and size-dependent thermodynamics, the influence of defects, and substrate-dependent activities. Here, we report three-dimensional (3D) imaging of single gold nanoparticles during catalysis of ascorbic acid decomposition using Bragg coherent diffractive imaging (BCDI). Local strains were measured in single nanoparticles and modeled using reactive molecular dynamics (RMD) simulations and finite element analysis (FEA) simulations. RMD reveals the pathway for local strain generation in the gold lattice:more » chemisorption of hydroxyl ions. FEA reveals that the RMD results are transferable to the nanocrystal sizes studied in the experiment. Our study probes the strain-activity connection and opens a powerful avenue for theoretical and experimental studies of nanocrystal catalysis.« less

Improved Catalytic Activity and Stability of a Palladium Pincer Complex by Incorporation into a Metal-Organic Framework.

PubMed

Burgess, Samantha A; Kassie, Abebu; Baranowski, Sarah A; Fritzsching, Keith J; Schmidt-Rohr, Klaus; Brown, Craig M; Wade, Casey R

2016-02-17

A porous metal-organic framework Zr6O4(OH)4(L-PdX)3 (1-X) has been constructed from Pd diphosphinite pincer complexes ([L-PdX](4-) = [(2,6-(OPAr2)2C6H3)PdX](4-), Ar = p-C6H4CO2(-), X = Cl, I). Reaction of 1-X with PhI(O2CCF3)2 facilitates I(-)/CF3CO2(-) ligand exchange to generate 1-TFA and I2 as a soluble byproduct. 1-TFA is an active and recyclable catalyst for transfer hydrogenation of benzaldehydes using formic acid as a hydrogen source. In contrast, the homogeneous analogue (t)Bu(L-PdTFA) is an ineffective catalyst owing to decomposition under the catalytic conditions, highlighting the beneficial effects of immobilization.

Pd/C Synthesized with Citric Acid: An Efficient Catalyst for Hydrogen Generation from Formic Acid/Sodium Formate

PubMed Central

Wang, Zhi-Li; Yan, Jun-Min; Wang, Hong-Li; Ping, Yun; Jiang, Qing

2012-01-01

A highly efficient hydrogen generation from formic acid/sodium formate aqueous solution catalyzed by in situ synthesized Pd/C with citric acid has been successfully achieved at room temperature. Interestingly, the presence of citric acid during the formation and growth of the Pd nanoparticles on carbon can drastically enhance the catalytic property of the resulted Pd/C, on which the conversion and turnover frequency for decomposition of formic acid/sodium formate system can reach the highest values ever reported of 85% within 160 min and 64 mol H2 mol−1 catalyst h−1, respectively, at room temperature. The present simple, low cost, but highly efficient CO-free hydrogen generation system at room temperature is believed to greatly promote the practical application of formic acid system on fuel cells. PMID:22953041

The influence of reaction time on hydrogen sulphide removal from air by means of Fe(III)-EDTA/Fiban catalysts

NASA Astrophysics Data System (ADS)

Wasag, H.; Cel, W.; Chomczynska, M.; Kujawska, J.

2018-05-01

The paper deals with a new method of hydrogen sulphide removal from air by its filtration and selective catalytic oxidation with the use of fibrous carriers of Fe(III)-EDTA complex. The basis of these filtering materials includes fibrous ion exchangers with the complex immobilized on their functional groups. It has been established that the degree of catalytic hydrogen sulphide decomposition depends on the reaction time. Thus, the required degree of hydrogen sulphide removal from air could be easily controlled by applying appropriate thickness of the filtering layer under a given filtering velocity. It allows applying very thin filtering layers of the Fe(III)-EDTA/Fiban AK-22 or Fiban A-6 catalysts. The obtained results of the research confirm the applicability of these materials for deep air purification from hydrogen sulphide.

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.

Kinetics and Efficiency of H2O2 Activation by Iron-Containing Minerals and Aquifer Materials

PubMed Central

Pham, Anh Le-Tuan; Doyle, Fiona M.; Sedlak, David L.

2014-01-01

To gain insight into factors that control H2O2 persistence and ˙OH yield in H2O2-based in situ chemical oxidation systems, the decomposition of H2O2 and transformation of phenol were investigated in the presence of iron-containing minerals and aquifer materials. Under conditions expected during remediation of soil and groundwater, the stoichiometric efficiency, defined as the amount of phenol transformed per mole of H2O2 decomposed, varied from 0.005 to 0.28%. Among the iron-containing minerals, iron oxides were 2 to 10 times less efficient in transforming phenol than iron-containing clays and synthetic iron-containing catalysts. In both iron-containing mineral and aquifer materials systems, the stoichiometric efficiency was inversely correlated with the rate of H2O2 decomposition. In aquifer materials systems, the stoichiometric efficiency was also inversely correlated with the Mn content, consistent with the fact that the decomposition of H2O2 on manganese oxides does not produce ˙OH. Removal of iron and manganese oxide coatings from the surface of aquifer materials by extraction with citrate-bicarbonate-dithionite slowed the rate of H2O2 decomposition on aquifer materials and increased the stoichiometric efficiency. In addition, the presence of 2 mM of dissolved SiO2 slowed the rate of H2O2 decomposition on aquifer materials by over 80% without affecting the stoichiometric efficiency. PMID:23047055

Kinetics and efficiency of H2O2 activation by iron-containing minerals and aquifer materials.

PubMed

Pham, Anh Le-Tuan; Doyle, Fiona M; Sedlak, David L

2012-12-01

To gain insight into factors that control H(2)O(2) persistence and ·OH yield in H(2)O(2)-based in situ chemical oxidation systems, the decomposition of H(2)O(2) and transformation of phenol were investigated in the presence of iron-containing minerals and aquifer materials. Under conditions expected during remediation of soil and groundwater, the stoichiometric efficiency, defined as the amount of phenol transformed per mole of H(2)O(2) decomposed, varied from 0.005 to 0.28%. Among the iron-containing minerals, iron oxides were 2-10 times less efficient in transforming phenol than iron-containing clays and synthetic iron-containing catalysts. In both iron-containing mineral and aquifer materials systems, the stoichiometric efficiency was inversely correlated with the rate of H(2)O(2) decomposition. In aquifer materials systems, the stoichiometric efficiency was also inversely correlated with the Mn content, consistent with the fact that the decomposition of H(2)O(2) on manganese oxides does not produce ·OH. Removal of iron and manganese oxide coatings from the surface of aquifer materials by extraction with citrate-bicarbonate-dithionite slowed the rate of H(2)O(2) decomposition on aquifer materials and increased the stoichiometric efficiency. In addition, the presence of 2 mM of dissolved SiO(2) slowed the rate of H(2)O(2) decomposition on aquifer materials by over 80% without affecting the stoichiometric efficiency. Copyright © 2012 Elsevier Ltd. All rights reserved.

Boron nitride encapsulated copper nanoparticles: a facile one-step synthesis and their effect on thermal decomposition of ammonium perchlorate.

PubMed

Huang, Caijin; Liu, Qiuwen; Fan, Wenjie; Qiu, Xiaoqing

2015-11-16

Reactivity is of great importance for metal nanoparticles used as catalysts, biomaterials and advanced sensors, but seeking for high reactivity seems to be conflict with high chemical stability required for metal nanoparticles. There is a subtle balance between reactivity and stability. This could be reached for colloidal metal nanoparticles using organic capping reagents, whereas it is challenging for powder metal nanoparticles. Here, we developed an alternative approach to encapsulate copper nanoparticles with a chemical inertness material--hexagonal boron nitride. The wrapped copper nanoparticles not only exhibit high oxidation resistance under air atmosphere, but also keep excellent promoting effect on thermal decomposition of ammonium perchlorate. This approach opens the way to design metal nanoparticles with both high stability and reactivity for nanocatalysts and their technological application.

Boron nitride encapsulated copper nanoparticles: a facile one-step synthesis and their effect on thermal decomposition of ammonium perchlorate

PubMed Central

Huang, Caijin; liu, Qiuwen; Fan, Wenjie; Qiu, Xiaoqing

2015-01-01

Reactivity is of great importance for metal nanoparticles used as catalysts, biomaterials and advanced sensors, but seeking for high reactivity seems to be conflict with high chemical stability required for metal nanoparticles. There is a subtle balance between reactivity and stability. This could be reached for colloidal metal nanoparticles using organic capping reagents, whereas it is challenging for powder metal nanoparticles. Here, we developed an alternative approach to encapsulate copper nanoparticles with a chemical inertness material—hexagonal boron nitride. The wrapped copper nanoparticles not only exhibit high oxidation resistance under air atmosphere, but also keep excellent promoting effect on thermal decomposition of ammonium perchlorate. This approach opens the way to design metal nanoparticles with both high stability and reactivity for nanocatalysts and their technological application. PMID:26567862

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

Xing, Rong; Dagle, Vanessa Lebarbier; Flake, Matthew

In this study we examine feasibility for steam reforming the mixed oxygenate aqueous fraction derived from mildly hydrotreated fast pyrolysis bio-oils. Catalysts selective towards hydrogen formation and resistant to carbon formation utilizing feeds with relatively low steam-to-carbon (S/C) ratios are desired. Rh (5 wt%), Pt (5 wt%), Ru (5 wt%), Ir (5 wt%), Ni (15 wt%), and Co (15 wt%) metals supported on MgAl 2O 4 were evaluated for catalytic performance at 500°C and 1 atm using a complex feed mixture comprising of acids, polyols, cycloalkanes, and phenolic compounds. The Rh catalyst was found to be the most active andmore » resistant to carbon formation. The Ni and Co catalysts were found to be more active than the other noble metal catalysts investigated (Pt, Ru, and Ir). However, Ni was found to form significantly more carbon (coke) on the catalyst surface. Furthermore, Co was found to be the most selective towards H 2 formation. Evaluating the effect of temperature on stability for the Rh catalyst we found that catalyst stability was best when operated at 500°C as compared to the higher temperatures investigated (700, 800°C). When operating at 700°C significantly more graphitic formation was observed on the spent catalyst surface. Operating at 800°C resulted in reactor plugging as a result of thermal decomposition of the reactants. Thus, a concept analogous to the petroleum industries’ use of a pre-reformer, operated at approximately 500°C for steam reforming of the heavier naphtha components, followed by a high temperature methane reforming operated in the 600-850°C temperature range, could be applied in the case of steam reforming biomass derived oxygenates. Moreover, stability evaluations were performed over the Rh, Ni, and Co catalysts at 500°C and 1 atm, under similar initial conversions, reveal the Co catalyst to be the most stable and selective towards H 2 production. Conversion and selectivity to CH 4 over Co remained relatively stable at approximately 80% and 1.2%, respectively. By contrast, the Rh and Ni catalysts CH 4 selectivity’s were approximately 7-8%. Thus suggesting that a Co type catalyst may be more suitable for the steam reforming of biomass derived oxygenates as compared to the more conventional Ni and Rh type steam reforming catalysts. However, deposition of carbon on the surface was observed. High resolution TEM on the spent catalysts revealed the formation of graphitic carbon on the Rh catalyst, and filamentous carbon formation was observed on both the Ni and Co catalysts, albeit less pronounced on Co. Thus there is certainly opportunity for improvement in Co catalyst design and/or with process optimization.« less

HOMOGENEOUS AIR OXIDATION OF HYDROCARBONS UTILIZING MN AND CO CATALYSTS

EPA Science Inventory

Homogeneous Air Oxidation of Hydrocarbons Utilizing Mn and Co Catalysts

Thomas M. Becker and Michael A. Gonzalez*, Sustainable Technology Division, Office of Research and Development; United States Environmental Protection Agency, 26 West Martin Luther King Drive, Mail Sto...

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

Dayton, David C; Kataria, Atish; Gupta, Rabhubir

The objective of the project is to develop and demonstrate a novel fluidized-bed process module called a Therminator to simultaneously destroy and/or remove tar, NH3 and H2S from raw syngas produced by a fluidized-bed biomass gasifier. The raw syngas contains as much as 10 g/m3 of tar, 4,000 ppmv of NH3 and 100 ppmv of H2S. The goal of the Therminator module would be to use promising regenerable catalysts developed for removing tar, ammonia, and H2S down to low levels (around 10 ppm). Tars are cracked to a non-condensable gas and coke that would deposit on the acid catalyst. Wemore » will deposit coke, much like a fluid catalytic cracker (FCC) in a petroleum refinery. The deposited coke fouls the catalyst, much like FCC, but the coke would be burned off in the regenerator and the regenerated catalyst would be returned to the cracker. The rapid circulation between the cracker and regenerator would ensure the availability of the required amount of regenerated catalyst to accomplish our goal. Also, by removing sulfur down to less than 10 ppmv, NH3 decomposition would also be possible in the cracker at 600-700°C. In the cracker, tar decomposes and lays down coke on the acid sites of the catalyst, NH3 is decomposed using a small amount of metal (e.g., nickel or iron) catalyst incorporated into the catalyst matrix, and H2S is removed by a small amount of a metal oxide (e.g. zinc oxide or zinc titanate) by the H2S-metal oxide reaction to form metal sulfide. After a tolerable decline in activity for these reactions, the catalyst particles (and additives) are transported to the regenerator where they are exposed to air to remove the coke and to regenerate the metal sulfide back to metal oxide. Sulfate formation is avoided by running the regeneration with slightly sub-stoichiometric quantity of oxygen. Following regeneration, the catalyst is transported back to the cracker and the cycling continues. Analogous to an FCC reactor system, rapid cycling will allow the use of very active cracking catalysts that lose activity due to coking within the order of several seconds.« less

A durable PtRu/C catalyst with a thin protective layer for direct methanol fuel cells.

PubMed

Shimazaki, Yuzuru; Hayasaka, Sho; Koyama, Tsubasa; Nagao, Daisuke; Kobayashi, Yoshio; Konno, Mikio

2010-11-15

A methanol oxidation catalyst with improved durability in acidic environments is reported. The catalyst consists of PtRu alloy nanoparticles on a carbon support that were stabilized with a silane-coupling agent. The catalyst was prepared by reducing ions of Pt and Ru in the presence of a carbon support and the silane-coupling agent. The careful choice of preparatory conditions such as the concentration of the silane-coupling agent and solution pH resulted in the preparation of catalyst in which the PtRu nanoparticles were dispersively adsorbed onto the carbon support. The catalytic activity was similar to that of a commercial catalyst and was unchanged after immersion in sulfuric acid solution for 1000 h, suggesting the high durability of the PtRu catalyst for the anode of direct methanol fuel cells. Copyright © 2010 Elsevier Inc. All rights reserved.

Electrochemical Protection of Thin Film Electrodes in Solid State Nanopores

PubMed Central

Harrer, Stefan; Waggoner, Philip S.; Luan, Binquan; Afzali-Ardakani, Ali; Goldfarb, Dario L.; Peng, Hongbo; Martyna, Glenn; Rossnagel, Stephen M.; Stolovitzky, Gustavo A.

2011-01-01

We have eliminated electrochemical surface oxidation and reduction as well as water decomposition inside sub-5-nm wide nanopores in conducting TiN membranes using a surface passivation technique. Nanopore ionic conductances, and therefore pore diameters, were unchanged in passivated pores after applying potentials of ±4.5 V for as long as 24 h. Water decomposition was eliminated by using aqueous 90% glycerol solvent. The use of a protective self-assembled monolayer of hexadecylphosphonic acid was also investigated. PMID:21597142

(Non) formation of methanol by direct hydrogenation of formate on copper catalysts

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

Yang, Yong; Mims, Charles A.; Disselkamp, Robert S.

2010-10-14

We have attempted to hydrogenate adsorbed formate species on copper catalysts to probe the importance of this postulated mechanistic step in methanol synthesis. Surface formate coverages up to 0.25 were produced at temperatures between 413K and 453K on supported (Cu/SiO2) copper and unsupported copper catalysts. The adlayers were produced by various methods including (1) steady state catalytic conditions in CO2-H2 (3:1, 6 bar) atmospheres, and (2) by exposure of the catalysts to formic acid. As reported in earlier work, the catalytic surface at steady state contains bidentate formate species with coverages up to saturation levels of ~ 0.25 at themore » low temperatures of this study. The reactivity of these formate adlayers was investigated at relevant reaction temperatures in atmospheres containing up to 6 bar H2 partial pressure by simultaneous mass spectrometry (MS) and infrared (IR) spectroscopy measurements. The yield of methanol during the attempted hydrogenation (“titration”) of these adlayers was insignificant (<0.2 mol % of the formate adlayer) even in dry hydrogen partial pressures up to 6 bar. Hydrogen titration of formate species produced from formic acid also failed to produce significant quantities of methanol, and attempted titration in gases consisting of CO-hydrogen mixtures or dry CO2 were also unproductive. The formate decomposition kinetics, measured by IR, were also unaffected by these changes in the gas composition. Similar experiments on unsupported copper also failed to show any methanol. From these results, we conclude that methanol synthesis on copper cannot result from the direct hydrogenation of (bidentate) formate species in simple steps involving adsorbed H species alone. Furthermore, experiments performed on both supported (Cu/SiO2) and unsupported copper catalysts gave similar results implying that the methanol synthesis reaction mechanism only involves metal surface chemistry. Pre-exposure of the bidentate formate adlayer to oxidation by O2 or N2O produces a change to a monodentate configuration. Attempted titration of this monodentate formate/O coadsorbed layer in dry hydrogen produces significant quantities of methanol, although decomposition of formate to carbon dioxide and hydrogen remains the dominant reaction pathway. Simultaneous production of water is also observed during this titration as the copper surface is re-reduced. These results indicate that co-adsorbates related to surface oxygen or water-derived species may be critical to methanol production on copper, perhaps assisting in the hydrogenation of adsorbed formate to adsorbed methoxyl.« less

Pt and Pd catalyzed oxidation of Li 2O 2 and DMSO during Li–O 2 battery charging

DOE PAGES

Gittleson, Forrest S.; Ryu, Won-Hee; Schwab, Mark; ...

2016-01-01

Rechargeable Li-O 2 and Li-air batteries require electrode and electrolyte materials that synergistcally promote long-term cell operation. We investigate the role of noble metals Pt and Pd as catalysts for the Li-O 2 oxidation process and their compatibility with a dimethyl sulfoxide (DMSO) based electrolyte. Lastly, we identify a basis for low potential Li 2O 2 evolution followed by oxidative decomposition of the electrolyte to form carbonate side products.

Production of metal particles and clusters

NASA Technical Reports Server (NTRS)

Mcmanus, S. P.

1982-01-01

The feasibility of producing novel metals or metal clusters in a low gravity environment was studied. The production of coordinately unsaturated metal carbonyls by thermolysis or photolysis of stable metal carbonyls has the potential to generate novel catalysts by this technique. Laser irradiation of available metal carbonyls was investigated. It is found that laser induced decomposition of metal carbonyls is feasible for producing a variety of coordinately unsaturated species. Formation of clustered species does occur but is hampered by weak metal-metal bonds.

Sorptive Activity and Hydrophobic Behavior of Aerogels Based on Reduced Graphene Oxide and Carbon Nanotubes

NASA Astrophysics Data System (ADS)

Sultanov, F.; Bakbolat, B.; Daulbaev, Ch.; Urazgalieva, A.; Azizov, Z.; Mansurov, Z.; Tulepov, M.; Pei, S. S.

2017-07-01

A study has been made of the possibility of obtaining three-dimensional porous aerogel structures based on reduced graphene oxide and carbon nanotubes. Carbon nanotubes in the structure of the finished aerogel based on reduced graphene oxide were grown by thermal decomposition of ferrocene into cyclopentadienyl and iron ions which served as the source of carbon and a catalyst respectively. The obtained composite aerogels exhibit high sorptive activity for organic liquids of different densities.

An Overview of Hydrogen Generation and Storage for Low-Temperature PEM Fuel Cells

DTIC Science & Technology

1999-11-01

environment. Otherwise, the wt % of stored hydrogen is attractive; e.g., LiH is 25 percent. Thermal stability of pure alkali and alkaline earth- metal ...nanofibers can be prepared by metal -catalyzed decomposition (at 450 to 750 °C) of carbon-containing gases to possess a cross-sectional area between 30 to ...respect to the face of the metal particle. Separation distance between layers depends on the type of catalyst, gas, and reaction conditions used

Ozonation of clofibric acid catalyzed by titanium dioxide.

PubMed

Rosal, Roberto; Gonzalo, María S; Rodríguez, Antonio; García-Calvo, Eloy

2009-09-30

The removal of clofibric acid from aqueous solution has been investigated in catalytic and non-catalytic semicontinuous ozonation runs. Kinetic data were analyzed using second order expressions for the reaction between organics and ozone or hydroxyl radicals. Catalytic runs used a commercial titanium dioxide catalyst consisting of fumed colloidal particles. The kinetic constant of the non-catalytic ozonation of clofibric acid at pH 3 was 8.16 x 10(-3)+/-3.4 x 10(-4)L mmol(-1)s(-1). The extent of mineralization during non-catalytic runs ranged from 50% at pH 7 to 20% at pH 3 in a reaction that essentially took place during the first 10-20 min. The catalyst increased the total extent of mineralization, its effect being more important during the first part of the reaction. The pseudo-homogeneous catalytic rate constant was 2.17 x 10(-2) L mmol(-1)s(-1) at pH 3 and 6.80 x 10(-1)L mmol(-1)s(-1) at pH 5, with up to a threefold increase with respect to non-catalytic constants using catalyst load of 1g/L. A set of stopped-flow experiments were designed to elucidate the role of catalyst, whose effect was probably due to the adsorption of organics on catalytic sites rather than to the promotion of ozone decomposition.

Methanol-Water Aqueous-Phase Reforming with the Assistance of Dehydrogenases at Near-Room Temperature.

PubMed

Shen, Yangbin; Zhan, Yulu; Li, Shuping; Ning, Fandi; Du, Ying; Huang, Yunjie; He, Ting; Zhou, Xiaochun

2018-03-09

As an excellent hydrogen-storage medium, methanol has many advantages, such as high hydrogen content (12.6 wt %), low cost, and availability from biomass or photocatalysis. However, conventional methanol-water reforming usually proceeds at high temperatures. In this research, we successfully designed a new effective strategy to generate hydrogen from methanol at near-room temperature. The strategy involved two main processes: CH 3 OH→HCOOH→H 2 and NADH→HCOOH→H 2 . The first process (CH 3 OH→HCOOH→H 2 ) was performed by an alcohol dehydrogenase (ADH), an aldehyde dehydrogenase (ALDH), and an Ir catalyst. The second procedure (NADH→HCOOH→H 2 ) was performed by formate dehydrogenase (FDH) and the Ir catalyst. The Ir catalyst used was a previously reported polymer complex catalyst [Cp*IrCl 2 (ppy); Cp*=pentamethylcyclopentadienyl, ppy=polypyrrole] with high catalytic activity for the decomposition of formic acid at room temperature and is compatible with enzymes, coenzymes, and poisoning chemicals. Our results revealed that the optimum hydrogen generation rate could reach up to 17.8 μmol h -1  g cat -1 under weak basic conditions at 30 °C. This will have high impact on hydrogen storage, production, and applications and should also provide new inspiration for hydrogen generation from methanol. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simulation of the Dynamics of Isothermal Growth of Single-Layer Graphene on a Copper Catalyst in the Process of Chemical Vapor Deposition of Hydrocarbons

NASA Astrophysics Data System (ADS)

Futko, S. I.; Shulitskii, B. G.; Labunov, V. A.; Ermolaeva, E. M.

2018-01-01

A new kinetic model of isothermal growth of single-layer graphene on a copper catalyst as a result of the chemical vapor deposition of hydrocarbons on it at a low pressure has been developed on the basis of in situ measurements of the growth of graphene in the process of its synthesis. This model defines the synthesis of graphene with regard for the chemisorption and catalytic decomposition of ethylene on the surface of a copper catalyst, the diffusion of carbon atoms in the radial direction to the nucleation centers within the thin melted near-surface copper layer, and the nucleation and autocatalytic growth of graphene domains. It is shown that the time dependence of the rate of growth of a graphene domain has a characteristic asymmetrical bell-like shape. The dependences of the surface area and size of a graphene domain and the rate of its growth on the time at different synthesis temperatures and ethylene concentrations have been obtained. Time characteristics of the growth of graphene domains depending on the parameters of their synthesis were calculated. The results obtained can be used for determining optimum regimes of synthesis of graphene in the process of chemical vapor deposition of hydrocarbons on different catalysts with a low solubility of carbon.

Magnetite/Fe-Al-montmorillonite as a Fenton catalyst with efficient degradation of phenol.

PubMed

Wei, Xipeng; Wu, Honghai; Sun, Feng

2017-10-15

A Fe-Al-MPM material assembled from nanosized magnetite and Fe-Al-pillared montmorillonite (Fe-Al-Mt) was characterized by XRD, XPS, BET, SEM and TEM. Fe-Al-Mt was proven to be capable of facilitating the dispersion of magnetite nanoparticles and inhibiting their aggregation. The coupling of Fe-Al-Mt with magnetite in Fe-Al-MPM improved its Fenton catalytic activity. Complete conversion of phenol within 80min with a high TOC removal rate (>78%) was achieved using Fe-Al-MPM as a heterogeneous Fenton catalyst under optimized conditions. The Fenton process first underwent a slow induction reaction, followed by the rapid oxidative decomposition of phenol. The existence of the induction reaction period was attributed to the need for activation of the iron species on the catalyst surfaces, and the duration depended on the solution temperature, pH and catalyst's nature. More importantly, Fe-Al-MPM showed high stability, with a low iron-release even after it was recycled 5 times. The minimal iron-leaching from Fe-Al-MPM was ascribed to the competitive adsorption of the incorporated aluminum and all the iron species for the residual (low ecotoxicity) organic ligands. These organic acids were among the main products that remained at the end of the Fenton process. Also important was the ease of separation of Fe-Al-MPM under a magnetic field. Copyright © 2017 Elsevier Inc. All rights reserved.

Molecular water oxidation mechanisms followed by transition metals: state of the art.

PubMed

Sala, Xavier; Maji, Somnath; Bofill, Roger; García-Antón, Jordi; Escriche, Lluís; Llobet, Antoni

2014-02-18

One clean alternative to fossil fuels would be to split water using sunlight. However, to achieve this goal, researchers still need to fully understand and control several key chemical reactions. One of them is the catalytic oxidation of water to molecular oxygen, which also occurs at the oxygen evolving center of photosystem II in green plants and algae. Despite its importance for biology and renewable energy, the mechanism of this reaction is not fully understood. Transition metal water oxidation catalysts in homogeneous media offer a superb platform for researchers to investigate and extract the crucial information to describe the different steps involved in this complex reaction accurately. The mechanistic information extracted at a molecular level allows researchers to understand both the factors that govern this reaction and the ones that derail the system to cause decomposition. As a result, rugged and efficient water oxidation catalysts with potential technological applications can be developed. In this Account, we discuss the current mechanistic understanding of the water oxidation reaction catalyzed by transition metals in the homogeneous phase, based on work developed in our laboratories and complemented by research from other groups. Rather than reviewing all of the catalysts described to date, we focus systematically on the several key elements and their rationale from molecules studied in homogeneous media. We organize these catalysts based on how the crucial oxygen-oxygen bond step takes place, whether via a water nucleophilic attack or via the interaction of two M-O units, rather than based on the nuclearity of the water oxidation catalysts. Furthermore we have used DFT methodology to characterize key intermediates and transition states. The combination of both theory and experiments has allowed us to get a complete view of the water oxidation cycle for the different catalysts studied. Finally, we also describe the various deactivation pathways for these catalysts.

Novel process and catalytic materials for converting CO2 and H2 containing mixtures to liquid fuels and chemicals.

PubMed

Meiri, Nora; Dinburg, Yakov; Amoyal, Meital; Koukouliev, Viatcheslav; Nehemya, Roxana Vidruk; Landau, Miron V; Herskowitz, Moti

2015-01-01

Carbon dioxide and water are renewable and the most abundant feedstocks for the production of chemicals and fungible fuels. However, the current technologies for production of hydrogen from water are not competitive. Therefore, reacting carbon dioxide with hydrogen is not economically viable in the near future. Other alternatives include natural gas, biogas or biomass for the production of carbon dioxide, hydrogen and carbon monoxide mixtures that react to yield chemicals and fungible fuels. The latter process requires a high performance catalyst that enhances the reverse water-gas-shift (RWGS) reaction and Fischer-Tropsch synthesis (FTS) to higher hydrocarbons combined with an optimal reactor system. Important aspects of a novel catalyst, based on a Fe spinel and three-reactor system developed for this purpose published in our recent paper and patent, were investigated in this study. Potassium was found to be a key promoter that improves the reaction rates of the RWGS and FTS and increases the selectivity of higher hydrocarbons while producing mostly olefins. It changed the texture of the catalyst, stabilized the Fe-Al-O spinel, thus preventing decomposition into Fe3O4 and Al2O3. Potassium also increased the content of Fe5C2 while shifting Fe in the oxide and carbide phases to a more reduced state. In addition, it increased the relative exposure of carbide iron on the catalysts surface, the CO2 adsorption and the adsorption strength. A detailed kinetic model of the RWGS, FTS and methanation reactions was developed for the Fe spinel catalyst based on extensive experimental data measured over a range of operating conditions. Significant oligomerization activity of the catalyst was found. Testing the pelletized catalyst with CO2, CO and H2 mixtures over a range of operating conditions demonstrated its high productivity to higher hydrocarbons. The composition of the liquid (C5+) was found to be a function of the potassium content and the composition of the feedstock.

In-use catalyst surface area and its relation to HC conversion efficiency and FTP emissions

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

Donahue, K.S.; Sabourin, M.A.; Larson, R.E.

1986-01-01

Surface area data, steady-state hydrocarbon conversion efficiency data, and hydrocarbon emissions results have been determined for catalysts collected by the U.S. Environmental Protection Agency from properly maintained 1981 and 1982 model year vehicles. Catalysts covered in this study were limited to those with three-way-plus-oxidation monolith technologies. Catalyst surface areas were measured using the BET method, conversion efficiencies were measured on an exhaust gas generator, and emissions results were determined using the Urban Driving Schedule of the Federal Test Procedure. Results indicate that correlation of catalyst surface area data with hydrocarbon conversion efficiency data and hydrocarbon emissions results is significant formore » the sample studied.« less

Simple citric acid-catalyzed surface esterification of cellulose nanocrystals.

PubMed

Ávila Ramírez, Jhon Alejandro; Fortunati, Elena; Kenny, José María; Torre, Luigi; Foresti, María Laura

2017-02-10

A simple straightforward route for the surface esterification of cellulose nanocrystals (CNC) is herein proposed. CNC obtained from microcrystalline cellulose were acetylated using as catalyst citric acid, a α-hydroxy acid present in citrus fruits and industrially produced by certain molds in sucrose or glucose-containing medium. No additional solvent was added to the system; instead, the acylant (acetic anhydride) was used in sufficient excess to allow CNC dispersion and proper suspension agitation. By tuning the catalyst load, CNC with two different degree of substitution (i.e. DS=0.18 and 0.34) were obtained. Acetylated cellulose nanocrystals were characterized in terms of chemical structure, crystallinity, morphology, thermal decomposition and dispersion in a non-polar solvent. Results illustrated for the first time the suitability of the protocol proposed for the simple surface acetylation of cellulose nanocrystals. Copyright © 2016 Elsevier Ltd. All rights reserved.

Patterned carbon nanotubes fabricated by the combination of microcontact printing and diblock copolymer micelles.

PubMed

Xu, Peng; Ji, Xin; Qi, Junlei; Yang, Hongmin; Zheng, Weitao; Abetz, Volker; Jiang, Shimei; Shen, Jiacong

2010-01-01

A convenient approach to synthesize patterned carbon nanotubes (CNTs) of three morphologies on printed substrates by combination of microcontact printing (microCP) and a plasma-enhanced chemical vapor deposition (PECVD) process is presented. Micelles of polystyrene-block-poly-(2-vinylpyridine) (PS-b-P2VP) in toluene were used as nanoreactors to fabricate FeCl3 in the core domains, and the complex solution was used as an ink to print films with polydimethylsiloxane (PDMS) stamps, different morphologies (porous, dots and stripes patterns) of the FeCl3-loaded micellar films were left onto silicon substrates after printed. After removing the polymer by thermal decomposition, the left iron oxide cluster arrays on the substrate were used as catalysts for the growth of CNTs by the process of PECVD, where the CNTs uniformly distributed on the substrates according to the morphologies of patterned catalysts arrays.

Non-metal doped TiO2 nanotube arrays for high efficiency photocatalytic decomposition of organic species in water

NASA Astrophysics Data System (ADS)

Szkoda, Mariusz; Siuzdak, Katarzyna; Lisowska-Oleksiak, Anna

2016-10-01

Titanium dioxide is a well-known photoactive semiconductor with a variety of possible applications. The procedure of pollutant degradation is mainly performed using TiO2 powder suspension. It can also be exploited an immobilized catalyst on a solid support. Morphology and chemical doping have a great influence on TiO2 activity under illumination. Here we compare photoactivity of titania nanotube arrays doped with non-metal atoms: nitrogen, iodine and boron applied for photodegradation of organic dye - methylene blue and terephtalic acid. The doped samples act as a much better photocatalyst in the degradation process of methylene blue and lead to the formation of much higher amount of hydroxyl radicals (•OH) than undoped TiO2 nanotube arrays. The use of a catalyst active under solar light illumination in the form of thin films on a stable substrate can be scaled up for an industrial application.

NOx Binding and Dissociation: Enhanced Ferroelectric Surface Chemistry by Catalytic Monolayers

NASA Astrophysics Data System (ADS)

Kakekhani, Arvin; Ismail-Beigi, Sohrab

2013-03-01

NOx molecules are regulated air pollutants produced during automotive combustion. As part of an effort to design viable catalysts for NOx decomposition operating at higher temperatures that would allow for improved fuel efficiency, we examine NOx chemistry on ferroelectric perovskite surfaces. Changing the direction of ferroelectric polarization can modify surface electronic properties and may lead to switchable surface chemistry. Here, we describe our recent work on potentially enhanced surface chemistry using catalytic RuO2 monolayers on perovskite ferroelectric substrates. In addition to thermodynamic stabilization of the RuO2 layer, we present results on the polarization-dependent binding of NO, O2, N2, and atomic O and N. We present results showing that one key problem with current catalysts, involving the difficulty of releasing dissociation products (especially oxygen), can be ameliorated by this method. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.

Method for forming porous sintered bodies with controlled pore structure

DOEpatents

Whinnery, LeRoy Louis; Nichols, Monte Carl

2000-01-01

The present invention is based, in part, on a method for combining a mixture of hydroxide and hydride functional siloxanes to form a polysiloxane polymer foam, that leaves no residue (zero char yield) upon thermal decomposition, with ceramic and/or metal powders and appropriate catalysts to produce porous foam structures having compositions, densities, porosities and structures not previously attainable. The siloxanes are mixed with the ceramic and/or metal powder, wherein the powder has a particle size of about 400 .mu.m or less, a catalyst is added causing the siloxanes to foam and crosslink, thereby forming a polysiloxane polymer foam having the metal or ceramic powder dispersed therein. The polymer foam is heated to thermally decompose the polymer foam and sinter the powder particles together. Because the system is completely nonaqueous, this method further provides for incorporating reactive metals such as magnesium and aluminum, which can be further processed, into the foam structure.

Systematic Identification of Promoters for Methane Oxidation Catalysts Using Size- and Composition-Controlled Pd-Based Bimetallic Nanocrystals.

PubMed

Willis, Joshua J; Goodman, Emmett D; Wu, Liheng; Riscoe, Andrew R; Martins, Pedro; Tassone, Christopher J; Cargnello, Matteo

2017-08-30

Promoters enhance the performance of catalytic active phases by increasing rates, stability, and/or selectivity. The process of identifying promoters is in most cases empirical and relies on testing a broad range of catalysts prepared with the random deposition of active and promoter phases, typically with no fine control over their localization. This issue is particularly relevant in supported bimetallic systems, where two metals are codeposited onto high-surface area materials. We here report the use of colloidal bimetallic nanocrystals to produce catalysts where the active and promoter phases are colocalized to a fine extent. This strategy enables a systematic approach to study the promotional effects of several transition metals on palladium catalysts for methane oxidation. In order to achieve these goals, we demonstrate a single synthetic protocol to obtain uniform palladium-based bimetallic nanocrystals (PdM, M = V, Mn, Fe, Co, Ni, Zn, Sn, and potentially extendable to other metal combinations) with a wide variety of compositions and sizes based on high-temperature thermal decomposition of readily available precursors. Once the nanocrystals are supported onto oxide materials, thermal treatments in air cause segregation of the base metal oxide phase in close proximity to the Pd phase. We demonstrate that some metals (Fe, Co, and Sn) inhibit the sintering of the active Pd metal phase, while others (Ni and Zn) increase its intrinsic activity compared to a monometallic Pd catalyst. This procedure can be generalized to systematically investigate the promotional effects of metal and metal oxide phases for a variety of active metal-promoter combinations and catalytic reactions.

Probing platinum degradation in polymer electrolyte membrane fuel cells by synchrotron X-ray microscopy.

PubMed

Berejnov, Viatcheslav; Martin, Zulima; West, Marcia; Kundu, Sumit; Bessarabov, Dmitri; Stumper, Jürgen; Susac, Darija; Hitchcock, Adam P

2012-04-14

Synchrotron-based scanning transmission X-ray spectromicroscopy (STXM) was used to characterize the local chemical environment at and around the platinum particles in the membrane (PTIM) which form in operationally tested (end-of-life, EOL) catalyst coated membranes (CCMs) of polymer electrolyte membrane fuel cells (PEM-FC). The band of metallic Pt particles in operationally tested CCM membranes was imaged using transmission electron microscopy (TEM). The cathode catalyst layer in the beginning-of-life (BOL) CCMs was fabricated using commercially available catalysts created from Pt precursors with and without nitrogen containing ligands. The surface composition of these catalyst powders was measured by X-ray Photoelectron Spectroscopy (XPS). The local chemical environment of the PTIM in EOL CCMs was found to be directly related to the Pt precursor used in CCM fabrication. STXM chemical mapping at the N 1s edge revealed a characteristic spectrum at and around the dendritic Pt particles in CCMs fabricated with nitrogen containing Pt-precursors. This N 1s spectrum was identical to that of the cathode and different from the membrane. For CCM samples fabricated without nitrogen containing Pt-precursors the N 1s spectrum at the Pt particles was indistinguishable from that of the adjacent membrane. We interpret these observations to indicate that nitrogenous ligands in the nitrogen containing precursors, or decomposition product(s) from that source, are transported together with the dissolved Pt from the cathode into the membrane as a result of the catalyst degradation process. This places constraints on possible mechanisms for the PTIM band formation process.

Efficient Removal of Methane over Cobalt-Monoxide-Doped AuPd Nanocatalysts.

PubMed

Xie, Shaohua; Liu, Yuxi; Deng, Jiguang; Zang, Simiao; Zhang, Zhenhua; Arandiyan, Hamidreza; Dai, Hongxing

2017-02-21

To overcome deactivation of Pd-based catalysts at high temperatures, we herein design a novel pathway by introducing a certain amount of CoO to the supported Au-Pd alloy nanoparticles (NPs) to generate high-performance Au-Pd-xCoO/three-dimensionally ordered macroporous (3DOM) Co 3 O 4 (x is the Co/Pd molar ratio) catalysts. The doping of CoO induced the formation of PdO-CoO active sites, which was beneficial for the improvement in adsorption and activation of CH 4 and catalytic performance. The Au-Pd-0.40CoO/3DOM Co 3 O 4 sample performed the best (T 90% = 341 °C at a space velocity of 20 000 mL g -1 h -1 ). Deactivation of the 3DOM Co 3 O 4 -supported Au-Pd, Pd-CoO, and Au-Pd-xCoO nanocatalysts resulting from water vapor addition was due to the formation and accumulation of hydroxyl on the catalyst surface, whereas deactivation of the Pd-CoO/3DOM Co 3 O 4 catalyst at high temperatures (680-800 °C) might be due to decomposition of the PdO y active phase into aggregated Pd 0 NPs. The Au-Pd-xCoO/3DOM Co 3 O 4 nanocatalysts exhibited better thermal stability and water tolerance ability compared to the 3DOM Co 3 O 4 -supported Au-Pd and Pd-CoO nanocatalysts. We believe that the supported Au-Pd-xCoO nanomaterials are promising catalysts in practical applications for organic combustion.

Nickel-catalyzed asymmetric α-arylation and heteroarylation of ketones with chloroarenes: effect of halide on selectivity, oxidation state, and room-temperature reactions.

PubMed

Ge, Shaozhong; Hartwig, John F

2011-10-19

We report the α-arylation of ketones with a range of aryl chlorides with enantioselectivities from 90 to 99% ee catalyzed by the combination of Ni(COD)(2) and (R)-BINAP and the coupling of ketones with a range of heteroaryl chlorides with enantioselectivities up to 99% ee catalyzed by Ni(COD)(2) and (R)-DIFLUORPHOS. The analogous reactions of bromoarenes occur with much lower enantioselectivities. Mechanistic studies showed that the difference in the rates of decomposition of the arylnickel(II) halide intermediates to {[(R)-BINAP]NiX}(2) likely accounts for the difference in the enantioselectivities of the reactions of bromoarenes and chloroarenes. This catalyst decomposition can be overcome by conducting the reactions with [(R)-BINAP]Ni(η(2)-NC-Ph) (4), which undergoes oxidative addition to haloarenes at room temperature.

Synergistic integration of ion-exchange and catalytic reduction for complete decomposition of perchlorate in waste water.

PubMed

Kim, You-Na; Choi, Minkee

2014-07-01

Ion-exchange has been frequently used for the treatment of perchlorate (ClO4(-)), but disposal or regeneration of the spent resins has been the major hurdle for field application. Here we demonstrate a synergistic integration of ion-exchange and catalytic decomposition by using Pd-supported ion-exchange resin as an adsorption/catalysis bifunctional material. The ion-exchange capability of the resin did not change after generation of the Pd clusters via mild ethanol reduction, and thus showed very high ion-exchange selectivity and capacity toward ClO4(-). After the resin was saturated with ClO4(-) in an adsorption mode, it was possible to fully decompose the adsorbed ClO4(-) into nontoxic Cl(-) by the catalytic function of the Pd catalysts under H2 atmosphere. It was demonstrated that prewetting the ion-exchange resin with ethanol significantly accelerate the decomposition of ClO4(-) due to the weaker association of ClO4(-) with the ion-exchange sites of the resin, which allows more facile access of ClO4(-) to the catalytically active Pd-resin interface. In the presence of ethanol, >90% of the adsorbed ClO4(-) could be decomposed within 24 h at 10 bar H2 and 373 K. The ClO4(-) adsorption-catalytic decomposition cycle could be repeated up to five times without loss of ClO4(-) adsorption capacity and selectivity.

Hydrothermal performance of catalyst supports

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

Elam, Jeffrey W.; Marshall, Christopher L.; Libera, Joseph A.

A high surface area catalyst with a mesoporous support structure and a thin conformal coating over the surface of the support structure. The high surface area catalyst support is adapted for carrying out a reaction in a reaction environment where the thin conformal coating protects the support structure within the reaction environment. In various embodiments, the support structure is a mesoporous silica catalytic support and the thin conformal coating comprises a layer of metal oxide resistant to the reaction environment which may be a hydrothermal environment.

Porous carbon supported Fe-N-C composite as an efficient electrocatalyst for oxygen reduction reaction in alkaline and acidic media

NASA Astrophysics Data System (ADS)

Liu, Baichen; Huang, Binbin; Lin, Cheng; Ye, Jianshan; Ouyang, Liuzhang

2017-07-01

In recent years, non-precious metal electrocatalysts for oxygen reduction reaction (ORR) have attracted tremendous attention due to their high catalytic activity, long-term stability and excellent methanol tolerance. Herein, the porous carbon supported Fe-N-C catalysts for ORR were synthesized by direct pyrolysis of ferric chloride, 6-Chloropyridazin-3-amine and carbon black. Variation of pyrolysis temperature during the synthesis process leads to the difference in ORR catalytic activity. High pyrolysis temperature is beneficial to the formation of the "N-Fe" active sites and high electrical conductivity, but the excessive temperature will cause the decomposition of nitrogen-containing active sites, which are revealed by Raman, TGA and XPS. A series of synthesis and characterization experiments with/without nitrogen or iron in carbon black indicate that the coordination of iron and nitrogen plays a crucial role in achieving excellent ORR performances. Electrochemical test results show that the catalyst pyrolyzed at 800 °C (Fe-N-C-800) exhibits excellent ORR catalytic activity, better methanol tolerance and higher stability compared with commercial Pt/C catalyst in both alkaline and acidic conditions.

CO2 as a hydrogen vector - transition metal diamine catalysts for selective HCOOH dehydrogenation.

PubMed

Fink, Cornel; Laurenczy, Gábor

2017-01-31

The homogeneous catalytic dehydrogenation of formic acid in aqueous solution provides an efficient in situ method for hydrogen production, under mild conditions, and at an adjustable rate. We synthesized a series of catalysts with the chemical formula [(Cp*)M(N-N')Cl] (M = Ir, Rh; Cp* = pentamethylcyclopentadienyl; N-N = bidentate chelating nitrogen donor ligands), which have been proven to be active in selective formic acid decomposition in aqueous media. The scope of the study was to examine the relationship between stability and activity of catalysts for formic acid dehydrogenation versus electronic and steric properties of selected ligands, following a bottom-up approach by increasing the complexity of the N,N'-ligands progressively. The highest turnover frequency, TOF = 3300 h -1 was observed with a Cp*Ir(iii) complex bearing 1,2-diaminocyclohexane as the N,N'-donor ligand. From the variable temperature studies, the activation energy of formic acid dehydrogenation has been determined, E a = 77.94 ± 3.2 kJ mol -1 . It was observed that the different steric and electronic properties of the bidentate nitrogen donor ligands alter the catalytic activity and stability of the Ir and Rh compounds profoundly.

Evaluations of catalysts for wet oxidation waste management in CELSS

NASA Astrophysics Data System (ADS)

Oguchi, Mitsuo; Nitta, Keiji

1992-11-01

A wet oxidation method is considered to be one of the most effective methods of waste processing and recycling in CELSS (Controlled Ecological Life Support System). The first test using rabbit waste as raw material was conducted under a decomposition temperature of 280 °C for 30 minutes and an initial pure oxygen pressure of 4.9 MPa (50 kgf/cm2) before heating, and the following results were obtained. The value of COD (Chemical Oxygen Demand) was reduced 82.5 % by the wet oxidation. And also the Kjeldahl nitrogen concentration was decreased 98.8%. However, the organic carbon compound in the residual solution was almost acetic acid and ammonia was produced. In order to activate the oxidation more strongly, the second tests using catalysts such as Pd, Ru and Ru+Rh were conducted. As the results of these tests, the effectiveness of catalysts for oxidizing raw material ws shown as follows: COD and the Kjeldahl nitrogen values were drastically decreased 99.65 % and 99.88 %, respectively. Furthermore, the quantity of acetic acid and ammonia were reduced considerably. On the other hand, nitrate was showed a value 30 times as much as without catalytic oxidation.

Green synthesis of Pt and Ag nanoparticles and their use towards nitric oxide abatement

NASA Astrophysics Data System (ADS)

Castegnaro, Marcus V.; Alexandre, Jéssica; Baibich, Ione M.; Alves, Maria C. M.; Morais, Jonder

2014-12-01

Pt and Ag nanoparticles (NPs) were synthesized by eco-friendly room-temperature chemical reduction routes based on trisodium citrate and L-ascorbic acid (for Pt NPs) and on gelatin and trisodium citrate (for Ag NPs). The as-prepared NPs were characterized by UV-visible absorption spectroscopy and transmission electron microscopy analyses, which confirmed the formation of sub-10 nm metal particles. Then, the colloidal solutions were used to obtain activated carbon-supported catalysts (metal/AC) for direct NO decomposition. X-ray photoelectron spectroscopy and x-ray diffraction measurements proved that the NPs hosted on the support surface were present in the metallic chemical state. In situ infrared absorption spectroscopy investigations during NO reduction catalytic reactions showed that the Pt/AC and Ag/AC catalysts were highly active at 373 K. At 573 K, we observed different behaviors for each catalyst. While Ag/AC performed similarly to the reaction at 373 K, Pt/AC was found to participate in a redox mechanism, where the catalyst’s active sites were oxidized by NO and reduced by carbon, thus emitting CO2 and enhancing its catalytic activity, an effect that we have also observed in carbon-supported Pd NPs.

Dual Heteroatom-Doped Carbon Nanofoam-Wrapped Iron Monosulfide Nanoparticles: An Efficient Cathode Catalyst for Li-O2 Batteries.

PubMed

Ramakrishnan, Prakash; Shanmugam, Sangaraju; Kim, Jae Hyun

2017-04-10

Cost-effective dual heteroatom-doped 3D carbon nanofoam-wrapped FeS nanoparticles (NPs), FeS-C, act as efficient bifunctional catalysts for Li-O 2 batteries. This cathode exhibits a maximum deep discharge capacity of 14 777.5 mA h g -1 with a 98.1 % columbic efficiency at 0.1 mA cm -2 . The controlled capacity (500 mA h g -1 ) test of this cathode delivers a minimum polarization gap of 0.73 V at 0.1 mA cm -2 and is sustained for 100 cycles with an energy efficiency of approximately 64 % (1st cycle) and 52 % (100th cycle) at 0.3 mA cm -2 , under the potential window of 2.0-4.5 V. X-ray photoelectron spectroscopy reveals the substantial reversible formation and complete decomposition of Li 2 O 2 . The excellent recharging ability, high rate performance, and cycle stability of this catalyst is attributed to the synergistic effect of FeS catalytic behavior and textural properties of heteroatom-doped carbon nanostructures. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method of forming semiconducting amorphous silicon films from the thermal decomposition of fluorohydridodisilanes

DOEpatents

Sharp, Kenneth G.; D'Errico, John J.

1988-01-01

The invention relates to a method of forming amorphous, photoconductive, and semiconductive silicon films on a substrate by the vapor phase thermal decomposition of a fluorohydridodisilane or a mixture of fluorohydridodisilanes. The invention is useful for the protection of surfaces including electronic devices.

Modeling of the HiPco process for carbon nanotube production. II. Reactor-scale analysis

NASA Technical Reports Server (NTRS)

Gokcen, Tahir; Dateo, Christopher E.; Meyyappan, M.

2002-01-01

The high-pressure carbon monoxide (HiPco) process, developed at Rice University, has been reported to produce single-walled carbon nanotubes from gas-phase reactions of iron carbonyl in carbon monoxide at high pressures (10-100 atm). Computational modeling is used here to develop an understanding of the HiPco process. A detailed kinetic model of the HiPco process that includes of the precursor, decomposition metal cluster formation and growth, and carbon nanotube growth was developed in the previous article (Part I). Decomposition of precursor molecules is necessary to initiate metal cluster formation. The metal clusters serve as catalysts for carbon nanotube growth. The diameter of metal clusters and number of atoms in these clusters are some of the essential information for predicting carbon nanotube formation and growth, which is then modeled by the Boudouard reaction with metal catalysts. Based on the detailed model simulations, a reduced kinetic model was also developed in Part I for use in reactor-scale flowfield calculations. Here this reduced kinetic model is integrated with a two-dimensional axisymmetric reactor flow model to predict reactor performance. Carbon nanotube growth is examined with respect to several process variables (peripheral jet temperature, reactor pressure, and Fe(CO)5 concentration) with the use of the axisymmetric model, and the computed results are compared with existing experimental data. The model yields most of the qualitative trends observed in the experiments and helps to understanding the fundamental processes in HiPco carbon nanotube production.

Low-Temperature Catalytic Decomposition of 130 Tetra- to Octa-PCDD/Fs Congeners over CuOX and MnOX Modified V2O5/TiO2-CNTs with the Assistance of O3.

PubMed

Zhao, Rixiao; Jin, Dongdong; Yang, Hangsheng; Lu, Shengyong; Potter, Phillip M; Du, Cuicui; Peng, Yaqi; Li, Xiaodong; Yan, Jianhua

2016-10-07

In this study, a reliable and steady PCDD/F generation system was utilized to investigate the performance of catalysts, in which 130 congeners of tetra- to octapolychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) vapors were studied under simulated flue gas with/without O 3 . TiO 2 and carbon nanotubes (CNTs) supported vanadium oxides (VO X /TiO 2 -CNTs) modified with MnO X and CuO X , which were reported to be beneficial to the decomposition of model molecules, were found to have a negative effect on the removal of real PCDD/Fs in the simulated flue gas without O 3 . Moreover, the addition of MnO X presented different effects depending on whether CuO X existed in catalysts or not, which was also contrary to its effects on the degradation of model molecules. In an O 3 -containing atmosphere, low chlorination level PCDD/Fs congeners were removed well over VO X -MnO X /TiO 2 -CNTs, while high chlorination level PCDD/Fs congeners were removed well over VO X -CuO X /TiO 2 -CNTs. Fortunately, all PCDD/Fs congeners decomposed well over VO X -MnO X -CuO X /TiO 2 -CNTs. Finally, the effects of tetra- to octachlorination level for the adsorption and degradation behaviors of PCDD/Fs congeners were also investigated.

Review of iron-free Fenton-like systems for activating H2O2 in advanced oxidation processes.

PubMed

Bokare, Alok D; Choi, Wonyong

2014-06-30

Iron-catalyzed hydrogen peroxide decomposition for in situ generation of hydroxyl radicals (HO(•)) has been extensively developed as advanced oxidation processes (AOPs) for environmental applications. A variety of catalytic iron species constituting metal salts (in Fe(2+) or Fe(3+) form), metal oxides (e.g., Fe2O3, Fe3O4), and zero-valent metal (Fe(0)) have been exploited for chemical (classical Fenton), photochemical (photo-Fenton) and electrochemical (electro-Fenton) degradation pathways. However, the requirement of strict acidic conditions to prevent iron precipitation still remains the bottleneck for iron-based AOPs. In this article, we present a thorough review of alternative non-iron Fenton catalysts and their reactivity towards hydrogen peroxide activation. Elements with multiple redox states (like chromium, cerium, copper, cobalt, manganese and ruthenium) all directly decompose H2O2 into HO(•) through conventional Fenton-like pathways. The in situ formation of H2O2 and decomposition into HO(•) can be also achieved using electron transfer mechanism in zero-valent aluminum/O2 system. Although these Fenton systems (except aluminum) work efficiently even at neutral pH, the H2O2 activation mechanism is very specific to the nature of the catalyst and critically depends on its composition. This review describes in detail the complex mechanisms and emphasizes on practical limitations influencing their environmental applications. Copyright © 2014 Elsevier B.V. All rights reserved.

Preparation and photocatalytic activity of magnetic samarium-doped mesoporous titanium dioxide at the decomposition of methylene blue under visible light

NASA Astrophysics Data System (ADS)

Shi, Zhongliang; Lai, Hong; Yao, Shuhua

2012-08-01

Preparation of samarium-doped mesoporous titanium dioxide (Sm/MTiO2) coated magnetite (Fe3O4) photocatalysts (Sm/MTiO2/Fe3O4) and their activities under visible light were reported. The catalysts with Sm/MTiO2 shell and a Fe3O4 core were prepared by coating photoactive Sm/MTiO2 onto a magnetic Fe3O4 core through the hydrolysis of tetrabutyltitanate (Ti(OBu)4, TBT) with precursors of Sm(NO3)3 and TBT in the presence of Fe3O4 nanoparticles. The morphological, structural and optical properties of the prepared samples were characterized by BET surface area, transmission electron microscopy (TEM), X-ray diffraction (XRD) and UV-vis absorption spectroscopy. The effect of Sm ion content on the photocatalytic activity was studied. The photocatalytic activities of obtained photocatalysts under visible light were estimated by measuring the decomposition rate of methylene blue (MB, 50 mg/L) in an aqueous solution. The results showed that the prepared photocatalyst was activated by visible light and used as effective catalyst in photooxidation reactions. In addition, the possibility of cyclic usage of the prepared photocatalyst was also confirmed. Moreover, Sm/MTiO2 was tightly bound to Fe3O4 and could be easily recovered from the medium by a simple magnetic process. It can therefore be potentially applied for the treatment of water contaminated by organic pollutants.

Synthesis of ACNT on quartz substrate with catalytic decomposition reaction from Cinnamomum camphora by using FC-CVD method

NASA Astrophysics Data System (ADS)

Wulan, Praswasti P. D. K.; Silaen, Toni Partogi Johannes

2017-05-01

Camphor is a renewable carbon source that can be used as raw material for synthesizing Carbon Nanotube (CNT). Camphor is a substance that can be found on the Cinnamomum camphora tree. In this research, the method used to synthesize Aligned Carbon Nanotube (ACNT) from camphor is Floating Catalyst Chemical Vapor Deposition (FC-CVD) with Ferrocene as catalyst at temperature of 800°C, hydrogen gas as the co-reactant and argon gas as carrier gas. This method is the most popular method of synthesizing ACNT which oriented and have a high density. Camphor decomposes into benzene, toluene, and xylene at a temperature of 800°C. By using GC-FID for characterization test, the results showed decomposition at a temperature of 800°C camphor dominated by benzene with a concentration of 92.422 to 97.656%. The research was conducted by varying the flow rate of carrier gas such as argon at 40, 55, 70, 85 and 100 mL / min at a temperature of 800°C for 60 minutes of reaction time. Argon carrier gas flow rate of 70 mL / min producing CNT with the highest yield, but this is not followed by best quality of CNT. CNT with best quality is obtained at a flow rate of argon carrier gas at 55 mL / min based on test results characterization by using SEM, EDX, Mapping, and RAMAN Spectroscopy. This research have not obtained CNT with aligned structured.

Clean hydrogen generation through the electrocatalytic oxidation of ethanol in a Proton Exchange Membrane Electrolysis Cell (PEMEC): Effect of the nature and structure of the catalytic anode

NASA Astrophysics Data System (ADS)

Lamy, Claude; Jaubert, Thomas; Baranton, Stève; Coutanceau, Christophe

2014-01-01

The electrocatalytic oxidation of ethanol was investigated in a Proton Exchange Membrane Electrolysis Cell (PEMEC) working at low temperature (20°C) on several Pt-based catalysts (Pt/C, PtSn/C, PtSnRu/C) in order to produce very clean hydrogen by electrolysis of a biomass compound. The electrocatalytic activity was determined by cyclic voltammetry and the rate of hydrogen evolution was measured for each catalyst at different current densities. The cell voltages UEtOH were recorded as a function of time for each current density. At 100 mA cm-2, i.e. 0.5 A with the 5 cm2 surface area PEMEC used, the cell voltage did not exceed 0.9 V for an evolution rate of about 220 cm3 of hydrogen per hour and the electrical energy consumed was less than 2.3 kWh (Nm3)-1, i.e. less than one half of the energy needed for water electrolysis (4.7 kWh (Nm3)-1 at UH2O = 2 V). This result is valid for the decomposition of any organic compound, particularly those originated from biomass resource, provided that their electro-oxidation rate is sufficient (>100 mA cm-2) at a relatively low cell voltage (Ucell < 1 V) which necessitates the development of efficient electrocatalysts for the electrochemical decomposition of this compound.

Coating for components requiring hydrogen peroxide compatibility

NASA Technical Reports Server (NTRS)

Yousefiani, Ali (Inventor)

2010-01-01

The present invention provides a heretofore-unknown use for zirconium nitride as a hydrogen peroxide compatible protective coating that was discovered to be useful to protect components that catalyze the decomposition of hydrogen peroxide or corrode when exposed to hydrogen peroxide. A zirconium nitride coating of the invention may be applied to a variety of substrates (e.g., metals) using art-recognized techniques, such as plasma vapor deposition. The present invention further provides components and articles of manufacture having hydrogen peroxide compatibility, particularly components for use in aerospace and industrial manufacturing applications. The zirconium nitride barrier coating of the invention provides protection from corrosion by reaction with hydrogen peroxide, as well as prevention of hydrogen peroxide decomposition.

Effect of cuprous oxide with different sizes on thermal and combustion behaviors of unsaturated polyester resin.

PubMed

Hou, Yanbei; Hu, Weizhao; Gui, Zhou; Hu, Yuan

2017-07-15

Cuprous oxide (Cu 2 O) as an effective catalyst has been applied to enhance the fire safety of unsaturated polyester resin (UPR), but the particle size influence on combustion behaviors has not been previously reported. Herein, the UPR/Cu 2 O composites (metal oxide particles with average particle-size of 10, 100, and 200nm) were successfully synthesized by thermosetting process. The effects of Cu 2 O with different sizes on thermostability and combustion behaviors of UPR were characterized by TGA, MCC, TG-IR, FTIR, and SSTF. The results revel that the addition of Cu 2 O contributes to sufficient decomposition of oxygen-containing compounds, which is beneficial to the release of nontoxic compounds. The smallest-sized Cu 2 O performs the excellent catalytic decomposition effect and promotes the complete combustion of UPR, which benefits the enhancement of fire safety. While the other additives retard pyrolysis process and yield more char residue, and thus the flame retardancy of UPR composites was improved. Therefore, catalysis plays a major role for smaller-sized particles during thermal decomposition of matrix, while flame retarded effect became gradual distinctly for the larger-sized additives. Copyright © 2017 Elsevier B.V. All rights reserved.

Targets of vascular protection in acute ischemic stroke differ in type 2 diabetes

PubMed Central

Kelly-Cobbs, Aisha I.; Prakash, Roshini; Li, Weiguo; Pillai, Bindu; Hafez, Sherif; Coucha, Maha; Johnson, Maribeth H.; Ogbi, Safia N.; Fagan, Susan C.

2013-01-01

Hemorrhagic transformation is an important complication of acute ischemic stroke, particularly in diabetic patients receiving thrombolytic treatment with tissue plasminogen activator, the only approved drug for the treatment of acute ischemic stroke. The objective of the present study was to determine the effects of acute manipulation of potential targets for vascular protection [i.e., NF-κB, peroxynitrite, and matrix metalloproteinases (MMPs)] on vascular injury and functional outcome in a diabetic model of cerebral ischemia. Ischemia was induced by middle cerebral artery occlusion in control and type 2 diabetic Goto-Kakizaki rats. Treatment groups received a single dose of the peroxynitrite decomposition catalyst 5,10,15,20-tetrakis(4-sulfonatophenyl)prophyrinato iron (III), the nonspecific NF-κB inhibitor curcumin, or the broad-spectrum MMP inhibitor minocycline at reperfusion. Poststroke infarct volume, edema, hemorrhage, neurological deficits, and MMP-9 activity were evaluated. All acute treatments reduced MMP-9 and hemorrhagic transformation in diabetic groups. In addition, acute curcumin and minocycline therapy reduced edema in these animals. Improved neurological function was observed in varying degrees with treatment, as indicated by beam-walk performance, modified Bederson scores, and grip strength; however, infarct size was similar to untreated diabetic animals. In control animals, all treatments reduced MMP-9 activity, yet bleeding was not improved. Neuroprotection was only conferred by curcumin and minocycline. Uncovering the underlying mechanisms contributing to the success of acute therapy in diabetes will advance tailored stroke therapies. PMID:23335797

Stepped Single Crystals as Improved Model for Supported Catalysts: Ethylene, Methanol and Assorted Molecules on PLATINUM(511) and PLATINUM(331)

NASA Astrophysics Data System (ADS)

Spaendonk, Vincent Van

Past research has shown unusual activity of the (1 x 1)Pt(110) surface to break carbon-carbon and carbon -oxygen bonds. Methane formation from ethylene or ethane has been reported for supported platinum catalysts. A model for the methane formation on (1 x 1)Pt(110), was proposed by Yagasaki. In this study, the mechanism of methane formation has been further investigated, and Yagasaki's model tested, by studying the decomposition of ethylene and methanol on the stepped surfaces Pt(511) and Pt(331) with Temperature Programmed Desorption. The experiments have been carried out in a Ultra High Vacuum system, equipped with a mass spectrometer, LEED and AES. Hydrogen and carbon monoxide desorption show that on Pt(511) different adsorption sites are available than on Pt(331). Ethylene decomposition on Pt(511) leads to small amounts of methane formation compared to (1 x 1)Pt(110). The metastable (1 x 1) phase of Pt(511) is 2-3 times more active than the stable (hex) phase. When ^{13}C_2H _4 is used, ^{13 }CH_4 is not detected. Methane formation is not seen on the Pt(331) surface. Arguments are given why Pt(511) is a superior model for supported catalysts compared to (1 x 1)Pt(110). The carbon-oxygen bond of methanol is not broken on either Pt(511) or Pt(331), whether the surface is clean or covered with oxygen. Hydrogen saturating the surface, prevents the chemisorption of ethylene and the formation of methane. Postadsorption of hydrogen does not lead to an increase in methane formation. Coadsorption of ethylene with carbon monoxide shows a maximum methane formation at 0.3 L carbon monoxide exposure. Poison experiments with 'oxide' and carbon indicate that the active site for methane formation is located at the step. The amount of carbon deposited during ethylene decomposition, increases in the order (1 x 1)Pt(511) to (hex)Pt(511) to Pt(331). This is also the order for decreasing methane activity. In a new model, it is proposed that in order to be active for methane formation, a surface has to prevent the polymerization of single carbon species to inactive graphite. The model predicts that surfaces with large enough (111) terraces have higher diffusion rates and allow the single carbon species to convert to graphite before the species can be hydrogenated.

A copyright protection scheme for digital images based on shuffled singular value decomposition and visual cryptography.

PubMed

Devi, B Pushpa; Singh, Kh Manglem; Roy, Sudipta

2016-01-01

This paper proposes a new watermarking algorithm based on the shuffled singular value decomposition and the visual cryptography for copyright protection of digital images. It generates the ownership and identification shares of the image based on visual cryptography. It decomposes the image into low and high frequency sub-bands. The low frequency sub-band is further divided into blocks of same size after shuffling it and then the singular value decomposition is applied to each randomly selected block. Shares are generated by comparing one of the elements in the first column of the left orthogonal matrix with its corresponding element in the right orthogonal matrix of the singular value decomposition of the block of the low frequency sub-band. The experimental results show that the proposed scheme clearly verifies the copyright of the digital images, and is robust to withstand several image processing attacks. Comparison with the other related visual cryptography-based algorithms reveals that the proposed method gives better performance. The proposed method is especially resilient against the rotation attack.

Method to prepare nanoparticles on porous mediums

DOEpatents

Vieth, Gabriel M [Knoxville, TN; Dudney, Nancy J [Oak Ridge, TN; Dai, Sheng [Knoxville, TN

2010-08-10

A method to prepare porous medium decorated with nanoparticles involves contacting a suspension of nanoparticles in an ionic liquid with a porous medium such that the particles diffuse into the pores of the medium followed by heating the resulting composition to a temperature equal to or greater than the thermal decomposition temperature of the ionic liquid resulting in the removal of the liquid portion of the suspension. The nanoparticles can be a metal, an alloy, or a metal compound. The resulting compositions can be used as catalysts, sensors, or separators.

Metathesis depolymerizable surfactants

DOEpatents

Jamison, Gregory M [Albuquerque, NM; Wheeler, David R [Albuquerque, NM; Loy, Douglas A [Tucson, AZ; Simmons, Blake A [San Francisco, CA; Long, Timothy M [Evanston, IL; McElhanon, James R [Manteca, CA; Rahimian, Kamyar [Albuquerque, NM; Staiger, Chad L [Albuquerque, NM

2008-04-15

A class of surfactant molecules whose structure includes regularly spaced unsaturation in the tail group and thus, can be readily decomposed by ring-closing metathesis, and particularly by the action of a transition metal catalyst, to form small molecule products. These small molecules are designed to have increased volatility and/or enhanced solubility as compared to the original surfactant molecule and are thus easily removed by solvent extraction or vacuum extraction at low temperature. By producing easily removable decomposition products, the surfactant molecules become particularly desirable as template structures for preparing meso- and microstructural materials with tailored properties.

40 CFR 63.6620 - What performance tests and other procedures must I use?

Code of Federal Regulations, 2010 CFR

2010-07-01

... an oxidation catalyst, if you comply with the emission limitation to reduce formaldehyde and you are... formaldehyde in the stationary RICE exhaust and you are not using an oxidation catalyst or NSCR, you must... 40 Protection of Environment 13 2010-07-01 2010-07-01 false What performance tests and other...

Lanthanum(III)-catalyzed disproportionation of hydrogen peroxide: a heterogeneous generator of singlet molecular oxygen-1O2 (1Deltag)-in near-neutral aqueous and organic media for peroxidation of electron-rich substrates.

PubMed

Nardello, Véronique; Barbillat, Jacques; Marko, Jean; Witte, Peter T; Alsters, Paul L; Aubry, Jean-Marie

2003-01-20

The decomposition of hydrogen peroxide into singlet molecular oxygen-(1)O(2) ((1)Delta(g))-in the presence of lanthanum(iii) salts was studied by monitoring its characteristic IR luminescence at 1270 nm. The process was found to be heterogeneously catalyzed by La(III), provided that the heterogeneous catalyst is generated in situ. The yield of (1)O(2) generation was assessed as 45+/-5 % both in water and in methanol. The pH-dependence on the rate of (1)O(2) generation corresponds to a bell-shaped curve from pH 4.5 to 13 with a maximum around pH 8. The study of the influence of H(2)O(2) showed that the formation of (1)O(2) begins as soon as one equivalent of H(2)O(2) is introduced. It then increases drastically up to two equivalents and more smoothly above. Unlike all other metal salt catalyst systems known to date for H(2)O(2) disproportionation, this chemical source of (1)O(2) is able to generate (1)O(2) not only in basic media, but also under neutral and slightly acidic conditions. In addition, this La-based catalyst system has a very low tendency to induce unwanted oxygenating side reactions, such as epoxidation of alkenes. These two characteristics of the heterogeneous lanthanum catalyst system allow non-photochemical (i.e., "dark") singlet oxygenation of substrate classes that cannot be peroxidized successfully with conventional molybdate catalysts, such as allylic alcohols and alkenyl amines.

Catalytic microwave pyrolysis of oil palm fiber (OPF) for the biochar production.

PubMed

Hossain, Md Arafat; Ganesan, Poo Balan; Sandaran, Shanti Chandran; Rozali, Shaifulazuar Bin; Krishnasamy, Sivakumar

2017-12-01

Microwave pyrolysis of oil palm fiber (OPF) with three types of Na-based catalysts was experimentally investigated to produce biochar. Sodium hydroxide (NaOH), sodium chloride (NaCl), and sodium carbonate (Na 2 CO 3 ) with purity 99.9% were selected for this investigation. Microwave muffle reactor (Model: HAMiab-C1500) with a microwave power controller including a microwave generator was used to perform the microwave pyrolysis. OPF particles were used after removing foreign materials, impurities, and dust. Microwave power ranges from 400 to 900 W, temperature ranges from 450 to 700 °C, and N 2 flow rates ranges from 200 to -1200 cm 3 /min were used along with all three Na-based catalysts for this investigation. Lower microwave power, temperature, and N 2 flow rate have been found favorable for higher yield of biochar. NaOH is to be found as the more suitable catalyst than NaCl and Na 2 CO 3 to produce biochar. A maximum biochar yield (51.42 wt%) has been found by using the catalysts NaOH at N 2 flow rate of 200 cm 3 /min. One sample of the biochar (maximum yield without catalysts) was selected for further characterization via thermo gravimetric analysis (TGA), scanning electron microscopy (SEM), BET surface area, Fourier transform infrared spectroscopy (FTIR), and ultimate and proximate analysis. SEM and BET surface area analysis showed the presence of some pores in the biochar. High percentage of carbon (60.24 wt%) was also recorded in the sample biochar. The pores and high percentage of carbon of biochar have significant impact on soil fertilization by increasing the carbon sequestration in the soil. It assists to slow down the decomposition rate of nutrients from soil and therefore enhances the soil quality.

Enhanced room-temperature catalytic decomposition of formaldehyde on magnesium-aluminum hydrotalcite/boehmite supported platinum nanoparticles catalyst.

PubMed

Yan, Zhaoxiong; Yang, Zhihua; Xu, Zhihua; An, Liang; Xie, Fang; Liu, Jiyan

2018-08-15

Magnesium-aluminum hydrotalcite (Mg-Al HT)/boehmite (AlOOH) composite supported Pt catalysts were obtained via one-pot microemulsion synthesis of Mg-Al HT/AlOOH composite and NaBH 4 -reduction of Pt precursor processes. The catalytic performances of the catalysts were evaluated for formaldehyde (HCHO) removal at room temperature. The performance tests showed that the catalyst obtained by immobilizing Pt nanoparticles (NPs) on Mg-Al HT/AlOOH support with Al/Mg molar ratio equivalent to 9:1 (Pt/Al 9 Mg 1 ) displayed a superior catalytic activity and stability for HCHO removal. In order to find out the causes of its higher activity, X-ray diffraction, transmission electron microscopy, N 2 adsorption/desorption, X-ray photoelectron spectroscopy, temperature programmed desorption of CO 2 and reduction of H 2 were used to analyze the physicochemical properties of Pt/Al 9 Mg 1 and Pt/AlOOH. The remarkable catalytic performance of Pt/Al 9 Mg 1 is mainly attributed to the relatively larger amount of surface oxygen species, and more reactive oxygen species led by the interaction of Mg-Al HT and AlOOH/Pt, and relatively larger number of weak base sites caused by Mg-Al HT. The formate species are the main reaction intermediate over Pt/Al 9 Mg 1 during HCHO oxidation at room temperature, which could be further oxidized into CO 2 and H 2 O in the presence of O 2 . This study might shed some light on further improving the catalytic performance of the catalyst for indoor air purification at room temperature. Copyright © 2018 Elsevier Inc. All rights reserved.

I. Direct observation of zirconocene-catalyzed alkene polymerization via NMR and the role of an aluminum alkyl during polymerization. II. Design and evaluation of an online nanoscience course for teachers

NASA Astrophysics Data System (ADS)

Tomasik, Janice Hall

The plastics industry has been revolutionalized by development of group 4 metallocene polymerization catalysts. These catalysts have higher activities and stereoselectivities than traditional heterogeneous Ziegler-Natta polymerization catalysts, and produce polymers with narrower molecular weight distributions and with better control of the polymer stereochemistry. The reaction kinetics of catalytic alkene polymerizations are complicated and difficult to resolve macroscopically. To overcome these difficulties, research has used NMR spectroscopy to directly observe catalytic reaction intermediates; many advances in our understanding of the complex mechanisms behind these polymerization reactions have resulted. In this work, the direct observation of alkene insertion into zirconocene-polymeryls via NMR spectroscopy is presented. Alkenes studied are 3-methylpentene, styrene, and 1,4-pentadiene. Kinetic measurements are reported for the polymerization of 3-methylpentene by rac-(EBI)Zr(Me)(MeB(C6F 5)3) (EBI = C2H4(1-indenyl)2) and rac-(EBI)Zr(polyhexenyl)(MeB(C6F5) 3). Also presented are NMR spectroscopic characterizations of rac-(EBI)Zr(styrenyl)(MeB(C6F5)3) and rac-(EBI)Zr(1,4-pentadienyl)(MeB(C6F 5)3). In addition, NMR spectroscopy is used to directly monitor the behavior of an aluminum alkyl during the polymerization of 1-hexene by rac -(EBI)2Zr(Me)(MeB(C6F5)3). The rates of polymerization are not inhibited by Al(iBu) 2(BHT), Al(Me)(BHT)2, or Al(iBu)3 (BHT = 2,6-di- tert-butyl-4-methylphenyl). Detailed measurement of polymerization rate and catalyst speciation demonstrate that BHT modified aluminum alkyls protect active sites from decomposition in the presence of protic impurities such as methanol. Also presented in this work is the design and evaluation of an online course for teachers about nanoscience. Nanotechnology is an important emerging field that is estimated to need about 2 million workers worldwide by 2015. Therefore the educational system is being encouraged to incorporate major nanoscience concepts into curricula. In order to facilitate the integration of nanoscience, an online professional development course for teachers has been developed and offered at the University of Wisconsin-Madison. Evaluation results from the first three versions of the course indicate the online learning environment was very close to ideal. Comparisons of pre-instruction to post-instruction quiz responses indicate significant learning gains by participants. Importantly, survey results show the online course helped teachers to successfully incorporate nanoscience into their curricula.

Spectroscopic investigation and direct comparison of the reactivities of iron pyridyl oxidation catalysts

NASA Astrophysics Data System (ADS)

Song, Yang; Mayes, Howard G.; Queensen, Matthew J.; Bauer, Eike B.; Dupureur, Cynthia M.

2017-03-01

The growing interest in green chemistry has fueled attention to the development and characterization of effective iron complex oxidation catalysts. A number of iron complexes are known to catalyze the oxidation of organic substrates utilizing peroxides as the oxidant. Their development is complicated by a lack of direct comparison of the reactivities of the iron complexes. To begin to correlate reactivity with structural elements, we compare the reactivities of a series of iron pyridyl complexes toward a single dye substrate, malachite green (MG), for which colorless oxidation products are established. Complexes with tetradentate, nitrogen-based ligands with cis open coordination sites were found to be the most reactive. While some complexes reflect sensitivity to different peroxides, others are similarly reactive with either H2O2 or tBuOOH, which suggests some mechanistic distinctions. [Fe(S,S-PDP)(CH3CN)2](SbF6)2 and [Fe(OTf)2(tpa)] transition under the oxidative reaction conditions to a single intermediate at a rate that exceeds dye degradation (PDP = bis(pyridin-2-ylmethyl) bipyrrolidine; tpa = tris(2-pyridylmethyl)amine). For the less reactive [Fe(OTf)2(dpa)] (dpa = dipicolylamine), this reaction occurs on a timescale similar to that of MG oxidation. Thus, the spectroscopic method presented herein provides information about the efficiency and mechanism of iron catalyzed oxidation reactions as well as about potential oxidative catalyst decomposition and chemical changes of the catalyst before or during the oxidation reaction.

Photocatalytic removal of perfluoroalkyl substances from water and wastewater: Mechanism, kinetics and controlling factors.

PubMed

Xu, Bentuo; Ahmed, Mohammad Boshir; Zhou, John L; Altaee, Ali; Wu, Minghong; Xu, Gang

2017-12-01

This review focuses on heterogeneous photocatalysis of perfluoroalkyl substances (PFAS) which are of worldwide concern as emerging persistent organic contaminants. Heterogeneous photocatalysis is an effective and advanced technology for PFAS removal from water with relatively high efficacy. During photocatalysis, various short chain perfluorocarboxylic acids (PFCA) are produced as intermediates and the efficacy is related to the photo-generated hole (h + ) and photo-generated electron (e - ). PFAS photodegradation in water under UV irradiation is most effective by using In 2 O 3 as the catalyst, followed by Ga 2 O 3 and TiO 2 . Significantly, modifying the chemical composition or morphology of the catalyst can improve its efficacy for PFAS removal. In 2 O 3 porous nanoplates were found to have the best performance of 100% PFAS decomposition under UV light with rate constant (k t ) and half-time (τ 1/2 ) of 0.158 min -1 and 4.4 min, respectively. Catalysts perform well in acidic solution and increasing temperature to a certain extent. The photocatalytic performance is reduced when treating wastewater due to the presence of dissolved organic matter (DOM), with the catalysts following the order: needle-like Ga 2 O 3  > In 2 O 3  > TiO 2 . Future studies should focus on the development of novel photocatalysts, and their immobilization and application for PFAS removal in wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

Anchoring and Upgrading Ultrafine NiPd on Room-Temperature-Synthesized Bifunctional NH2 -N-rGO toward Low-Cost and Highly Efficient Catalysts for Selective Formic Acid Dehydrogenation.

PubMed

Yan, Jun-Min; Li, Si-Jia; Yi, Sha-Sha; Wulan, Ba-Ri; Zheng, Wei-Tao; Jiang, Qing

2018-03-01

Hydrogen is widely considered to be a sustainable and clean energy alternative to the use of fossil fuels in the future. Its high hydrogen content, nontoxicity, and liquid state at room temperature make formic acid a promising hydrogen carrier. Designing highly efficient and low-cost heterogeneous catalysts is a major challenge for realizing the practical application of formic acid in the fuel-cell-based hydrogen economy. Herein, a simple but effective and rapid strategy is proposed, which demonstrates the synthesis of NiPd bimetallic ultrafine particles (UPs) supported on NH 2 -functionalized and N-doped reduced graphene oxide (NH 2 -N-rGO) at room temperature. The introduction of the NH 2 N group to rGO is the key reason for the formation of the ultrafine and well-dispersed Ni 0.4 Pd 0.6 UPs (1.8 nm) with relatively large surface area and more active sites. Surprisingly, the as-prepared low-cost NiPd/NH 2 -N-rGO dsiplays excellent hydrophilicity, 100% H 2 selectivity, 100% conversion, and remarkable catalytic activity (up to 954.3 mol H 2 (mol catalyst) -1 h -1 ) for FA decomposition at room temperature even with no additive, which is much higher than that of the best catalysts so far reported. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Changing Morphology of BaO/AI₂O₃ during NO₂ Uptake and Release

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

Szanyi, Janos; Kwak, Ja Hun; Hanson, Jonathan

2005-04-21

The changes in the morphology of Ba-oxide-based NOx storage/reduction catalysts were investigated using time resolved x-ray diffraction, transmission electron microscopy and energy dispersed spectroscopy. Large Ba(NO₃)₂ crystallites form on the alumina support when the catalyst is prepared by the incipient wetness method using an aqueous Ba(NO₃)₂ solution. Heating the sample to 873K in a He flow results in the decomposition of the Ba(NO₃)₂ phase and the formation of both a monolayer BaO film strongly interacting with the alumina support, and nano crystalline BaO particles. Upon NO₂ exposure of these BaO phases at room temperature, small (nano-sized) Ba(NO₃)₂ crystals and amore » monolayer of surface nitrate form. Heating this sample in NO₂ results in the coalescence of the nano crystalline Ba(NO₃)₂ particles into large crystals. The average crystal size in the re-formed Ba(NO₃)₂ layer is significantly smaller than that measured after the catalyst preparation. Evidence is also presented for the existence of a monolayer Ba(NO₃)₂ phase after thermal treatment in NO₂, in addition to these large crystals. These results clearly demonstrate the dynamic nature of the Ba-containing phases that are active in the NOx storage/reduction process. The proposed morphology cycle may contribute to the understanding of the changes observed in the performances of these catalysts during actual operating conditions.« less

DFT investigations of hydrogen storage materials

NASA Astrophysics Data System (ADS)

Wang, Gang

Hydrogen serves as a promising new energy source having no pollution and abundant on earth. However the most difficult problem of applying hydrogen is to store it effectively and safely, which is smartly resolved by attempting to keep hydrogen in some metal hydrides to reach a high hydrogen density in a safe way. There are several promising metal hydrides, the thermodynamic and chemical properties of which are to be investigated in this dissertation. Sodium alanate (NaAlH4) is one of the promising metal hydrides with high hydrogen storage capacity around 7.4 wt. % and relatively low decomposition temperature of around 100 °C with proper catalyst. Sodium hydride is a product of the decomposition of NaAlH4 that may affect the dynamics of NaAlH4. The two materials with oxygen contamination such as OH- may influence the kinetics of the dehydriding/rehydriding processes. Thus the solid solubility of OH - groups (NaOH) in NaAlH4 and NaH is studied theoretically by DFT calculations. Magnesium boride [Mg(BH4)2] is has higher hydrogen capacity about 14.9 wt. % and the decomposition temparture of around 250 °C. However one flaw restraining its application is that some polyboron compounds like MgB12H12 preventing from further release of hydrogen. Adding some transition metals that form magnesium transition metal ternary borohydride [MgaTMb(BH4)c] may simply the decomposition process to release hydrogen with ternary borides (MgaTMbBc). The search for the probable ternary borides and the corresponding pseudo phase diagrams as well as the decomposition thermodynamics are performed using DFT calculations and GCLP method to present some possible candidates.

Constructing Sheet-On-Sheet Structured Graphitic Carbon Nitride/Reduced Graphene Oxide/Layered MnO₂ Ternary Nanocomposite with Outstanding Catalytic Properties on Thermal Decomposition of Ammonium Perchlorate.

PubMed

Xu, Jianhua; Li, Dongnan; Chen, Yu; Tan, Linghua; Kou, Bo; Wan, Fushun; Jiang, Wei; Li, Fengsheng

2017-12-15

We unprecedentedly report that layered MnO₂ nanosheets were in situ formed onto the surface of covalently bonded graphitic carbon nitride/reduced graphene oxide nanocomposite (g-C₃N₄/rGO), forming sheet-on-sheet structured two dimension (2D) graphitic carbon nitride/reduced graphene oxide/layered MnO₂ ternary nanocomposite (g-C₃N₄/rGO/MnO₂) with outstanding catalytic properties on thermal decomposition of ammonium perchlorate (AP). The covalently bonded g-C₃N₄/rGO was firstly prepared by the calcination of graphene oxide-guanidine hydrochloride precursor (GO-GndCl), following by its dispersion into the KMnO₄ aqueous solution to construct the g-C₃N₄/rGO/MnO₂ ternary nanocomposite. FT-IR, XRD, Raman as well as the XPS results clearly demonstrated the chemical interaction between g-C₃N₄, rGO and MnO₂. TEM and element mapping indicated that layered g-C₃N₄/rGO was covered with thin MnO₂ nanosheets. Furthermore, the obtained g-C₃N₄/rGO/MnO₂ nanocomposite exhibited promising catalytic capacity on thermal decomposition of AP. Upon addition of 2 wt % g-C₃N₄/rGO/MnO₂ ternary nanocomposite as catalyst, the thermal decomposition temperature of AP was largely decreased up by 142.5 °C, which was higher than that of pure g-C₃N₄, g-C₃N₄/rGO and MnO₂, respectively, demonstrating the synergistic catalysis of the as-prepared nanocomposite.

Current advances in precious metal core-shell catalyst design.

PubMed

Wang, Xiaohong; He, Beibei; Hu, Zhiyu; Zeng, Zhigang; Han, Sheng

2014-08-01

Precious metal nanoparticles are commonly used as the main active components of various catalysts. Given their high cost, limited quantity, and easy loss of catalytic activity under severe conditions, precious metals should be used in catalysts at low volumes and be protected from damaging environments. Accordingly, reducing the amount of precious metals without compromising their catalytic performance is difficult, particularly under challenging conditions. As multifunctional materials, core-shell nanoparticles are highly important owing to their wide range of applications in chemistry, physics, biology, and environmental areas. Compared with their single-component counterparts and other composites, core-shell nanoparticles offer a new active interface and a potential synergistic effect between the core and shell, making these materials highly attractive in catalytic application. On one hand, when a precious metal is used as the shell material, the catalytic activity can be greatly improved because of the increased surface area and the closed interfacial interaction between the core and the shell. On the other hand, when a precious metal is applied as the core material, the catalytic stability can be remarkably improved because of the protection conferred by the shell material. Therefore, a reasonable design of the core-shell catalyst for target applications must be developed. We summarize the latest advances in the fabrications, properties, and applications of core-shell nanoparticles in this paper. The current research trends of these core-shell catalysts are also highlighted.

Subnanometer and nanometer catalysts, method for preparing size-selected catalysts

DOEpatents

Vajda, Stefan , Pellin, Michael J.; Elam, Jeffrey W [Elmhurst, IL; Marshall, Christopher L [Naperville, IL; Winans, Randall A [Downers Grove, IL; Meiwes-Broer, Karl-Heinz [Roggentin, GR

2012-04-03

Highly uniform cluster based nanocatalysts supported on technologically relevant supports were synthesized for reactions of top industrial relevance. The Pt-cluster based catalysts outperformed the very best reported ODHP catalyst in both activity (by up to two orders of magnitude higher turn-over frequencies) and in selectivity. The results clearly demonstrate that highly dispersed ultra-small Pt clusters precisely localized on high-surface area supports can lead to affordable new catalysts for highly efficient and economic propene production, including considerably simplified separation of the final product. The combined GISAXS-mass spectrometry provides an excellent tool to monitor the evolution of size and shape of nanocatalyst at action under realistic conditions. Also provided are sub-nanometer gold and sub-nanometer to few nm size-selected silver catalysts which possess size dependent tunable catalytic properties in the epoxidation of alkenes. Invented size-selected cluster deposition provides a unique tool to tune material properties by atom-by-atom fashion, which can be stabilized by protective overcoats.

Subnanometer and nanometer catalysts, method for preparing size-selected catalysts

DOEpatents

Vajda, Stefan [Lisle, IL; Pellin, Michael J [Naperville, IL; Elam, Jeffrey W [Elmhurst, IL; Marshall, Christopher L [Naperville, IL; Winans, Randall A [Downers Grove, IL; Meiwes-Broer, Karl-Heinz [Roggentin, GR

2012-03-27

Highly uniform cluster based nanocatalysts supported on technologically relevant supports were synthesized for reactions of top industrial relevance. The Pt-cluster based catalysts outperformed the very best reported ODHP catalyst in both activity (by up to two orders of magnitude higher turn-over frequencies) and in selectivity. The results clearly demonstrate that highly dispersed ultra-small Pt clusters precisely localized on high-surface area supports can lead to affordable new catalysts for highly efficient and economic propene production, including considerably simplified separation of the final product. The combined GISAXS-mass spectrometry provides an excellent tool to monitor the evolution of size and shape of nanocatalyst at action under realistic conditions. Also provided are sub-nanometer gold and sub-nanometer to few nm size-selected silver catalysts which possess size dependent tunable catalytic properties in the epoxidation of alkenes. Invented size-selected cluster deposition provides a unique tool to tune material properties by atom-by-atom fashion, which can be stabilized by protective overcoats.

Commercialization of the Chevron FCC vanadium trap

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

Kennedy, J.V.; Kuehler, C.W.; Krishna, A.S.

1995-09-01

Vanadium, present to varying degrees in FCC feed, deposits on the catalyst virtually quantitatively in the cracking process. In resid operations, vanadium levels on catalyst can reach 10,000 ppm at typical catalyst make-up rates. Once on the catalyst, vanadium destroys the zeolite and restricts access to active sites. This reduces catalyst activity. A vanadium trap is a material that when introduced into the catalyst inventory selectively reacts with migrating vanadium, thus protecting the zeolite and other active components of the catalyst. The trap may be incorporated into the catalyst, or introduced as a separate particle. Only a limited amount ofmore » trap can be incorporated into the catalyst without limiting the amount of zeolite that can be included. Gulf began development of a vanadium trap during the early 1980`s. The work produced a variety of promising materials whose use as vanadium traps was subsequently patented. The work ultimately led to a formulation with a phase very active for trapping vanadium while still quite sulfur tolerant. Based on these results, an extensive pilot plant evaluation was undertaken by Chevron after the Chevron-Gulf merger to better simulate commercial operation. The paper describes pilot plant tests as well as 3 commercial tests of this vanadium trap.« less

Surface chemistry of aromatic reactants on Pt- and Mo-modified Pt catalysts

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

Robinson, Allison M.; Mark, Lesli; Rasmussen, Mathew J.

Supported catalysts containing an oxophilic metal such as Mo and a noble metal such as Pt have shown promising activity and selectivity for deoxygenation of biomass-derived compounds. Here, we report that PtMo catalysts also promote hydrogenolysis of the model compound benzyl alcohol, while decarbonylation is most prevalent over unmodified Pt. A combination of single crystal surface science studies, density functional theory (DFT) calculations, and vapor phase upgrading experiments using supported catalysts was carried out to better understand the mechanism by which Mo promotes deoxygenation. Molybdenum was deposited in submonolayer quantities on a Pt(111) surface and reduced at high temperature. Temperature-programmedmore » desorption (TPD) experiments using benzyl alcohol as a reactant showed greatly enhanced yields of the deoxygenation product toluene at moderate Mo coverages. To understand how the interaction of the aromatic group with the surface influenced this reactivity, we investigated the adsorption of toluene as a probe molecule. We found that the addition of Mo to Pt(111) resulted in a significant decrease in toluene decomposition. DFT calculations indicated that this decrease was consistent with decreased aromatic adsorption strengths that accompany incorporation of Mo into the Pt subsurface. The weaker aromatic-surface interaction on Pt/Mo surfaces led to a tilted adsorption geometry for benzyl alcohol, which presumably promotes hydrogenolysis to produce toluene instead of decarbonylation to produce benzene and CO. Alumina-supported Pt and PtMo catalysts were also tested for benzyl alcohol deoxygenation. PtMo catalysts had a higher rate of toluene production and lower rates of benzene and benzaldehyde production. Additionally, when benzaldehyde was used as the reactant to measure decarbonylation activity the mass-normalized rate of benzene production was 2.5 times higher on Pt than PtMo. Altogether, the results of TPD, DFT, and supported catalyst experiments suggest that subsurface Mo sites weaken the binding of aromatic rings on PtMo surfaces; the weakened aromatic-surface interaction is correlated with an improvement in selectivity to C-O bond scission.« less

Surface chemistry of aromatic reactants on Pt- and Mo-modified Pt catalysts

DOE PAGES

Robinson, Allison M.; Mark, Lesli; Rasmussen, Mathew J.; ...

2016-11-01

Supported catalysts containing an oxophilic metal such as Mo and a noble metal such as Pt have shown promising activity and selectivity for deoxygenation of biomass-derived compounds. Here, we report that PtMo catalysts also promote hydrogenolysis of the model compound benzyl alcohol, while decarbonylation is most prevalent over unmodified Pt. A combination of single crystal surface science studies, density functional theory (DFT) calculations, and vapor phase upgrading experiments using supported catalysts was carried out to better understand the mechanism by which Mo promotes deoxygenation. Molybdenum was deposited in submonolayer quantities on a Pt(111) surface and reduced at high temperature. Temperature-programmedmore » desorption (TPD) experiments using benzyl alcohol as a reactant showed greatly enhanced yields of the deoxygenation product toluene at moderate Mo coverages. To understand how the interaction of the aromatic group with the surface influenced this reactivity, we investigated the adsorption of toluene as a probe molecule. We found that the addition of Mo to Pt(111) resulted in a significant decrease in toluene decomposition. DFT calculations indicated that this decrease was consistent with decreased aromatic adsorption strengths that accompany incorporation of Mo into the Pt subsurface. The weaker aromatic-surface interaction on Pt/Mo surfaces led to a tilted adsorption geometry for benzyl alcohol, which presumably promotes hydrogenolysis to produce toluene instead of decarbonylation to produce benzene and CO. Alumina-supported Pt and PtMo catalysts were also tested for benzyl alcohol deoxygenation. PtMo catalysts had a higher rate of toluene production and lower rates of benzene and benzaldehyde production. Additionally, when benzaldehyde was used as the reactant to measure decarbonylation activity the mass-normalized rate of benzene production was 2.5 times higher on Pt than PtMo. Altogether, the results of TPD, DFT, and supported catalyst experiments suggest that subsurface Mo sites weaken the binding of aromatic rings on PtMo surfaces; the weakened aromatic-surface interaction is correlated with an improvement in selectivity to C-O bond scission.« less

Recent Developments of Electrochemical Promotion of Catalysis in the Techniques of DeNOx

PubMed Central

Tang, Xiaolong; Yi, Honghong; Chen, Chen; Wang, Chuan

2013-01-01

Electrochemical promotion of catalysis reactions (EPOC) is one of the most significant discoveries in the field of catalytic and environmental protection. The work presented in this paper focuses on the aspects of reaction mechanism, influencing factors, and recent positive results. It has been shown with more than 80 different catalytic systems that the catalytic activity and selectivity of conductive catalysts deposited on solid electrolytes can be altered in the last 30 years. The active ingredient of catalyst can be activated by applying constant voltage or constant current to the catalysts/electrolyte interface. The effect of EPOC can improve greatly the conversion rate of NOx. And it can also improve the lifetime of catalyst by inhibiting its poisoning. PMID:23970835

Effect of Oxygen Defects on the Catalytic Performance of VOx/CeO2 Catalysts for Oxidative Dehydrogenation of Methanol

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

Li, Yan; Wei, Zhehao; Gao, Feng

2015-05-01

In this work, CeO2 nanocubes with controlled particle size and dominating (100) facets are synthesized as supports for VOx catalysts. Combined TEM, SEM, XRD, and Raman study reveals that the oxygen vacancy density of CeO2 supports can be tuned by tailoring the particle sizes without altering the dominating facets, where smaller particle sizes result in larger oxygen vacancy densities. At the same vanadium coverage, the VOx catalysts supported on small-sized CeO2 supports with higher oxygen defect densities exhibit promoted redox property and lower activation energy for methoxyl group decomposition, as evidenced by H2-TPR and methanol TPD study. These results furthermore » confirm that the presence of oxygen vacancies plays an important role in promoting the activity of VOx species in methanol oxidation. We gratefully acknowledge financial support from the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Part of this work was conducted in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for the DOE by Battelle.« less

Influence of the Crystal Structure of Titanium Oxide on the Catalytic Activity of Rh/TiO2 in Steam Reforming of Propane at Low Temperature.

PubMed

Yu, Lin; Sato, Katsutoshi; Toriyama, Takaaki; Yamamoto, Tomokazu; Matsumura, Syo; Nagaoka, Katsutoshi

2018-06-21

Solid oxide fuel cells (SOFCs) with liquefied petroleum gas (LPG) reduce CO 2 emissions due to their high-energy-conversion efficiency. Although SOFCs can convert LPG directly, coking occurs easily by decomposition of hydrocarbons, including C-C bonds on the electrode of fuel cell stacks. It is therefore necessary to develop an active steam pre-reforming catalyst that eliminates the hydrocarbons at low temperature, in which waste heat of SOFCs is used. Herein, we show that the crystal structure of the TiO 2 that anchors Rh particles is crucial for catalytic activity of Rh/TiO 2 catalysts for propane pre-reforming. Our experimental results revealed that strong metal support interaction (SMSI) induced during H 2 pre-reduction were optimized over Rh/TiO 2 with a rutile structure; this catalyst catalyzed the reaction much more effectively than conventional Rh/γ-Al 2 O 3 . In contrast, the SMSI was too strong for Rh/TiO 2 with an anatase structure, and the surface of the Rh particles was therefore covered mostly with partially reduced TiO 2 . The result was very low activity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-performance bimetallic alloy catalyst using Ni and N co-doped composite carbon for the oxygen electro-reduction.

PubMed

Jung, Won Suk

2018-03-15

In this study, a novel synthesis method for the bimetallic alloy catalyst is reported, which is subsequently used as an oxygen reduction catalyst in polymer electrolyte membrane fuel cells (PEMFCs). The support prepared from the Ni-chelate complex shows a mesoporous structure with a specific surface area of ca. 400 m 2  g -1 indicating the suitable support for PEMFC applications. Ethylenediamine is converted to the nitrogen and carbon layers to protect the Ni particles which will diffuse into the Pt lattice at 800 °C. The PtNi/NCC catalyst with PtNi cores and Pt-rich shells is successfully formed when acid-treated as evidenced by line scan profiles. The catalyst particles thus synthesized are well-dispersed on the N-doped carbon support, while the average particle size is ca. 3 nm. In the PEMFC test, the maximum power density of the PtNi/NCC catalyst shows approximately 25% higher than that of the commercial Pt/C catalyst. The mass activity of the PtNi/NCC catalyst showed approximately 3-fold higher than that of the commercial Pt/C catalyst. The mass activity strongly depends on the ratio of Pt to Ni since the strain effect can be strong for catalysts due to the mismatch of lattice parameters of the Ni and Pt. Copyright © 2017 Elsevier Inc. All rights reserved.

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.

Method for the protection of extreme ultraviolet lithography optics

DOEpatents

Grunow, Philip A.; Clift, Wayne M.; Klebanoff, Leonard E.

2010-06-22

A coating for the protection of optical surfaces exposed to a high energy erosive plasma. A gas that can be decomposed by the high energy plasma, such as the xenon plasma used for extreme ultraviolet lithography (EUVL), is injected into the EUVL machine. The decomposition products coat the optical surfaces with a protective coating maintained at less than about 100 .ANG. thick by periodic injections of the gas. Gases that can be used include hydrocarbon gases, particularly methane, PH.sub.3 and H.sub.2S. The use of PH.sub.3 and H.sub.2S is particularly advantageous since films of the plasma-induced decomposition products S and P cannot grow to greater than 10 .ANG. thick in a vacuum atmosphere such as found in an EUVL machine.

Exploring the potential of fulvalene dimetals as platforms for molecular solar thermal energy storage: computations, syntheses, structures, kinetics, and catalysis.

PubMed

Börjesson, Karl; Ćoso, Dušan; Gray, Victor; Grossman, Jeffrey C; Guan, Jingqi; Harris, Charles B; Hertkorn, Norbert; Hou, Zongrui; Kanai, Yosuke; Lee, Donghwa; Lomont, Justin P; Majumdar, Arun; Meier, Steven K; Moth-Poulsen, Kasper; Myrabo, Randy L; Nguyen, Son C; Segalman, Rachel A; Srinivasan, Varadharajan; Tolman, Willam B; Vinokurov, Nikolai; Vollhardt, K Peter C; Weidman, Timothy W

2014-11-17

A study of the scope and limitations of varying the ligand framework around the dinuclear core of FvRu2 in its function as a molecular solar thermal energy storage framework is presented. It includes DFT calculations probing the effect of substituents, other metals, and CO exchange for other ligands on ΔHstorage . Experimentally, the system is shown to be robust in as much as it tolerates a number of variations, except for the identity of the metal and certain substitution patterns. Failures include 1,1',3,3'-tetra-tert-butyl (4), 1,2,2',3'-tetraphenyl (9), diiron (28), diosmium (24), mixed iron-ruthenium (27), dimolybdenum (29), and ditungsten (30) derivatives. An extensive screen of potential catalysts for the thermal reversal identified AgNO3 -SiO2 as a good candidate, although catalyst decomposition remains a challenge. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Ji Shidong; Murakami, Setsuaki; Kamitakahara, Masanobu

The titania/hydroxyapatite composite granular photo-catalyst with novel microstructure was fabricated by the process based on the liquid immiscibility effect and followed by precalcination and hydrothermal treatment from commercially available powders of {alpha}-Tri-calcium phosphate and TiO{sub 2}. XRD, SEM, BET, optical microscopy and UV-vis spectrophotometer were applied to characterize the prepared photo-catalyst. Microstructure analysis indicated that the granule was weaved by rod-shaped hydroxyapatite crystals whose surface was covered by nano-sized TiO{sub 2}. In the composite granules, the active surface of anatase was retained effectively. With the hybridization of TiO{sub 2} and HAp, a 16-nm blue-shift of absorption edge could be observedmore » and the crystallinity of anatase could be enhanced by precalcination. The granules with the rod-shaped hydroxyapatite crystals performing as scaffold work as three-dimensional high porous, size-controllable small reactor. The phase and microstructure transformation of the granule before and after hydrothermal treatment was investigated and its decomposition ability was evaluated by using Methylene blue as a target pollutant compound.« less

Bridging the pressure gap: In situ atomic-level investigations of model platinum catalyst surfaces under reaction conditions by scanning tunneling microscopy

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

McIntyre, Brian James

1994-05-01

Results of this thesis show that STM measurements can provide information about the surfaces and their adsorbates. Stability of Pt(110) under high pressures of H 2, O 2, and CO was studied (Chap. 4). In situ UHV and high vacuum experiments were carried out for sulfur on Pt(111) (Chap.5). STM studies of CO/S/Pt(111) in high CO pressures showed that the Pt substrate undergoes a stacking-fault-domain reconstruction involving periodic transitions from fcc to hcp stacking of top-layer atoms (Chap.6). In Chap.7, the stability of propylene on Pt(111) and the decomposition products were studied in situ with the HPSTM. Finally, in Chap.8,more » results are presented which show how the Pt tip of the HPSTM was used to locally rehydrogenate and oxidize carbonaceous clusters deposited on the Pt(111) surface; the Pt tip acted as a catalyst after activation by short voltage pulses.« less

ATOM-ECONOMICAL PATHWAYS TO METHANOL FUEL CELL FROM BIOMASS

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

MAHAJAN,D.; WEGRZYN,J.E.

1999-03-01

An economical production of alcohol fuels from biomass, a feedstock low in carbon and high in water content, is of interest. At Brookhaven National Laboratory (BNL), a Liquid Phase Low Temperature (LPLT) concept is under development to improve the economics by maximizing the conversion of energy carrier atoms (C,H) into energy liquids (fuel). So far, the LPLT concept has been successfully applied to obtain highly efficient methanol synthesis. This synthesis was achieved with specifically designed soluble catalysts, at temperatures < 150 C. A subsequent study at BNL yielded a water-gas-shift (WGS) catalyst for the production of hydrogen from a feedstockmore » of carbon monoxide and H{sub 2}O at temperatures < 120 C. With these LPLT technologies as a background, this paper extends the discussion of the LPLT concept to include methanol decomposition into 3 moles of H{sub 2} per mole of methanol. The implication of these technologies for the atom-economical pathways to methanol fuel cell from biomass is discussed.« less

Electrocatalysis of the HER in acid and alkaline media

DOE PAGES

Danilovic, Nemanja; Subbaraman, Ram; Strmcnik, Dusan; ...

2013-01-01

Trends in the HER are studied on selected metals (M= Cu, Ag, Au, Pt, Ru, Ir, Ti) in acid and alkaline environments. Here, we found that with the exception of Pt, Ir and Au, due to high coverage by spectator species on non-noble metal catalysts, experimentally established positions of Cu , Ag, Ru and Ti in the observed volcano relations are still uncertain. We also found that while in acidic solutions the M-Hupd binding energy most likely is controlling the activity trends, the trends in activity in alkaline solutions are controlled by a delicate balance between two descriptors: the M-Hadmore » interaction as well as the energetics required to dissociate water molecules. We confirm the importance of the second descriptor by introducing bifunctional catalysts such as M modified by Ni(OH); e.g. while the latter serves to enhance catalytic decomposition of water, the metal sites are required for collecting and recombining the produced hydrogen intermediates.« less

Recent advancements in supporting materials for immobilised photocatalytic applications in waste water treatment.

PubMed

Srikanth, B; Goutham, R; Badri Narayan, R; Ramprasath, A; Gopinath, K P; Sankaranarayanan, A R

2017-09-15

The aim of this paper is to provide a review on the usage of different anchoring media (supports) for immobilising commonly employed photocatalysts for degradation of organic pollutants. The immobilisation of nano-sized photocatalysts can eliminate costly and impractical post-treatment recovery of spent photocatalysts in largescale operations. Some commonly employed immobilisation aids such as glass, carbonaceous substances, zeolites, clay and ceramics, polymers, cellulosic materials and metallic agents that have been previously discussed by various research groups have been reviewed. The study revealed that factors such as high durability, ease of availability, low density, chemical inertness and mechanical stability are primary factors responsible for the selection of suitable supports for catalysts. Common techniques for immobilisation namely, dip coating, cold plasma discharge, polymer assisted hydrothermal decomposition, RF magnetron sputtering, photoetching, solvent casting, electrophoretic deposition and spray pyrolysis have been discussed in detail. Finally, some common techniques adopted for the characterisation of the catalyst particles and their uses are also discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

VUV photo-oxidation of gaseous benzene combined with ozone-assisted catalytic oxidation: Effect on transition metal catalyst

NASA Astrophysics Data System (ADS)

Huang, Haibao; Lu, Haoxian; Zhan, Yujie; Liu, Gaoyuan; Feng, Qiuyu; Huang, Huiling; Wu, Muyan; Ye, Xinguo

2017-01-01

Volatile organic compounds (VOCs) cause the major air pollution concern. In this study, a series of ZSM-5 supported transition metals were prepared by impregnation method. They were combined with vacuum UV (VUV) photo-oxidation in a continuous-flow packed-bed reactor and used for the degradation of benzene, a typical toxic VOCs. Compared with VUV photo-oxidation alone, the introduction of catalysts can greatly enhance benzene oxidation under the help of O3, the by-products from VUV irradiation, via ozone-assisted catalytic oxidation (OZCO). The catalytic activity of transition metals towards benzene oxidation followed the order: Mn > Co > Cu > Ni > Fe. Mn achieved the best catalytic activity due to the strongest capability for O3 catalytic decomposition and utilization. Benzene and O3 removal efficiency reached as high as 97% and 100% after 360 min, respectively. O3 was catalytically decomposed, generating highly reactive oxidants such as rad OH and rad O for benzene oxidation.

Theoretical Study of the Thermal Decomposition of Carboxylic Acids at Pyrolysis Temperature

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

Clark, J. M.; Robichaud, D. J.; Nimlos, M. R.

2013-01-01

Carboxylic acids are important in the processing of biomass into renewable fuels and chemicals. They are formed from the pretreatment and pyrolysis of hemicellulose biopolymers and are released from the decomposition of sugars. They result from the deconstruction of polyhydroxyalkanoates (bacterial carbon storage polymers) from fatty acids derived from algae, bacteria, and oil crops. The thermal deoxygenation of carboxylic acids is an important step in the conversion of biomass into aliphatic hydrocarbons suitable for use in renewable biofuels and as petrochemical replacements. Decarboxylation, a primary decomposition pathway under pyrolysis conditions, represents an ideal conversion process, because it eliminates two atomsmore » of oxygen for every carbon atom removed. Problematically, additional deoxygenation processes exist (e.g. dehydration) that are in direct competition with decarboxylation and result in the formation of reactive and more fragmented end products. To better understand the competition between decarboxylation and other deoxygenation processes and to gain insight into possible catalysts that would favor decarboxylation, we have investigated the mechanisms and thermochemistry of the various unimolecular and bimolecular deoxygenation pathways for a family of C1-C4 organic acids using electronic structure calculations at the M06-2X/6-311++G(2df,p) level of theory.« less

Geometrical flexibility of platinum nanoclusters: impacts on catalytic decomposition of ethylene glycol.

PubMed

Mahmoodinia, Mehdi; Trinh, Thuat T; Åstrand, Per-Olof; Tran, Khanh-Quang

2017-11-01

Catalytic decomposition of ethylene glycol on the Pt 13 cluster was studied as a model system for hydrogen production from a lignocellulosic material. Ethylene glycol was chosen as a starting material because of two reasons, it is the smallest oxygenate with a 1 : 1 carbon to oxygen ratio and it contains the C-H, O-H, C-C, and C-O bonds also present in biomass. Density functional theory calculations were employed for predictions of reaction pathways for C-H, O-H, C-C and C-O cleavages, and Brønsted-Evans-Polanyi relationships were established between the final state and the transition state for all mechanisms. The results show that Pt 13 catalyzes the cleavage reactions of ethylene glycol more favourably than a Pt surface. The flexibility of Pt 13 clusters during the reactions is the key factor in reducing the activation barrier. Overall, the results demonstrate that ethylene glycol and thus biomass can be efficiently converted into hydrogen using platinum nanoclusters as catalysts.

Reforming and decomposition of glucose in an aqueous phase

NASA Technical Reports Server (NTRS)

Amin, S.; Reid, R. C.; Modell, M.

1975-01-01

Exploratory experiments have been carried out to study the decomposition of glucose, a typical carbohydrate, in a high temperature-high pressure water reactor. The objective of the study was to examine the feasibility of such a process to decompose cellulosic waste materials in long-term space missions. At temperatures below the critical point of water, glucose decomposed to form liquid products and char. Little gas was noted with or without reforming catalysts present. The rate of the primary glucose reaction increased significantly with temperature. Partial identification of the liquid phase was made and the C:H:O ratios determined for both the liquid and solid products. One of the more interesting results from this study was the finding that when glucose was injected into a reactor held at the critical temperature (and pressure) of water, no solid products formed. Gas production increased, but the majority of the carbon was found in soluble furans (and furan derivatives). This significant result is now being investigated further.

Selective C-O Hydrogenolysis and Decarboxylation of Biomass-Derived Heterocyclic Compounds over Heterogeneous Catalysts

NASA Astrophysics Data System (ADS)

Chia, Mei

The catalytic deoxygenation of biomass-derived compounds through selective C-O hydrogenolysis, catalytic transfer hydrogenation and lactonization, and decarboxylation to value-added chemicals over heterogeneous catalysts was examined under liquid phase reaction conditions. The reactions studied involve the conversion or production of heterocyclic compounds, specifically, cyclic ethers, lactones, and 2-pyrones. A bimetallic RhRe/C catalyst was found to be selective for the hydrogenolysis of secondary C-O bonds for a broad range cyclic ethers and polyols. Results from experimentally-observed reactivity trends, NH3 temperature-programmed desorption, fructose dehydration reaction studies, and first-principles density functional theory (DFT) calculations are consistent with the hypothesis of a bifunctional catalyst which facilitates acid-catalyzed ring-opening and dehydration coupled with metal-catalyzed hydrogenation. C-O hydrogenolysis and fructose dehydration activities were observed to decrease with an increase in reduction temperature and a decrease in the number of surface metallic Re atoms measured by in situ X-ray absorption spectroscopy. No C-O hydrogenolysis activity was detected over RhRe/C under water-free conditions. The activation of water molecules by Re atoms on the surface of metallic Rh is suggested to result in the formation of Bronsted acidity over RhRe/C. The catalytic transfer hydrogenation and lactonization of levulinic acid and its esters to gamma-valerolactone was accomplished through the Meerwein-Ponndorf-Verley reaction over metal oxide catalysts using secondary alcohols as the hydrogen donor. ZrO2 was a highly active material for CTH under batch and continuous flow reaction conditions; the initial activity of the catalyst was repeatedly regenerable by calcination in air, with no observable loss in catalytic activity. Lastly, the 2-pyrone, triacetic acid lactone, is shown to be a promising biorenewable platform chemical from which a wide range of chemical intermediates and end products can be obtained using heterogeneous catalysts or by thermal decomposition. Mechanistic insights from experimentally-observed reactivity trends and results from DFT calculations indicate that 2-pyrones undergo reactions unique to their structure such as keto-enol tautomerization, retro Diels-Alder, and nucleophilic attack by water. Ring-opening and decarboxylation reactions were found to be governed by key structural features such as the degree of saturation in the ring (e.g., C4=C5 bond), nature of the solvent, and presence of an acid catalyst.

Influences of operational practices on municipal solid waste landfill storage capacity.

PubMed

Li, Yu-Chao; Liu, Hai-Long; Cleall, Peter John; Ke, Han; Bian, Xue-Cheng

2013-03-01

The quantitative effects of three operational factors, that is initial compaction, decomposition condition and leachate level, on municipal solid waste (MSW) landfill settlement and storage capacity are investigated in this article via consideration of a hypothetical case. The implemented model for calculating landfill compression displacement is able to consider decreases in compressibility induced by biological decomposition and load dependence of decomposition compression for the MSW. According to the investigation, a significant increase in storage capacity can be achieved by intensive initial compaction, adjustment of decomposition condition and lowering of leachate levels. The quantitative investigation presented aims to encourage landfill operators to improve management to enhance storage capacity. Furthermore, improving initial compaction and creating a preferential decomposition condition can also significantly reduce operational and post-closure settlements, respectively, which helps protect leachate and gas management infrastructure and monitoring equipment in modern landfills.

The direct reductive amination of electron-deficient amines with aldehydes: the unique reactivity of the Re2O7 catalyst.

PubMed

Das, Braja Gopal; Ghorai, Prasanta

2012-08-25

An unprecedented direct reductive amination of electron-deficient amines such as Cbz-, Boc-, EtOCO-, Fmoc-, Bz-, ArSO(2)-, Ar(2)PO-, etc. protected amines with aldehydes is achieved using the Re(2)O(7) catalyst and silanes as the hydride source. Excellent regioselective mono-alkylation and chemoselective reductive-amination were observed.

System for thermochemical hydrogen production

DOEpatents

Werner, R.W.; Galloway, T.R.; Krikorian, O.H.

1981-05-22

Method and apparatus are described for joule boosting a SO/sub 3/ decomposer using electrical instead of thermal energy to heat the reactants of the high temperature SO/sub 3/ decomposition step of a thermochemical hydrogen production process driven by a tandem mirror reactor. Joule boosting the decomposer to a sufficiently high temperature from a lower temperature heat source eliminates the need for expensive catalysts and reduces the temperature and consequent materials requirements for the reactor blanket. A particular decomposer design utilizes electrically heated silicon carbide rods, at a temperature of 1250/sup 0/K, to decompose a cross flow of SO/sub 3/ gas.

A Highly Practical Copper(I)/TEMPO Catalyst System for Chemoselective Aerobic Oxidation of Primary Alcohols

PubMed Central

Hoover, Jessica M.; Stahl, Shannon S.

2011-01-01

Aerobic oxidation reactions have been the focus of considerable attention, but their use in mainstream organic chemistry has been constrained by limitations in their synthetic scope and by practical factors, such as the use of pure O2 as the oxidant or complex catalyst synthesis. Here, we report a new (bpy)CuI/TEMPO catalyst system that enables efficient and selective aerobic oxidation of a broad range of primary alcohols, including allylic, benzylic and aliphatic derivatives, to the corresponding aldehydes using readily available reagents, at room temperature with ambient air as the oxidant. The catalyst system is compatible with a wide range of functional groups and the high selectivity for 1° alcohols enables selective oxidation of diols that lack protecting groups. PMID:21861488

The carburization of transition metal molybdates (MxMoO₄, M= Cu, Ni or Co) and the generation of highly active metal/carbide catalysts for CO₂ hydrogenation

DOE PAGES

Rodriguez, Jose A.; Xu, Wenqian; Ramirez, Pedro J.; ...

2015-05-06

A new approach has been tested for the preparation of metal/Mo₂C catalysts using mixed-metal oxide molybdates as precursors. Synchrotron-based in situ time-resolved X-ray diffraction was used to study the reduction and carburization processes of Cu₃(MoO₄)₂(OH)₂, a-NiMoO₄ and CoMoO₄• nH₂O by thermal treatment under mixtures of hydrogen and methane. In all cases, the final product was β-Mo₂C and a metal phase (Cu, Ni, or Co), but the transition sequence varied with the different metals, and it could be related to the reduction potential of the Cu²⁺, Ni²⁺ and Co²⁺ cations inside each molybdate. The synthesized Cu/Mo₂C, Ni/Mo₂C and Co/Mo₂C catalysts weremore » highly active for the hydrogenation of CO₂. The metal/Mo₂C systems exhibited large variations in the selectivity towards methanol, methane and C nH₂ n₊₂ (n > 2) hydrocarbons depending on the nature of the supported metal and its ability to cleave C-O bonds. Cu/Mo₂C displayed a high selectivity for CO and methanol production. Ni/Mo₂C and Co/Mo₂C were the most active catalysts for the activation and full decomposition of CO₂, showing high selectivity for the production of methane (Ni case) and C nH₂ n₊₂ (n > 2) hydrocarbons (Co case).« less

The promoting effect of CeO2@Ce-O-P multi-core@shell structure on SO2 tolerance for selective catalytic reduction of NO with NH3 at low temperature

NASA Astrophysics Data System (ADS)

Yao, Weiyuan; Liu, Yue; Wu, Zhongbiao

2018-06-01

A series of CeO2@Ce-O-P "multi-core@shell" catalysts were synthesized in this paper for selective catalytic reduction (SCR) of NO with NH3. The experimental results had showed that CeO2@Ce-O-P-30:3 yielded best SO2 tolerance of an over 70% deNOx efficiency at 250 °C in the presence of 100 ppm SO2 for 20 h, which was much higher compared to pure Ce-O-P and CeO2 samples. Further characterization results indicated that Ce-O-P coating layer could somewhat inhibit sulfur depositing on the catalysts during SCR reaction in the presence of SO2, thereby protecting the active sites from SO2 poisoning. Especially, O2-TPD results illustrated that a great amount of active oxygen species were retained on used CeO2@Ce-O-P catalyst after a long term reaction. The synergetic effect of "multi-core@shell" structure could be attributed to such enhanced performances. The "core" CeO2 devoted abundant active oxygen sites to fulfill the SCR reaction. And the "shell" Ce-O-P could not only provide acid sites, but also protect the active oxygen species by avoiding the over-adsorption of SO2 on the catalyst. This work could provide a new way to increase the sulfur resistance for low temperature SCR catalysts.

Increasing Stability and Activity of Core-Shell Catalysts by Preferential Segregation of Oxide on Edges and Vertexes: Oxygen Reduction on Ti-Au@Pt/C

DOE PAGES

Hu, J.; Wu, L.; Kuttiyiel, K.; ...

2016-06-30

We describe a new class of core-shell nanoparticle catalysts having edges and vertexes covered by refractory metal oxide that preferentially segregates onto these catalyst sites. The monolayer shell is deposited on the oxidefree core atoms. The oxide on edges and vertexes induces high catalyst’s stability and activity. The catalyst and synthesis are exemplified by fabrication of Au nanoparticles doped by Ti atoms that segregate as oxide onto low–coordination sites of edges and vertexes. Pt monolayer shell deposited on Au sites has the mass and specific activities for the oxygen reduction reaction about 13 and 5 times higher than those ofmore » commercial Pt/C catalysts. The durability tests show no activity loss after 10000 potential cycles from 0.6 to 1.0V. The superior activity and durability of the Ti-Au@Pt catalyst originate from protective Ti oxide located at the most dissolution-prone edge and vertex sites, and Au-supported active and stable Pt shell.« less

Physico-chemical protection, rather than biochemical composition, governs the responses of soil organic carbon decomposition to nitrogen addition in a temperate agroecosystem.

PubMed

Tan, Wenbing; Wang, Guoan; Huang, Caihong; Gao, Rutai; Xi, Beidou; Zhu, Biao

2017-11-15

The heterogeneous responses of soil organic carbon (SOC) decomposition in different soil fractions to nitrogen (N) addition remain elusive. In this study, turnover rates of SOC in different aggregate fractions were quantified based on changes in δ 13 C following the conversion of C 3 to C 4 vegetation in a temperate agroecosystem. The turnover of both total organic matter and specific organic compound classes within each aggregate fraction was inhibited by N addition. Moreover, the intensity of inhibition increases with decreasing aggregate size and increasing N addition level, but does not vary among chemical compound classes within each aggregate fraction. Overall, the response of SOC decomposition to N addition is dependent on the physico-chemical protection of SOC by aggregates and minerals, rather than the biochemical composition of organic substrates. The results of this study could help to understand the fate of SOC in the context of increasing N deposition. Copyright © 2017 Elsevier B.V. All rights reserved.

16 CFR 453.3 - Misrepresentations.

Code of Federal Regulations, 2012 CFR

2012-01-01

... funeral services will delay the natural decomposition of human remains for a long-term or indefinite time; (2) Represent that funeral goods have protective features or will protect the body from gravesite... can use an alternative container. Alternative containers encase the body and can be made of materials...

16 CFR 453.3 - Misrepresentations.

Code of Federal Regulations, 2011 CFR

2011-01-01

... funeral services will delay the natural decomposition of human remains for a long-term or indefinite time; (2) Represent that funeral goods have protective features or will protect the body from gravesite... can use an alternative container. Alternative containers encase the body and can be made of materials...

16 CFR 453.3 - Misrepresentations.

Code of Federal Regulations, 2014 CFR

2014-01-01

... funeral services will delay the natural decomposition of human remains for a long-term or indefinite time; (2) Represent that funeral goods have protective features or will protect the body from gravesite... can use an alternative container. Alternative containers encase the body and can be made of materials...

16 CFR 453.3 - Misrepresentations.

Code of Federal Regulations, 2013 CFR

2013-01-01

... funeral services will delay the natural decomposition of human remains for a long-term or indefinite time; (2) Represent that funeral goods have protective features or will protect the body from gravesite... can use an alternative container. Alternative containers encase the body and can be made of materials...

Iron oxide nanoparticle layer templated by polydopamine spheres: a novel scaffold toward hollow-mesoporous magnetic nanoreactors

NASA Astrophysics Data System (ADS)

Huang, Liang; Ao, Lijiao; Xie, Xiaobin; Gao, Guanhui; Foda, Mohamed F.; Su, Wu

2014-12-01

Superparamagnetic iron oxide nanoparticle layers with high packing density and controlled thickness were in situ deposited on metal-affinity organic templates (polydopamine spheres), via one-pot thermal decomposition. The as synthesized hybrid structure served as a facile nano-scaffold toward hollow-mesoporous magnetic carriers, through surfactant-assisted silica encapsulation and its subsequent calcination. Confined but accessible gold nanoparticles were successfully incorporated into these carriers to form a recyclable catalyst, showing quick magnetic response and a large surface area (642.5 m2 g-1). Current nano-reactors exhibit excellent catalytic performance and high stability in reduction of 4-nitrophenol, together with convenient magnetic separability and good reusability. The integration of compact iron oxide nanoparticle layers with programmable polydopamine templates paves the way to fabricate magnetic-response hollow structures, with high permeability and multi-functionality.Superparamagnetic iron oxide nanoparticle layers with high packing density and controlled thickness were in situ deposited on metal-affinity organic templates (polydopamine spheres), via one-pot thermal decomposition. The as synthesized hybrid structure served as a facile nano-scaffold toward hollow-mesoporous magnetic carriers, through surfactant-assisted silica encapsulation and its subsequent calcination. Confined but accessible gold nanoparticles were successfully incorporated into these carriers to form a recyclable catalyst, showing quick magnetic response and a large surface area (642.5 m2 g-1). Current nano-reactors exhibit excellent catalytic performance and high stability in reduction of 4-nitrophenol, together with convenient magnetic separability and good reusability. The integration of compact iron oxide nanoparticle layers with programmable polydopamine templates paves the way to fabricate magnetic-response hollow structures, with high permeability and multi-functionality. Electronic supplementary information (ESI) available: Fig. S1-S5. See DOI: 10.1039/c4nr05931j

Pyrolysis and dehalogenation of plastics from waste electrical and electronic equipment (WEEE): a review.

PubMed

Yang, Xiaoning; Sun, Lushi; Xiang, Jun; Hu, Song; Su, Sheng

2013-02-01

Plastics from waste electrical and electronic equipment (WEEE) have been an important environmental problem because these plastics commonly contain toxic halogenated flame retardants which may cause serious environmental pollution, especially the formation of carcinogenic substances polybrominated dibenzo dioxins/furans (PBDD/Fs), during treat process of these plastics. Pyrolysis has been proposed as a viable processing route for recycling the organic compounds in WEEE plastics into fuels and chemical feedstock. However, dehalogenation procedures are also necessary during treat process, because the oils collected in single pyrolysis process may contain numerous halogenated organic compounds, which would detrimentally impact the reuse of these pyrolysis oils. Currently, dehalogenation has become a significant topic in recycling of WEEE plastics by pyrolysis. In order to fulfill the better resource utilization of the WEEE plastics, the compositions, characteristics and dehalogenation methods during the pyrolysis recycling process of WEEE plastics were reviewed in this paper. Dehalogenation and the decomposition or pyrolysis of WEEE plastics can be carried out simultaneously or successively. It could be 'dehalogenating prior to pyrolysing plastics', 'performing dehalogenation and pyrolysis at the same time' or 'pyrolysing plastics first then upgrading pyrolysis oils'. The first strategy essentially is the two-stage pyrolysis with the release of halogen hydrides at low pyrolysis temperature region which is separate from the decomposition of polymer matrixes, thus obtaining halogenated free oil products. The second strategy is the most common method. Zeolite or other type of catalyst can be used in the pyrolysis process for removing organohalogens. The third strategy separate pyrolysis and dehalogenation of WEEE plastics, which can, to some degree, avoid the problem of oil value decline due to the use of catalyst, but obviously, this strategy may increase the cost of whole recycling process. Copyright © 2012 Elsevier Ltd. All rights reserved.

Cerium incorporated MCM-48 (Ce-MCM-48) as a catalyst to inhibit bromate formation during ozonation of bromide-containing water: Efficacy and mechanism.

PubMed

Li, Weiwei; Lu, Xiaowei; Xu, Ke; Qu, Jiuhui; Qiang, Zhimin

2015-12-01

The composite mesoporous sieve Ce-MCM-48 (cerium incorporated MCM-48) with different Si/Ce molar ratios were synthesized hydrothermally and characterized with X-ray diffraction, X-ray photoelectron spectroscopy, BET surface area, and pHpzc. Results indicate that Ce-MCM-48, especially with a Si/Ce molar ratio of 66 (i.e., Ce66-MCM-48), could significantly inhibit bromate (BrO3(-)) formation during ozonation of Br(-)-containing water, achieving 91% of inhibition efficiency at pH 7.6 and 25 °C. An acidic or alkaline pH decreased the inhibition efficiency of Ce66-MCM-48 to some extent, but reaction temperature ranging from 15 to 30 °C had no significant impact. By comparing the bromine mass balance, aqueous O3 decomposition, and newly formed H2O2 between O3 and O3/Ce66-MCM-48 processes, the inhibition mechanism was proposed: Ce66-MCM-48 promoted aqueous O3 decomposition to generate hydroxyl radicals (OH) that could merge into H2O2, so the oxidative transformation of Br(-) and HOBr/OBr(-) by O3 and OH was primarily suppressed. The catalytic ability of Ce66-MCM-48 was continuously regenerated through the circulating reactions between Ce(III) and Ce(IV) occurring on the catalyst surface. Besides its inhibition on BrO3(-) formation, Ce66-MCM-48 could also enhance the degradation of refractory organic micropollutants. Because of these distinct merits, Ce66-MCM-48 has potential applications to water treatment by ozone. Copyright © 2015 Elsevier Ltd. All rights reserved.

Stability of carbon electrodes for aqueous lithium-air secondary batteries

NASA Astrophysics Data System (ADS)

Ohkuma, Hirokazu; Uechi, Ichiro; Matsui, Masaki; Takeda, Yasuo; Yamamoto, Osamu; Imanishi, Nobuyuki

2014-01-01

The air electrode performance of various carbon materials, such as Ketjen black (KB), acetylene black (AB and AB-S), Vulcan XC-72R (VX), and vapor grown carbon fiber (VGCF) with and without La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) catalyst were examined in an aqueous solution of saturated LiOH with 10 M LiCl in the current density range 0.2-2.0 mA cm-2. The best performance for oxygen reduction and evolution reactions was observed for the KB electrode, which has the highest surface area among the carbon materials examined. A steady over-potential of 0.2 V was obtained for the oxygen reduction reaction using the KB electrode without the catalyst, while the over-potential was 0.15 V for KB with the LSCF catalyst at 2.0 mA cm-2. The over-potentials for the oxygen evolution reaction were slightly higher than those for the oxygen reduction reaction, and gradually increased with the polarization period. Analysis of the gas in the cell after polarization above 0.4 V revealed the evolution of a small amount of CO during the oxygen evolution reaction by the decomposition of carbon in the electrode. The amount of CO evolved was significantly decreased by the addition of LSCF to the carbon electrode.

Effect of nitrogen-containing impurities on the activity of perovskitic catalysts for the catalytic combustion of methane.

PubMed

Buchneva, Olga; Gallo, Alessandro; Rossetti, Ilenia

2012-11-05

LaMnO(3), either pure or doped with 10 mol % Sr, has been prepared by flame pyrolysis in nanostructured form. Such catalysts have been tested for the catalytic flameless combustion of methane, achieving very high catalytic activity. The resistance toward poisoning by some model N-containing impurities has been checked in order to assess the possibility of operating the flameless catalytic combustion with biogas, possibly contaminated by S- or N-based compounds. This would be a significant improvement from the environmental point of view because the application of catalytic combustion to gas turbines would couple improved energy conversion efficiency and negligible noxious emissions, while the use of biogas would open the way to energy production from a renewable source by means of very efficient technologies. A different behavior has been observed for the two catalysts; namely, the undoped sample was more or less heavily poisoned, whereas the Sr-doped sample showed slightly increasing activity upon dosage of N-containing compounds. A possible reaction mechanism has been suggested, based on the initial oxidation of the organic backbone, with the formation of NO. The latter may adsorb more or less strongly depending on the availability of surface oxygen vacancies (i.e., depending on doping). Decomposition of NO may leave additional activated oxygen species on the surface, available for low-temperature methane oxidation and so improving the catalytic performance.

Preparation of highly active manganese oxides supported on functionalized MWNTs for low temperature NOx reduction with NH3

NASA Astrophysics Data System (ADS)

Pourkhalil, Mahnaz; Moghaddam, Abdolsamad Zarringhalam; Rashidi, Alimorad; Towfighi, Jafar; Mortazavi, Yadollah

2013-08-01

Manganese oxide catalysts (MnOx) supported on functionalized multi-walled carbon nanotubes (FMWNTs) for low temperature selective catalytic reduction (LTSCR) of nitrogen oxides (NOx) with NH3 in the presence of excess O2 were prepared by the incipient wetness impregnation method. These catalysts were characterized by N2 adsorption, Fourier transform infrared spectroscopy (FTIR), transmission electron microscope (TEM), X-ray diffraction (XRD), thermal gravimetric analysis (TGA) and H2-temperature programmed reduction (H2-TPR) methods. The effects of reaction temperature, MnOx loading, calcination temperature and calcination time were investigated. The presence of surface nitrate species under moderate calcination conditions may play a favorable role in the LTSCR of NOx with NH3. Under the reaction conditions of 200 °C, 1 bar, NO = NH3 = 900 ppm, O2 = 5 vol%, GHSV = 30,000 h-1 and 12 wt% MnOx, NOx conversion and N2 selectivity were 97% and 99.5%, respectively. The SCR activity was reduced in the presence of 100 ppm SO2 and 2.5 vol% H2O from 97% to 92% within 6 h at 200 °C, however such an effect was shown to be reversible by exposing the catalyst to a helium flow for 2 h at 350 °C due to thermal decomposition of ammonium sulphate salts.

Fe-Based Nano-Materials in Catalysis

PubMed Central

Konstantopoulos, Christos

2018-01-01

The role of iron in view of its further utilization in chemical processes is presented, based on current knowledge of its properties. The addition of iron to a catalyst provides redox functionality, enhancing its resistance to carbon deposition. FeOx species can be formed in the presence of an oxidizing agent, such as CO2, H2O or O2, during reaction, which can further react via a redox mechanism with the carbon deposits. This can be exploited in the synthesis of active and stable catalysts for several processes, such as syngas and chemicals production, catalytic oxidation in exhaust converters, etc. Iron is considered an important promoter or co-catalyst, due to its high availability and low toxicity that can enhance the overall catalytic performance. However, its operation is more subtle and diverse than first sight reveals. Hence, iron and its oxides start to become a hot topic for more scientists and their findings are most promising. The scope of this article is to provide a review on iron/iron-oxide containing catalytic systems, including experimental and theoretical evidence, highlighting their properties mainly in view of syngas production, chemical looping, methane decomposition for carbon nanotubes production and propane dehydrogenation, over the last decade. The main focus goes to Fe-containing nano-alloys and specifically to the Fe–Ni nano-alloy, which is a very versatile material. PMID:29772842

Density functional theory study for the enhanced sulfur tolerance of Ni catalysts by surface alloying

NASA Astrophysics Data System (ADS)

Hwang, Bohyun; Kwon, Hyunguk; Ko, Jeonghyun; Kim, Byung-Kook; Han, Jeong Woo

2018-01-01

Sulfur compounds in fuels deactivate the surface of anode materials in solid oxide fuel cells (SOFCs), which adversely affect the long-term durability. To solve this issue, it is important to design new SOFC anode materials with high sulfur tolerance. Unfortunately, it is difficult to completely replace the traditional Ni anode owing to its outstanding reactivity with low cost. As an alternative, alloying Ni with transition metals is a practical strategy to enhance the sulfur resistance while taking advantage of Ni metal. Therefore, in this study, we examined the effects of transition metal (Cu, Rh, Pd, Ag, Pt, and Au) doping into a Ni catalyst on not only the adsorption of H2S, HS, S, and H but also H2S decomposition using density functional theory (DFT) calculations. The dopant metals were selected rationally by considering the stability of the Ni-based binary alloys. The interactions between sulfur atoms produced by H2S dissociation and the surface are weakened by the dopant metals at the topmost layer. In addition, the findings show that H2S dissociation can be suppressed by doping transition metals. It turns out that these effects are maximized in the Au-doped Ni catalyst. Our DFT results will provide useful insights into the design of sulfur-tolerant SOFC anode materials.

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.

Fuel properties of biodiesel/ultra-low sulfur diesel (ULSD) blends

USDA-ARS?s Scientific Manuscript database

Biodiesel is an alternative fuel and fuel extender easily derived from vegetable oil or animal fat. In 2006, the U.S. Environmental Protection Agency mandated that maximum sulfur content of diesel fuels be reduced to 15 ppm to protect catalysts employed in exhaust after-treatment devices. Processi...

Aerosol processing: a wind of innovation in the field of advanced heterogeneous catalysts.

PubMed

Debecker, Damien P; Le Bras, Solène; Boissière, Cédric; Chaumonnot, Alexandra; Sanchez, Clément

2018-06-05

Aerosol processing is long known and implemented industrially to obtain various types of divided materials and nanomaterials. The atomisation of a liquid solution or suspension produces a mist of aerosol droplets which can then be transformed via a diversity of processes including spray-drying, spray pyrolysis, flame spray pyrolysis, thermal decomposition, micronisation, gas atomisation, etc. The attractive technical features of these aerosol processes make them highly interesting for the continuous, large scale, and tailored production of heterogeneous catalysts. Indeed, during aerosol processing, each liquid droplet undergoes well-controlled physical and chemical transformations, allowing for example to dry and aggregate pre-existing solid particles or to synthesise new micro- or nanoparticles from mixtures of molecular or colloidal precursors. In the last two decades, more advanced reactive aerosol processes have emerged as innovative means to synthesise tailored-made nanomaterials with tunable surface properties, textures, compositions, etc. In particular, the "aerosol-assisted sol-gel" process (AASG) has demonstrated tremendous potential for the preparation of high-performance heterogeneous catalysts. The method is mainly based on the low-cost, scalable, and environmentally benign sol-gel chemistry process, often coupled with the evaporation-induced self-assembly (EISA) concept. It allows producing micronic or submicronic, inorganic or hybrid organic-inorganic particles bearing tuneable and calibrated porous structures at different scales. In addition, pre-formed nanoparticles can be easily incorporated or formed in a "one-pot" bottom-up approach within the porous inorganic or hybrid spheres produced by such spray drying method. Thus, multifunctional catalysts with tailored catalytic activities can be prepared in a relatively simple way. This account is an overview of aerosol processed heterogeneous catalysts which demonstrated interesting performance in various relevant chemical reactions like isomerisation, hydrogenation, olefin metathesis, pollutant total oxidation, selective oxidation, CO2 methanation, etc. A short survey of patents and industrial applications is also presented. Our objective is to demonstrate the tremendous possibilities offered by the coupling between bottom up synthesis routes and these aerosol processing technologies which will most probably represent a major route of innovation in the mushrooming field of catalyst preparation research.

A Facile Molecular Precursor Route to Metal Phosphide Nanoparticles and Their Evaluation as Hydrodeoxygenation Catalysts

DOE PAGES

Habas, Susan E.; Baddour, Frederick G.; Ruddy, Daniel A.; ...

2015-11-05

Metal phosphides have been identified as a promising class of materials for the catalytic upgrading of bio-oils, which are renewable and potentially inexpensive sources for liquid fuels. Herein, we report the facile synthesis of a series of solid, phase-pure metal phosphide nanoparticles (NPs) (Ni 2P, Rh 2P, and Pd 3P) utilizing commercially available, air-stable metal–phosphine complexes in a one-pot reaction. This single-source molecular precursor route provides an alternative method to access metal phosphide NPs with controlled phases and without the formation of metal NP intermediates that can lead to hollow particles. The formation of the Ni 2P NPs was shownmore » to proceed through an amorphous Ni–P intermediate, leading to the desired NP morphology and metal-rich phase. This low-temperature, rapid route to well-defined metal NPs is expected to have broad applicability to a variety of readily available or easily synthesized metal–phosphine complexes with high decomposition temperatures. Hydrodeoxygenation of acetic acid, an abundant bio-oil component, was performed to investigate H 2 activation and deoxygenation pathways under conditions that are relevant to ex situ catalytic fast pyrolysis (high temperatures, low pressures, and near-stoichiometric H 2 concentrations). The catalytic performance of the silica-supported metal phosphide NPs was compared to the analogous incipient wetness (IW) metal and metal phosphide catalysts over the range 200–500 °C. Decarbonylation was the primary pathway for H 2 incorporation in the presence of all of the catalysts except NP-Pd 3P, which exhibited minimal productive activity, and IW-Ni, which evolved H 2. The highly controlled NP-Ni2P and NP-Rh2P catalysts, which were stable under these conditions, behaved comparably to the IW-metal phosphides, with a slight shift to higher product onset temperatures, likely due to the presence of surface ligands. Most importantly, the NP-Ni 2P catalyst exhibited H 2 activation and incorporation, in contrast to IW-Ni, indicating that the behavior of the metal phosphide is significantly different from that of the parent metal, and more closely resembles that of noble metal catalysts.« less

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.

Pyrolysis of poly(vinyl chloride) and-electric arc furnacedust mixtures.

PubMed

Al-Harahsheh, Mohammad; Al-Otoom, Awni; Al-Makhadmah, Leema; Hamilton, Ian E; Kingman, Sam; Al-Asheh, Sameer; Hararah, Muhanned

2015-12-15

An investigation into the pyrolysis kinetics of PVC mixed with electric arc furnace dust (EAFD) was performed. Mixtures of both materials with varying PVC ratios (1:1, 1:2, 1:3) were prepared and pyrolyzed in a nitrogen atmosphere under dynamic heating conditions at different heating rates (5, 10, 30 and 50 °C/min). The pyrolysis process proceeded through two main decomposition steps; the first step involved the release of HCl which reacted with the metal oxides present in the dust, subsequently forming metal chlorides and water vapor. Benzene was also found to release as detected by TGA-MS. The remaining hydrocarbons in the polymer backbone decomposed further in the second step releasing further volatile hydrocarbons. Different models were used to fit the kinetic data namely the integral, the Van Krevelen, and Coats and Red fern methods. The presence of EAFD during PVC decomposition resulted in a considerable decrease in the activation energy of the reaction occurring during the first decomposition region. Furthermore, iron oxides were retained in the pyrolysis residue, whilst other valuable metals, including Zn and Pb, were converted to chlorides that are recoverable by leaching in water. It is believed that EAFD can be utilized as an active catalyst to produce energy gases such as propyneas evident from the TGA-MS. Copyright © 2015 Elsevier B.V. All rights reserved.

Oxygen vacancies enabled enhancement of catalytic property of Al reduced anatase TiO2 in the decomposition of high concentration ozone

NASA Astrophysics Data System (ADS)

Ding, Yanhua; Zhang, Xiaolei; Chen, Li; Wang, Xiaorui; Zhang, Na; Liu, Yufeng; Fang, Yongzheng

2017-06-01

The catalytic decomposition of gaseous ozone (O3) is investigated using anatase TiO2 (A-TiO2) and Aluminum-reduced A-TiO2 (ARA-TiO2) at high concentration and high relative humidity (RH) without light illumination. Compared with the pristine A-TiO2, the ARA-TiO2 sample possesses a unique crystalline core-amorphous shell structure. It is proved to be an excellent solar energy ;capture; for solar thermal collectors due to lots of oxygen vacancies. The results indicate that the overall decomposition efficiency of O3 without any light irradiation has been greatly improved from 4.8% on A-TiO2 to 100% on ARA-TiO2 under the RH=100% condition. The ozone conversion over T500/ARA-TiO2 catalyst is still maintained at 95% after a 72 h test under the reaction condition of 18.5 g/m3 ozone initial concentration, and RH=90%. The results can be explained that T500/ARA-TiO2 possesses the largest amorphous contour, the lowest crystallinity, the most surface-active Ti3+/Ti4+couples, and the most oxygen vacancies. This result opens a new door to widen the application of TiO2 in the thermal-catalytic field.

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

Miller, David C.; Kempe, Michael D.; Muller, Matthew T.

We examined the durability of polymeric encapsulation materials using outdoor exposure at the nominal geometric concentration of 500 suns. The results for 36-month cumulative field deployment are presented for materials including: poly(ethylene-co-vinyl acetate), (EVA); polyvinyl butyral (PVB); ionomer; polyethylene/polyoctene copolymer (PO); thermoplastic polyurethane (TPU); poly(dimethylsiloxane) (PDMS); poly(diphenyl dimethyl siloxane) (PDPDMS); and poly(phenyl-methyl siloxane) (PPMS). Measurements of the field conditions including ambient temperature and ultraviolet (UV) dose were recorded at the test site during the experiment. Our measurements for the experiment included optical transmittance (with subsequent analysis of solar-weighted transmittance, UV cut-off wavelength, and yellowness index), mass, visual photography, photoelastic imaging,more » and fluorescence spectroscopy. While the results to date for EVA are presented and discussed, examination here focuses more on the siloxane materials. A specimen recently observed to fail by thermal decomposition is discussed in terms of the implementation of the experiment as well as its fluorescence signature, which was observed to become more pronounced with age. Modulated thermogravimetry (allowing determination of the activation energy of thermal decomposition) was performed on a subset of the siloxanes to quantify the propensity for decomposition at elevated temperatures. Supplemental, Pt-catalyst- and primer-solutions as well as peroxide-cured PDMS specimens were examined to assess the source of the luminescence. Furthermore, our results, including the change in optical transmittance, observed failure modes, and subsequent analyses of the failure modes are described in the conclusions.« less

Oxygen vacancies enabled enhancement of catalytic property of Al reduced anatase TiO{sub 2} in the decomposition of high concentration ozone

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

Ding, Yanhua; Zhang, Xiaolei; Chen, Li

The catalytic decomposition of gaseous ozone (O{sub 3}) is investigated using anatase TiO{sub 2} (A-TiO{sub 2}) and Aluminum-reduced A-TiO{sub 2} (ARA-TiO{sub 2}) at high concentration and high relative humidity (RH) without light illumination. Compared with the pristine A-TiO{sub 2}, the ARA-TiO{sub 2} sample possesses a unique crystalline core-amorphous shell structure. It is proved to be an excellent solar energy “capture” for solar thermal collectors due to lots of oxygen vacancies. The results indicate that the overall decomposition efficiency of O{sub 3} without any light irradiation has been greatly improved from 4.8% on A-TiO{sub 2} to 100% on ARA-TiO{sub 2} undermore » the RH=100% condition. The ozone conversion over T500/ARA-TiO{sub 2} catalyst is still maintained at 95% after a 72 h test under the reaction condition of 18.5 g/m{sup 3} ozone initial concentration, and RH=90%. The results can be explained that T500/ARA-TiO{sub 2} possesses the largest amorphous contour, the lowest crystallinity, the most surface-active Ti{sup 3+}/T{sup i4+}couples, and the most oxygen vacancies. This result opens a new door to widen the application of TiO{sub 2} in the thermal-catalytic field. - Graphical abstract: The anatase-TiO{sub 2} with various oxidation states and oxygen vacancies have been obtained by aluminum-reduction, and the decomposition efficiency of O{sub 3} has been greatly improved from 4.8% to 100% without irradiation under the RH=100% condition. - Highlights: • The decomposition of gaseous ozone over Al reduced TiO2 (ARA-TiO{sub 2}) is firstly reported. • The decomposition efficiency is up to 100% without any light irradiation on ARA-TiO{sub 2} under RH=100% condition. • The ozone conversion is maintained at 95% after a 72 h test, when C{sub inlet}=18.5 g/m{sup 3} and RH=90%.« less

Synthesis of Superparamagnetic Core-Shell Structure Supported Pd Nanocatalysts for Catalytic Nitrite Reduction with Enhanced Activity, No Detection of Undesirable Product of Ammonium, and Easy Magnetic Separation Capability.

PubMed

Sun, Wuzhu; Yang, Weiyi; Xu, Zhengchao; Li, Qi; Shang, Jian Ku

2016-01-27

Superparamagnetic nanocatalysts could minimize both the external and internal mass transport limitations and neutralize OH(-) produced in the reaction more effectively to enhance the catalytic nitrite reduction efficiency with the depressed product selectivity to undesirable ammonium, while possess an easy magnetic separation capability. However, commonly used qusi-monodispersed superparamagnetic Fe3O4 nanosphere is not suitable as catalyst support for nitrite reduction because it could reduce the catalytic reaction efficiency and the product selectivity to N2, and the iron leakage could bring secondary contamination to the treated water. In this study, protective shells of SiO2, polymethylacrylic acid, and carbon were introduced to synthesize Fe3O4@SiO2/Pd, Fe3O4@PMAA/Pd, and Fe3O4@C/Pd catalysts for catalytic nitrite reduction. It was found that SiO2 shell could provide the complete protection to Fe3O4 nanosphere core among these shells. Because of its good dispersion, dense structure, and complete protection to Fe3O4, the Fe3O4@SiO2/Pd catalyst demonstrated the highest catalytic nitrite reduction activity without the detection of NH4(+) produced. Due to this unique structure, the activity of Fe3O4@SiO2/Pd catalysts for nitrite reduction was found to be independent of the Pd nanoparticle size or shape, and their product selectivity was independent of the Pd nanoparticle size, shape, and content. Furthermore, their superparamagnetic nature and high saturation magnetization allowed their easy magnetic separation from treated water, and they also demonstrated a good stability during the subsequent recycling experiment.

40 CFR 267.111 - What general standards must I meet when I stop operating the unit?

Code of Federal Regulations, 2011 CFR

2011-07-01

... to protect human health and the environment, post-closure escape of hazardous waste, hazardous constituents, leachate, contaminated run-off, or hazardous waste decomposition products to the ground or... PROTECTION AGENCY (CONTINUED) SOLID WASTES (CONTINUED) STANDARDS FOR OWNERS AND OPERATORS OF HAZARDOUS WASTE...

40 CFR 267.111 - What general standards must I meet when I stop operating the unit?

Code of Federal Regulations, 2010 CFR

2010-07-01

... to protect human health and the environment, post-closure escape of hazardous waste, hazardous constituents, leachate, contaminated run-off, or hazardous waste decomposition products to the ground or... PROTECTION AGENCY (CONTINUED) SOLID WASTES (CONTINUED) STANDARDS FOR OWNERS AND OPERATORS OF HAZARDOUS WASTE...

Active sites of ligand-protected Au{sub 25} nanoparticle catalysts for CO{sub 2} electroreduction to CO

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

Alfonso, Dominic R., E-mail: alfonso@netl.doe.gov; Kauffman, Douglas; Matranga, Christopher

2016-05-14

Recent experimental studies have reported the electrochemical reduction of carbon dioxide (CO{sub 2}) into CO at atomically precise negatively charged Au{sub 25}{sup −} nanoclusters. The studies showed CO{sub 2} conversion at remarkably low overpotentials, but the exact mechanisms and nature of the active sites remain unclear. We used first-principles density functional theory and continuum solvation models to examine the role of the cluster during electrochemical CO{sub 2} reduction and analyze the free energies of proposed intermediate species. Contrary to previous assumptions, our results show that the fully ligand protected cluster is not an active CO{sub 2} reduction catalyst because formationmore » of the crucial carboxyl intermediate required very high electrochemical potentials. Instead, our calculations suggest that the reduction process likely occurs on a dethiolated gold site, and adsorbed carboxyl intermediate formation was significantly stabilized at dethiolated gold sites. These findings point to the crucial role of exposed metal sites during electrochemical CO{sub 2} reduction at gold nanocluster catalysts.« less

Catalysts for selective hydrogenation of furfural derived from the double complex salt [Pd(NH 3 ) 4 ](ReO 4 ) 2 on γ-Al 2 O 3

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

Thompson, Simon T.; Lamb, H. Henry

The double complex salt [Pd(NH3)4](ReO4)2 was employed as precursor of supported bimetallic catalysts for selective hydrogenation of furfural. Direct reduction of [Pd(NH3)4](ReO4)2 on γ-Al2O3 in flowing H2 at 400 °C yields bimetallic nanoparticles 1–2 nm in size that exhibit significant interaction between the metals, as evidenced by temperature-programmed hydride decomposition (complete suppression of β-PdHx formation), extended X-ray absorption fine structure spectroscopy at the Pd K and Re LIII edges (PdRe distance = 2.72 Å), and scanning transmission electron microscopy with energy dispersive X-ray analysis. In contrast, calcination of [Pd(NH3)4](ReO4)2 on γ-Al2O3 at 350 °C in air and subsequent reduction inmore » H2 at 400 °C results in metal segregation and formation of large (>50 nm) supported Pd particles; Re species cover the Pd particles and γ-Al2O3 support. A PdRe 1:2 catalyst prepared by sequential impregnation and calcination using HReO4 and [Pd(NH3)4](NO3)2 has a similar morphology. The catalyst derived by direct reduction of [Pd(NH3)4](ReO4)2 on γ-Al2O3 exhibits remarkably high activity for selective hydrogenation of furfural to furfuryl alcohol (FAL) at 150 °C and 1 atm. Suppression of H2 chemisorption via elimination of Pd threefold sites, as evidenced by CO diffuse-reflectance infrared Fourier transform spectroscopy, correlates with increased FAL selectivity.« less

Influence of oxalate ligand functionalization on Co/ZSM-5 activity in Fischer Tropsch synthesis and hydrodeoxygenation of oleic acid into hydrocarbon fuels.

PubMed

Ayodele, Olumide Bolarinwa

2017-08-30

Achieving high degree of active metal dispersions at the highest possible metal loading and high reducibility of the metal remains a challenge in Fischer Tropsch synthesis (FTS) as well as in hydrogeoxygenation (HDO).This study therefore reports the influence of oxalic acid (OxA) functionalization on the metal dispersion, reducibility and activity of Co supported ZSM-5 catalyst in FTS and HDO of oleic acid into paraffin biofuel. The Brunauer-Emmett-Teller (BET) results showed that cobalt oxalate supported ZSM-5 catalyst (CoOx/ZSM-5) synthesized from the incorporation of freshly prepared cobalt oxalate complex into ZSM-5 displayed increase in surface area, pore volume and average pore size while the nonfunctionalized cobalt supported on ZSM-5 (Co/ZSM-5) catalyst showed reduction in those properties. Furthermore, both XRD and XPS confirmed the presence of Co° formed from the decomposition of CoOx during calcination of CoOx/ZSM-5 under inert atmosphere. The HRTEM showed that Co species average particle sizes were smaller in CoOx/ZSM-5 than in Co/ZSM-5, and in addition, CoOx/ZSM-5 shows a clear higher degree of active metal dispersion. The FTS result showed that at CO conversion over Co/ZSM-5 and CoOx/ZSM-5 catalysts were 74.28% and 94.23% and their selectivity to C 5+ HC production were 63.15% and 75.4%, respectively at 4 h TOS. The HDO result also showed that the CoOx/ZSM-5 has higher OA conversion of 92% compared to 59% over Co/ZSM-5. In addition CoOx/ZSM-5 showed higher HDO and isomerization activities compared to Co/ZSM-5.

Recovery of iron oxides from acid mine drainage and their application as adsorbent or catalyst.

PubMed

Flores, Rubia Gomes; Andersen, Silvia Layara Floriani; Maia, Leonardo Kenji Komay; José, Humberto Jorge; Moreira, Regina de Fatima Peralta Muniz

2012-11-30

Iron oxide particles recovered from acid mine drainage represent a potential low-cost feedstock to replace reagent-grade chemicals in the production of goethite, ferrihydrite or magnetite with relatively high purity. Also, the properties of iron oxides recovered from acid mine drainage mean that they can be exploited as catalysts and/or adsorbents to remove azo dyes from aqueous solutions. The main aim of this study was to recover iron oxides with relatively high purity from acid mine drainage to act as a catalyst in the oxidation of dye through a Fenton-like mechanism or as an adsorbent to remove dyes from an aqueous solution. Iron oxides (goethite) were recovered from acid mine drainage through a sequential precipitation method. Thermal treatment at temperatures higher than 300 °C produces hematite through a decrease in the BET area and an increase in the point of zero charge. In the absence of hydrogen peroxide, the solids adsorbed the textile dye Procion Red H-E7B according to the Langmuir model, and the maximum amount adsorbed decreased as the temperature of the thermal treatment increased. The decomposition kinetics of hydrogen peroxide is dependent on the H(2)O(2) concentration and iron oxides dosage, but the second-order rate constant normalized to the BET surface area is similar to that for different iron oxides tested in this and others studies. These results indicate that acid mine drainage could be used as a source material for the production of iron oxide catalysts/adsorbents, with comparable quality to those produced using analytical-grade reagents. Copyright © 2012 Elsevier Ltd. All rights reserved.

Catalytic processing of lactic acid over Pt/Nb(2)O(5).

PubMed

Serrano-Ruiz, Juan Carlos; Dumesic, James A

2009-01-01

Dilute aqueous solutions of lactic acid (30 %wt.) can be catalytically processed at 573 K and 57 bar over a low-metal-content Pt(0.1 %)/Nb(2)O(5) catalyst in a spontaneously separating organic phase rich in valuable products such as C(4)-C(7) ketones. An increase in the lactic acid concentration to 60 wt % allows conversion of approximately 50 % of the carbon feed in this organic layer, while maintaining good stability of the catalyst. Experiments at low conversion showed that lactic acid reacts first over Pt(0.1 %)/Nb(2)O(5) to produce acetaldehyde and propanoic acid (along with CO and CO(2) in the gas phase). These compounds (less oxygenated than lactic acid but still reactive) are the key intermediates in the overall process, and they react differently depending on the nature of the catalyst support. In particular, reaction kinetics studies with propanoic acid as feed showed that Pt(0.1 %)/Nb(2)O(5) favored the formation of pentanones by ketonization reactions, whereas a monofunctional Pt(0.1 %)/carbon catalyst produced ethane and CO(x) by decomposition reactions. In the same manner, acetaldehyde was preferentially hydrogenated to ethanol over Pt(0.1 %)/carbon, whereas the presence of niobia allowed this intermediate to react (by successive aldol condensations) to form C(4)-C(7) condensation products stored in the organic phase. Finally, reaction pathways are proposed to explain the catalytic processing of lactic acid over bifunctional Pt(0.1 %)/Nb(2)O(5). In this scheme, metal sites catalyze hydrogenation reactions and niobia promotes C--C coupling processes (ketonization and aldol condensation), in contrast to C--C cleavage reactions which take place preferentially over Pt(0.1 %)/carbon and lead to loss of carbon in the gas effluent as CO, CO(2), and methane.

Heterogeneous Ag-TiO2-SiO2 composite materials as novel catalytic systems for selective epoxidation of cyclohexene by H2O2

PubMed Central

Wang, Xin; Xue, Jianyue; Wang, Xinyun; Liu, Xiaoheng

2017-01-01

TiO2-SiO2 composites were synthesized using cetyl trimethyl ammonium bromide (CTAB) as the structure directing template. Self-assembly hexadecyltrimethyl- ammonium bromide TiO2-SiO2/(CTAB) were soaked into silver nitrate (AgNO3) aqueous solution. The Ag-TiO2-SiO2(Ag-TS) composite were prepared via a precipitation of AgBr in soaking process and its decomposition at calcination stage. Structural characterization of the materials was carried out by various techniques including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 adsorption-desorption and ultraviolet visible spectroscopy (UV-Vis). Characterization results revealed that Ag particles were incorporated into hierarchical TiO2-SiO2 without significantly affecting the structures of the supports. Further heating-treatment at 723 K was more favorable for enhancing the stability of the Ag-TS composite. The cyclohexene oxide was the major product in the epoxidation using H2O2 as the oxidant over the Ag-TS catalysts. Besides, the optimum catalytic activity and stability of Ag-TS catalysts were obtained under operational conditions of calcined at 723 K for 2 h, reaction time of 120 min, reaction temperature of 353 K, catalyst amount of 80 mg, aqueous H2O2 (30 wt.%) as oxidant and chloroform as solvent. High catalytic activity with conversion rate up to 99.2% of cyclohexene oxide could be obtainable in water-bathing. The catalyst was found to be stable and could be reused three times without significant loss of catalytic activity under the optimized reaction conditions. PMID:28493879

The Harvard Catalyst Common Reciprocal IRB Reliance Agreement: An Innovative Approach to Multisite IRB Review and Oversight

PubMed Central

Winkler, Sabune J.; Witte, Elizabeth

2014-01-01

Abstract Reduction of duplicative Institutional Review Board (IRB) review for multiinstitutional studies is a desirable goal to improve IRB efficiency while enhancing human subject protections. Here we describe the Harvard Catalyst Master Reciprocal Common IRB Reliance Agreement (MRA), a system that provides a legal framework for IRB reliance, with the potential to streamline IRB review processes and reduce administrative burden and barriers to collaborative, multiinstitutional research. The MRA respects the legal autonomy of the signatory institutions while offering a pathway to eliminate duplicative IRB review when appropriate. The Harvard Catalyst MRA provides a robust and flexible model for reciprocal reliance that is both adaptable and scalable. PMID:25196592

The Harvard Catalyst Common Reciprocal IRB Reliance Agreement: an innovative approach to multisite IRB review and oversight.

PubMed

Winkler, Sabune J; Witte, Elizabeth; Bierer, Barbara E

2015-02-01

Reduction of duplicative Institutional Review Board (IRB) review for multiinstitutional studies is a desirable goal to improve IRB efficiency while enhancing human subject protections. Here we describe the Harvard Catalyst Master Reciprocal Common IRB Reliance Agreement (MRA), a system that provides a legal framework for IRB reliance, with the potential to streamline IRB review processes and reduce administrative burden and barriers to collaborative, multiinstitutional research. The MRA respects the legal autonomy of the signatory institutions while offering a pathway to eliminate duplicative IRB review when appropriate. The Harvard Catalyst MRA provides a robust and flexible model for reciprocal reliance that is both adaptable and scalable. © 2014 Wiley Periodicals, Inc.

Mössbauer study of Cu1-xZnxFe2O4 catalytic materials

NASA Astrophysics Data System (ADS)

Koleva, K.; Velinov, N.; Tsoncheva, T.; Mitov, I.

2014-04-01

Copper zinc ferrites (Cu1-xZnxFe2O4) with different composition (x = 1; 0.2; 0.5; 0.8) were prepared by conventional thermal method. Formation of well crystallized ferrite phase with cubic structure and crystallites size of about 19.08-24.39 nm was observed by Powder X-ray diffraction and Mössbauer spectroscopy. The ferrite materials were tested as catalysts in methanol decomposition to CO and H2. A strong dependence of the catalytic behaviour of Cu1-xZnxFe2O4 ferrites of their composition and the phase transformations which occurred under the reaction medium was established.

A Mild, Ferrocene-Catalyzed C–H Imidation of (Hetero)Arenes

PubMed Central

2015-01-01

A simple method for direct C–H imidation is reported using a new perester-based self-immolating reagent and a base-metal catalyst. The succinimide products obtained can be easily deprotected in situ (if desired) to reveal the corresponding anilines directly. The scope of the reaction is broad, the conditions are extremely mild, and the reaction is tolerant of oxidizable and acid-labile functionality, multiple heteroatoms, and aryl iodides. Mechanistic studies indicate that ferrocene (Cp2Fe) plays the role of an electron shuttle in the decomposition of the perester reagent, delivering a succinimidyl radical ready to add to an aromatic system. PMID:24654983

Platinum-paper micromotors: an urchin-like nanohybrid catalyst for green monopropellant bubble-thrusters.

PubMed

Claussen, Jonathan C; Daniele, Michael A; Geder, Jason; Pruessner, Marius; Mäkinen, Antti J; Melde, Brian J; Twigg, Mark; Verbarg, Jasenka M; Medintz, Igor L

2014-10-22

Platinum nanourchins supported on microfibrilated cellulose films (MFC) were fabricated and evaluated as hydrogen peroxide catalysts for small-scale, autonomous underwater vehicle (AUV) propulsion systems. The catalytic substrate was synthesized through the reduction of chloroplatinic acid to create a thick film of Pt coral-like microstructures coated with Pt urchin-like nanowires that are arrayed in three dimensions on a two-dimensional MFC film. This organic/inorganic nanohybrid displays high catalytic ability (reduced activation energy of 50-63% over conventional materials and 13-19% for similar Pt nanoparticle-based structures) during hydrogen peroxide (H2O2) decomposition as well as sufficient propulsive thrust (>0.5 N) from reagent grade H2O2 (30% w/w) fuel within a small underwater reaction vessel. The results demonstrate that these layered nanohybrid sheets are robust and catalytically effective for green, H2O2-based micro-AUV propulsion where the storage and handling of highly explosive, toxic fuels are prohibitive due to size-requirements, cost limitations, and close person-to-machine contact.

A facile synthesis for cauliflower like CeO2 catalysts from Ce-BTC precursor and their catalytic performance for CO oxidation

NASA Astrophysics Data System (ADS)

Zhang, Xiaodong; Hou, Fulin; Yang, Yang; Wang, Yuxin; Liu, Ning; Chen, Dan; Yang, Yiqiong

2017-11-01

The paper presents a novel and facile method for preparing cauliflowerlike CeO2 through direct decomposition of cerium based metal-organic framework (MOF) Ce-BTC (BTC = 1,3,5-benzenetricarboxylic acid) straw in air. Several analytical tools such as Scanning electron microscopy (SEM), X-ray diffraction (XRD), Thermogravimetric (TG), N2 adsorption-desorption, Temperature programmed reduction (TPR), Raman, X-ray photoelectron spectroscopic (XPS) and Photoluminescence (PL) have been used to characterize Ce-BTC and CeO2. The Ce-BTC calcined at 500 °C (CeO2-500) maintains the morphology of its template ;Ce-BTC; and forms a special cauliflower-like structure. XRD patterns showed that the catalyst has a perfect CeO2 crystal structure and has a smaller particle size. The prepared CeO2 cauliflowers exhibit excellent catalytic activities, long-term stability, and cycling stability for CO oxidation. The improved catalytic activities could be attributed to porous nanorods of CeO2 cauliflowers, which provide more active sites and oxygen vacancy for CO oxidation.

Selective Chemical Conversion of Sugars in Aqueous Solutions without Alkali to Lactic Acid Over a Zn-Sn-Beta Lewis Acid-Base Catalyst

NASA Astrophysics Data System (ADS)

Dong, Wenjie; Shen, Zheng; Peng, Boyu; Gu, Minyan; Zhou, Xuefei; Xiang, Bo; Zhang, Yalei

2016-05-01

Lactic acid is an important platform molecule in the synthesis of a wide range of chemicals. However, in aqueous solutions without alkali, its efficient preparation via the direct catalysis of sugars is hindered by a side dehydration reaction to 5-hydroxymethylfurfural due to Brønsted acid, which originates from organic acids. Herein, we report that a previously unappreciated combination of common two metal mixed catalyst (Zn-Sn-Beta) prepared via solid-state ion exchange synergistically promoted this reaction. In water without a base, a conversion exceeding 99% for sucrose with a lactic acid yield of 54% was achieved within 2 hours at 190 °C under ambient air pressure. Studies of the acid and base properties of the Zn-Sn-Beta zeolite suggest that the introduction of Zn into the Sn-Beta zeolite sequentially enhanced both the Lewis acid and base sites, and the base sites inhibited a series of side reactions related to fructose dehydration to 5-hydroxymethylfurfural and its subsequent decomposition.

Selective Chemical Conversion of Sugars in Aqueous Solutions without Alkali to Lactic Acid Over a Zn-Sn-Beta Lewis Acid-Base Catalyst

PubMed Central

Dong, Wenjie; Shen, Zheng; Peng, Boyu; Gu, Minyan; Zhou, Xuefei; Xiang, Bo; Zhang, Yalei

2016-01-01

Lactic acid is an important platform molecule in the synthesis of a wide range of chemicals. However, in aqueous solutions without alkali, its efficient preparation via the direct catalysis of sugars is hindered by a side dehydration reaction to 5-hydroxymethylfurfural due to Brønsted acid, which originates from organic acids. Herein, we report that a previously unappreciated combination of common two metal mixed catalyst (Zn-Sn-Beta) prepared via solid-state ion exchange synergistically promoted this reaction. In water without a base, a conversion exceeding 99% for sucrose with a lactic acid yield of 54% was achieved within 2 hours at 190 °C under ambient air pressure. Studies of the acid and base properties of the Zn-Sn-Beta zeolite suggest that the introduction of Zn into the Sn-Beta zeolite sequentially enhanced both the Lewis acid and base sites, and the base sites inhibited a series of side reactions related to fructose dehydration to 5-hydroxymethylfurfural and its subsequent decomposition. PMID:27222322

Single Pd Atoms on θ-Al2O3 (010) Surface do not Catalyze NO Oxidation.

PubMed

Narula, Chaitanya K; Allard, Lawrence F; Moses-DeBusk, Melanie; Stocks, G Malcom; Wu, Zili

2017-04-03

New convenient wet-chemistry synthetic routes have made it possible to explore catalytic activities of a variety of single supported atoms, however, the single supported atoms on inert substrates (e.g. alumina) are limited to adatoms and cations of Pt, Pd, and Ru. Previously, we have found that single supported Pt atoms are remarkable NO oxidation catalysts. In contrast, we report that Pd single atoms are completely inactive for NO oxidation. The diffuse reflectance infra-red spectroscopy (DRIFTS) results show the absence of nitrate formation on catalyst. To explain these results, we explored modified Langmuir-Hinshelwood type pathways that have been proposed for oxidation reactions on single supported atom. In the first pathway, we find that there is energy barrier for the release of NO 2 which prevent NO oxidation. In the second pathway, our results show that there is no driving force for the formation of O=N-O-O intermediate or nitrate on single supported Pd atoms. The decomposition of nitrate, if formed, is an endothermic event.

Unzipping of multi-wall carbon nanotubes with different diameter distributions: Effect on few-layer graphene oxide obtention

NASA Astrophysics Data System (ADS)

Torres, D.; Pinilla, J. L.; Suelves, I.

2017-12-01

Few-layer graphene oxide (FLGO) was obtained by chemical unzipping of multi-wall carbon nanotubes (MWCNT) of different diameter distributions. MWCNT were synthesized by catalytic decomposition of methane using Fe-Mo/MgO catalysts. The variation in the Fe/Mo ratio (1, 2 and 5) was very influential in MWCNT diameter distribution and type of MWCNT obtained, including textural, chemical, structural and morphological characteristics. MWCNT diameter distribution and surface defects content had a profound impact on the characteristics of the resulting FLGO. Thus, MWCNT obtained with the catalyst with a Fe/Mo: 5 and presenting a narrow diameter distribution centered at 8.6 ± 3.3 nm led to FLGO maintaining non-oxidized graphite stacking (according to XRD analysis), lower specific surface area and higher thermostability as compared to FLGO obtained from MWCNT showing wider diameter distributions. The presence of more oxygen-containing functionalities and structural defects in large diameter nanotubes promotes the intercalation of species towards the inner layers of the nanotube, resulting in an enhanced MWCNT oxidation and opening into FLGO, what improves both micro- and mesoporosity.