Sorption of Molecular Oxygen by Metal-Ion Exchanger Nanocomposites

NASA Astrophysics Data System (ADS)

Krysanov, V. A.; Plotnikova, N. V.; Kravchenko, T. A.

2018-03-01

Kinetic features are studied of the chemisorption and reduction of molecular oxygen from water by metal-ion exchanger nanocomposites that differ in the nature of the dispersed metal and state of oxidation. In the Pd < Ag < Cu series, the increasing chemical activity of metal nanoparticles raises the degree of oxygen sorption due to its chemisorption and subsequent reduction, while the role of the molecular chemisorption stage increases in the Cu < Ag < Pd series. Metal particles or their oxides are shown to act as adsorption sites on the surface and in the pores of the ion-exchanger matrix; the equilibrium sorption coefficient for oxygen dissolved in water ranges from 20 to 50, depending on the nature and oxidation state of the metal component.

Auger analysis of oxygen and sulfur interactions with various metals and the effect of sliding on these interactions

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1973-01-01

Various gases were adsorbed to copper, aluminum, and chromium surfaces. The gases included oxygen, hydrogen sulfide, methyl mercaptan, and sulfur dioxide. Chemisorption was conducted on static surfaces and during dynamic friction experiments. An Auger cyclindrical mirror analyzer was used to monitor surface films. The sulfur containing gases adsorbed readily to all surfaces. Exposures of as little as 0.000001 (torr)(sec) (1 langmuir) were sufficient to reduce friction. Sliding contact did not affect chemisorption of copper or aluminum but did affect chemisorption to chromium surfaces. Oxygen removed sulfur films from all surfaces at room temperature (23 C). Gaseous exposures were from 0.000001 to 0.01 (torr)(sec) (1 to 10,000 langmuirs).

General Overview: Atomistics of Environmentally-Induced Fracture.

DTIC Science & Technology

1981-05-01

might be affected, recent field ion microscopy by Clum 35 suggests that hydrogen may reduce the work required to nucleate dislocations at the surface...and, hence, induces plasticity. Lynch 3 6 has proposed similar behavior based on the view that chemisorption facilitates dislocation nucleation at...that chemisorption may facilitate the nucleation of dislocations at crack tips, although the mechanism by which this might occur is unclear. The basis

Use of X-ray absorption near edge structure (XANES) to identify physisorption and chemisorption of phosphate onto ferrihydrite-modified diatomite.

PubMed

Xiong, Wenhui; Peng, Jian; Hu, Yongfeng

2012-02-15

This paper presents a novel technique integrating bulk-sensitive and surface-sensitive XANES methods to distinguish between physisorption and chemisorption for phosphate adsorption onto ferrihydrite-modified diatomite (FHMD). XANES P K-edge, L-edge, and Fe M-edge spectra were obtained for reference samples (K(2)HPO(4) and FePO(4)·2H(2)O) and test samples (phosphate adsorbed onto FHMD (FHMD-Ps) and Si-containing ferrihydrite (FHYD-Ps)). A resolvable pre-edge peak in the P K-edge spectra of FHMD-Ps and FHYD-Ps provided direct evidence for the formation of P-O-Fe(III) coordination and the occurrence of chemisorption. The resemblance between the P L-edge spectra of K(2)HPO(4) and FHMD-Ps and the marked difference between the spectra of FHMD-Ps and FePO(4)·2H(2)O indicated the intact existence of the adsorbate and the adsorbent. The similarity between Fe M-edge spectra of FHMD and FHMD-Ps and the difference between the spectra of FHMD-Ps and FePO(4)·2H(2)O confirmed the findings from P L-edge analyses. Therefore, chemisorption and physisorption coexisted during phosphate adsorption onto FHMD. Phosphate chemisorption occurred in the deeper zone of FHMD (from 50 nm to 5 μm); whereas physisorption occurred in the zone of FHMD shallower than 50 nm since the probing depth of XANES P K-edge method is 5 μm and that of P L-edge and Fe M-edge methods is 50 nm. Copyright © 2011 Elsevier Inc. All rights reserved.

Trends in hydrogen chemisorption on transition metals

NASA Astrophysics Data System (ADS)

Muscat, J. P.

1981-10-01

A systematic study of H adsorption on the close-packed surfaces of the transition metals in the 3d and 4d series is presented. The effect of the TM d band on the chemisorption bond is investigated, by embedding a cluster of TM muffin tins at the surface of an effective jellium-like medium. It is found that the broad and incomplete H/jellium resonance is narrowed, shifted down and made to contain more electrons as a result of hybridization with the TM d states. These effects are larger in the case of the 4d metals, thus indicating a greater participation in the chemisorption bond of the d electrons for these metals than for the 3d metals. Calculation of one-electron energy differences on going from the H on jellium system to that of H on the TM cluster are presented. Trends for the one-electron energy differences are compared to trends in experimental chemisorption energy. H adsorption in the three-fold hollow site with no secondlayer TM atom below the H site is favoured for the hcp metals, while no discernible preference between the two hollow sites is recorded for the fcc metals, with the exception of Rh where the site with no second-layer TM atom below is preferred.

The influence of metal-support interactions on the accurate determination of Ru dispersion for Ru/TiO{sub 2}

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

Komaya, Takashi; Bell, A.T.; Weng-Sieh, Zara

1994-09-01

Titania-supported Ru catalysts have been characterized by TEM, {sup 1}H NMR, and H{sub 2} chemisorption to determine the metal particle size, the fraction of the metal surface available for H{sub 2} chemisorption, and the H{sub 2} adsorption capacity of the catalyst, as functions of the reduction temperature. TEM micrographs show that as the reduction temperature rises from 573 to 773K, the average particle size of Ru remains the same but the surface of the particles is covered to an increasing extent by an amorphous layer of titania. Quantitative estimates of the fraction of the Ru particle surface available for H{submore » 2} chemisorption were obtained by {sup 1}H NMR. The NMR spectra also show that a fraction of the adsorbed H{sub 2} spills over onto the support and that as a consequence measurements of total H{sub 2} chemisorption overestimate the number of Ru sites available for H{sub 2} adsorption. The implications of these results for the correct calculation of Ru dispersion and the determination of turnover frequencies for reactions carried out over Ru/TiO{sub 2} are discussed. 16 refs., 5 figs., 1 tab.« less

Chemisorption of 1,1-dichloroethene on the Si(1 1 1)-7 × 7 surface

NASA Astrophysics Data System (ADS)

Andersen, T. H.; Zahl, M. G.; Svenum, I.-H.; Børve, K. J.; Borg, A.; Sæthre, L. J.

2007-12-01

Chemisorption of 1,1-dichloroethene (Cl 2C dbnd CH 2) to a Si(1 1 1)-7 × 7 surface was studied by means of X-ray photoelectron spectroscopy using synchrotron radiation, recording chlorine 2p and carbon 1s spectra. For carbon 1s, spectral assignment of the chemisorbed species is based on quantum chemical calculations of chemical shifts in model compounds. The results confirm the identity of covalently bonded 1-chlorovinyl (-CCl dbnd CH 2) and vinylidene ( lbond2 C dbnd CH 2) adspecies. Upon chemisorption at room temperature it was found that about one-third of the molecules break one C-Cl bond while about two-thirds of the adsorbates break two C-Cl bonds. We do not, however, find evidence for isomerization of lbond2 C dbnd CH 2 to di-bonded vinylene (-CH dbnd CH-).

Mode Specific Electronic Friction in Dissociative Chemisorption on Metal Surfaces: H2 on Ag(111)

NASA Astrophysics Data System (ADS)

Maurer, Reinhard J.; Jiang, Bin; Guo, Hua; Tully, John C.

2017-06-01

Electronic friction and the ensuing nonadiabatic energy loss play an important role in chemical reaction dynamics at metal surfaces. Using molecular dynamics with electronic friction evaluated on the fly from density functional theory, we find strong mode dependence and a dominance of nonadiabatic energy loss along the bond stretch coordinate for scattering and dissociative chemisorption of H2 on the Ag(111) surface. Exemplary trajectories with varying initial conditions indicate that this mode specificity translates into modulated energy loss during a dissociative chemisorption event. Despite minor nonadiabatic energy loss of about 5%, the directionality of friction forces induces dynamical steering that affects individual reaction outcomes, specifically for low-incidence energies and vibrationally excited molecules. Mode-specific friction induces enhanced loss of rovibrational rather than translational energy and will be most visible in its effect on final energy distributions in molecular scattering experiments.

Sorption cryogenic refrigeration - Status and future

NASA Technical Reports Server (NTRS)

Jones, Jack A.

1988-01-01

The operation principles of sorption cryogenic refrigeration are discussed. Sorption refrigerators have virtually no wear-related moving parts, have negligible vibration, and offer extremely long life (at least ten years), making it possible to obtain efficient, long life and low vibration cooling to as low as 7 K for cryogenic sensors. The physisorption and chemisorption systems recommended for various cooling ranges down to 7 K are described in detail. For long-life cooling at 4-5 K temperatures, a hybrid chemisorption-mechanical refrigeration system is recommended.

First-principles quantum dynamical theory for the dissociative chemisorption of H2O on rigid Cu(111)

PubMed Central

Zhang, Zhaojun; Liu, Tianhui; Fu, Bina; Yang, Xueming; Zhang, Dong H.

2016-01-01

Despite significant progress made in the past decades, it remains extremely challenging to investigate the dissociative chemisorption dynamics of molecular species on surfaces at a full-dimensional quantum mechanical level, in particular for polyatomic-surface reactions. Here we report, to the best of our knowledge, the first full-dimensional quantum dynamics study for the dissociative chemisorption of H2O on rigid Cu(111) with all the nine molecular degrees of freedom fully coupled, based on an accurate full-dimensional potential energy surface. The full-dimensional quantum mechanical reactivity provides the dynamics features with the highest accuracy, revealing that the excitations in vibrational modes of H2O are more efficacious than increasing the translational energy in promoting the reaction. The enhancement of the excitation in asymmetric stretch is the largest, but that of symmetric stretch becomes comparable at very low energies. The full-dimensional characterization also allows the investigation of the validity of previous reduced-dimensional and approximate dynamical models. PMID:27283908

A flow-pulse adsorption-microcalorimetry system for studies of adsorption processes on powder catalysts

NASA Astrophysics Data System (ADS)

You, Rui; Li, Zhaorui; Zeng, Hongyu; Huang, Weixin

2018-06-01

A pulse chemisorption system combining a Tian-Calvet microcalorimeter (Setaram Sensys EVO 600) and an automated chemisorption apparatus (Micromeritics Autochem II 2920) was established to accurately measure differential adsorption heats of gas molecules' chemisorption on solid surfaces in a flow-pulse mode. Owing to high sensitivity and high degree of automation in a wide range of temperatures from -100 to 600 °C, this coupled system can present adsorption heats as a function of adsorption temperature and adsorbate coverage. The functions of this system were demonstrated by successful measurements of CO adsorption heats on Pd surfaces at various temperatures and also at different CO coverages by varying the CO concentration in the pulse dose. Key parameters, including adsorption amounts, integral adsorption heats, and differential adsorption heats of CO adsorption on a Pd/CeO2 catalyst, were acquired. Our adsorption-microcalorimetry system provides a powerful technique for the investigation of adsorption processes on powder catalysts.

Oxygen chemisorption compressor study for cryogenic J-T refrigeration

NASA Technical Reports Server (NTRS)

Jones, Jack A.; Blue, Gary D.

1987-01-01

Over twenty potentially reversible heat-powered oxide reactions have been studied and/or tested to determine their potential use as thermochemical oxygen compressors for cryogenic J-T LO2 refrigerators. One gas-solid compound family, Pr(1-n)Ce(n)O(x), proved to be completely reversible with fast kinetics for all pressure ranges tested below 650 C. With a heat-powered charcoal/methane physical adsorption upper stage and a Pr(1-n)Ce(n)O(x) chemisorption lower stage, temperatures should be attainable in the 55-80 K range for less power and over five times less weight than for charcoal/nitrogen sorption refrigeration systems. Total system power requirements with a hydride chemisorption lower stage (10 K to 7 K minimum) are about three times less than any mechanical refrigerator, and spacecraft refrigeration weights are about twenty times less. Due to the lack of wear-related moving parts in sorption refrigerators, life expectancy is at least ten years, and there essentially no vibration.

LCGTO-Xα model cluster study for the chemisorption of CO on twofold sites of Ni surfaces

NASA Astrophysics Data System (ADS)

Jörg, H.; Rösch, N.

The cluster Ni 2CO is studied as a simplified model for the chemisorption of CO on twofold bridging sites of transition metal surfaces. Using the LCGTO-Xα method we have calculated the potential energy surface for the totally symmetric stretching motion keeping the Ni-Ni distance fixed at the bulk value. The minimum energy is found at a Ni-C distance of 1.72 Å and a C-O bond length of 1.19 Å. The vibrational frequency for the CO bond (1850 cm -1) shows reasonable agreement with EELS data (1810, 1870 cm -1), whereas the (Ni 2)-C frequency of 495 cm -1 is remarkably higher than the experimental values (380, 400 cm -1) indicating an overestimation of the chemisorption bond strength in this simple cluster model. The bonding between CO and Ni is analyzed using orbital correlations, ionization energies and Mulliken population analysis. Important bonding contributions from π backdonation are identified while the a 1 orbital manifold exhibits strong antibonding effects.

LCGTO-Xα model cluster study for the chemisorption of CO on twofold sites of Ni surfaces

NASA Astrophysics Data System (ADS)

Jörg, H.; Rösch, N.

1985-11-01

The cluster Ni 2CO is studied as a simplified model for the chemisorption of CO on twofold bridging sites of transition metal surfaces. Using the LCGTO-Xα method we have calculated the potential energy surface for the totally symmetric stretching motion keeping the NiNi distance fixed at the bulk value. The minimum energy is found at a NiC distance of 1.72 Å and a CO bond length of 1.19 Å. The vibrational frequency for the CO bond (1850 cm -1) shows reasonable agreement with EELS data (1810, 1870 cm -1), whereas the (Ni 2)C frequency of 495 cm -1 is remarkably higher than the experimental values (380, 400 cm -1) indicating an overestimation of the chemisorption bond strength in this simple cluster model. The bonding between CO and Ni is analyzed using orbital correlations, ionization energies and Mulliken population analysis. Important bonding contributions from π backdonation are identified while the a 1orbital manifold exhibits strong antibonding effects.

Chemisorption of iodine-125 to gold nanoparticles allows for real-time quantitation and potential use in nanomedicine.

PubMed

Walsh, Adrian A

2017-01-01

Gold nanoparticles have been available for many years as a research tool in the life sciences due to their electron density and optical properties. New applications are continually being developed, particularly in nanomedicine. One drawback is the need for an easy, real-time quantitation method for gold nanoparticles so that the effects observed in in vitro cell toxicity assays and cell uptake studies can be interpreted quantitatively in terms of nanoparticle loading. One potential method of quantifying gold nanoparticles in real time is by chemisorption of iodine-125, a gamma emitter, to the nanoparticles. This paper revisits the labelling of gold nanoparticles with iodine-125, first described 30 years ago and never fully exploited since. We explore the chemical properties and usefulness in quantifying bio-functionalised gold nanoparticle binding in a quick and simple manner. The gold particles were labelled specifically and quantitatively simply by mixing the two items. The nature of the labelling is chemisorption and is robust, remaining bound over several weeks in a variety of cell culture media. Chemisorption was confirmed as potassium iodide can remove the label whereas sodium chloride and many other buffers had no effect. Particles precoated in polymers or proteins can be labelled just as efficiently allowing for post-labelling experiments in situ rather than using radioactive gold atoms in the production process. We also demonstrate that interparticle exchange of I-125 between different size particles does not appear to take place confirming the affinity of the binding.

CO Oxidation and Subsequent CO 2 Chemisorption on Alkaline Zirconates: Li 2 ZrO 3 and Na 2 ZrO 3

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

Alcántar-Vázquez, Brenda; Duan, Yuhua; Pfeiffer, Heriberto

Here, two different alkaline zirconates (Li 2ZrO 3 and Na 2ZrO 3) were studied as possible bifunctional catalytic-captor materials for CO oxidation and the subsequent CO 2 chemisorption process. Initially, CO oxidation reactions were analyzed in a catalytic reactor coupled to a gas chromatograph, using Li 2ZrO 3 and Na 2ZrO 3, under different O 2 partial flows. We found results clearly showed that Na 2ZrO 3 possesses much better catalytic properties than Li 2ZrO 3. After the CO-O 2 oxidation catalytic analysis, CO2 chemisorption process was analyzed by thermogravimetric analysis, only for the Na 2ZrO 3 ceramic. The resultsmore » confirmed that Na 2ZrO 3 is able to work as a bifunctional material (CO oxidation and subsequent CO 2 chemisorption), although the kinetic CO 2 capture process was not the best one under the physicochemical condition used in this case. For Na 2ZrO 3, the best CO conversions were found between 445 and 580 °C (100%), while Li 2ZrO 3 only showed a 35% of efficiency between 460 and 503 °C. However, in the Na 2ZrO 3 case, at temperatures higher than 580 °C its catalytic activity gradually decreases as a result of CO 2 capture process. Finally, all these experiments were compared and supported with theoretical thermodynamic data.« less

CO Oxidation and Subsequent CO 2 Chemisorption on Alkaline Zirconates: Li 2 ZrO 3 and Na 2 ZrO 3

DOE PAGES

Alcántar-Vázquez, Brenda; Duan, Yuhua; Pfeiffer, Heriberto

2016-08-26

Here, two different alkaline zirconates (Li 2ZrO 3 and Na 2ZrO 3) were studied as possible bifunctional catalytic-captor materials for CO oxidation and the subsequent CO 2 chemisorption process. Initially, CO oxidation reactions were analyzed in a catalytic reactor coupled to a gas chromatograph, using Li 2ZrO 3 and Na 2ZrO 3, under different O 2 partial flows. We found results clearly showed that Na 2ZrO 3 possesses much better catalytic properties than Li 2ZrO 3. After the CO-O 2 oxidation catalytic analysis, CO2 chemisorption process was analyzed by thermogravimetric analysis, only for the Na 2ZrO 3 ceramic. The resultsmore » confirmed that Na 2ZrO 3 is able to work as a bifunctional material (CO oxidation and subsequent CO 2 chemisorption), although the kinetic CO 2 capture process was not the best one under the physicochemical condition used in this case. For Na 2ZrO 3, the best CO conversions were found between 445 and 580 °C (100%), while Li 2ZrO 3 only showed a 35% of efficiency between 460 and 503 °C. However, in the Na 2ZrO 3 case, at temperatures higher than 580 °C its catalytic activity gradually decreases as a result of CO 2 capture process. Finally, all these experiments were compared and supported with theoretical thermodynamic data.« less

An ab initio study of the adsorption and dissociation of molecular oxygen on the (0 0 0 1) surface of double hexagonal close-packed americium

NASA Astrophysics Data System (ADS)

Dholabhai, Pratik P.; Atta-Fynn, Raymond; Ray, Asok K.

2008-12-01

In our continuing attempts to understand theoretically various surface properties such as corrosion and potential catalytic activity of actinide surfaces in the presence of environmental gases, we report here the first ab initio study of molecular adsorption on the double hexagonal close-packed (dhcp) americium (Am) (0 0 0 1) surface. Specifically, molecular oxygen adsorption on the (0 0 0 1) surface of dhcp Am has been studied in detail within the framework of density functional theory using a full-potential all-electron linearized augmented plane wave plus local orbitals (FP-LAPW+lo) method. Dissociative adsorption is found to be energetically more favorable compared to molecular adsorption. Chemisorption energies were optimized with respect to the distance of adsorbates from the surface for three approach positions at three adsorption sites, namely t1 (one-fold top), b2 (two-fold bridge), and h3 (three-fold hollow) sites. Chemisorption energies were computed at the scalar-relativistic-no-spin-orbit-coupling (SR-NSOC) and at the fully relativistic-with-spin-orbit-coupling (FR-SOC) levels of theory. The most stable configuration corresponds to a horizontal approach molecular dissociation with the oxygen atoms occupying neighboring h3 sites, with chemisorption energies at the NSOC and SOC theoretical levels being 9.395 and 9.886 eV, respectively. The corresponding distances of the oxygen molecule from the surface and oxygen-oxygen distance were found to be 0.953 and 3.731 Å, respectively. Overall our calculations indicate that chemisorption energies in cases with SOC are slightly more stable than those with NSOC in the 0.089-0.493 eV range. The work functions and net magnetic moments, respectively, increased and decreased in all cases compared to corresponding quantities of the bare dhcp-Am (0 0 0 1) surface. Adsorbate-substrate interactions have been analyzed in detail using partial charges inside muffin-tin spheres, difference charge density distributions, and the local density of states. The effects, if any, of chemisorption on Am5f electron localization-delocalization characteristics in the vicinity of the Fermi level are also discussed.

Dispersion measurement by the single introduction method coupled with the back-sorption procedure: A chemisorption and TPD study of the different chemisorbed hydrogen species

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

Ragaini, V.; Giannantonio, R.; Magni, P.

1994-03-01

The Single Introduction (S.I.) method for the measurement by hydrogen chemisorption of metal dispersion in supported metal catalysts has been tested on two commercial 5% Pd/Al[sub 2]O[sub 3] catalysts. The S.I. results are compared with those obtained by the classical method of determining the adsorption isotherm (i.e., the multiple introduction method) and by O[sub 2]/H[sub 2] titration. As in Part I of this work, both chemisorption and thermal desorption have been used to find the best experimental conditions for the [open quotes]Back-Sorption[close quotes] procedure. It is shown that [alpha]- and [beta]-palladium hydrides can be decomposed by outgassing the samples formore » less than 5 min at 305 K and 10[sup [minus]6] Torr and that 30 min pumping at the same temperature and pressure is sufficient to eliminate from the catalyst surface the weakly adsorbed hydrogen as well. It has also been verified that chemisorption of hydrogen on these catalysts at room temperature is complete at pressures lower than those required for the [alpha] [yields] [beta] phase transition, so that it is possible to perform dispersion measurements by means of a simple S.I. of hydrogen coupled with Back-Sorption below 15 Torr at 305 K. Temperature-programmed desorption of hydrogen on one of the samples outlines the need to discriminate among the different adsorbed species for a more detailed characterization of supported metal catalysts. 44 refs., 10 figs., 2 tabs.« less

Adsorption and dissociation of molecular oxygen on α-Pu (0 2 0) surface: A density functional study

NASA Astrophysics Data System (ADS)

Wang, Jianguang; Ray, Asok K.

2011-09-01

Molecular and dissociative oxygen adsorptions on the α-Pu (0 2 0) surface have been systematically studied using the full-potential linearized augmented-plane-wave plus local orbitals (FP-LAPW+lo) basis method and the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional. Chemisorption energies have been optimized for the distance of the admolecule from the Pu surface and the bond length of O-O atoms for four adsorption sites and three approaches of O 2 admolecule to the (0 2 0) surface. Chemisorption energies have been calculated at the scalar relativistic level with no spin-orbit coupling (NSOC) and at the fully relativistic level with spin-orbit coupling (SOC). Dissociative adsorptions are found at the two horizontal approaches (O 2 is parallel to the surface and perpendicular/parallel to a lattice vector). Hor2 (O 2 is parallel to the surface and perpendicular to a lattice vector) approach at the one-fold top site is the most stable adsorption site, with chemisorption energies of 8.048 and 8.415 eV for the NSOC and SOC cases, respectively, and an OO separation of 3.70 Å. Molecular adsorption occurs at the Vert (O 2 is vertical to the surface) approach of each adsorption site. The calculated work functions and net spin magnetic moments, respectively, increase and decrease in all cases upon chemisorption compared to the clean surface. The partial charges inside the muffin-tins, the difference charge density distributions, and the local density of states have been used to investigate the Pu-admolecule electronic structures and bonding mechanisms.

Influence of silicon defects on the adsorption of thiophene-like compounds on polycyclic aromatic hydrocarbons: a theoretical study using thiophene + coronene as the simplest model.

PubMed

Galano, Annia

2007-03-08

Physisorption and chemisorption processes of thiophene on coronene and 2Si-coronene have been studied using density functional theory and MP2 methods. These systems have been chosen as the simplest models to describe the adsorption of thiophene-like compounds on polycyclic aromatic hydrocarbons (PAHs). The calculated data suggest that the presence of silicon atoms in PAHs could favor their interaction with thiophene and similar compounds. Small stabilization energies have been found for several physisorbed complexes. The thiophene chemisorption on coronene seems very unlikely to occur, while that on 2Si-coronene leads to addition products which are very stable, with respect to the isolated reactants. These chemisorption processes were found to be exoergic (DeltaG < 0) in the gas phase and in the nonpolar liquid phase. The results reported in this work suggest that silicon defects on extended polycyclic aromatic hydrocarbons, such as graphite, soot, and large-diameter carbon nanotubes, could make them useful in the removal processes of aromatic sulfur compounds from oil hydrocarbons.

Bifunctional application of sodium cobaltate as a catalyst and captor through CO oxidation and subsequent CO 2 chemisorption processes

DOE PAGES

Vera, Elizabeth; Alcántar-Vázquez, Brenda; Duan, Yuhua; ...

2015-12-21

The potential bifunctional mechanism of sodium cobaltate (NaCoO 2) in the catalysis of CO oxidation and subsequent CO 2 chemisorption was systematically analysed. Different catalytic and gravimetric experiments were performed dynamically and isothermally at multiple temperatures. Initially, the CO oxidation process was evaluated using a catalytic reactor connected to a gas chromatograph. Once the production of CO 2 was confirmed, its chemisorption capacity with NaCoO 2 was studied gravimetrically. Catalytic and gravimetric analysis products were studied by XRD, FTIR and SEM to elucidate the double reaction mechanism. Sodium cobaltate exhibited interesting catalytic properties over a wide temperature range, although themore » NaCoO 2 crystalline structure and chemical composition changed during the CO 2 capture process. Furthermore, all the experiments were theoretically supported by first-principles density functional theory thermodynamic calculations. Finally, the calculated thermodynamic properties of the CO oxidation and CO 2 capture reactions with NaCoO 2 under different oxidation conditions were in good agreement with the experimental measurements.« less

Calcium oxalate crystal growth modification; investigations with confocal Raman microscopy

NASA Astrophysics Data System (ADS)

McMulkin, Calum J.; Massi, Massimiliano; Jones, Franca

2017-06-01

Confocal Raman Microscopy (CRM) in combination with a photophysical investigation has been employed to give insight into the interaction between calcium oxalate monohydrate (COM) and a series of tetrazole containing crystal growth modifier's (CGM's), in conjunction with characterisation of morphological changes using scanning electron and optical microscopy. The tetrazole CGM's were found to interact by surface adsorption with minimal morphological changes to the COM crystals however, significant interactions via chemisorption were observed; it was discovered that the chemisorption is sufficiently strong for aggregation of the tetrazole species to occur within the crystal during crystallisation.

The adsorption of methyl, acetylide, chlorine and phosphorus trifluoride on zinc oxide: A quantum-chemical study

NASA Astrophysics Data System (ADS)

Rodriguez, JoséA.

1989-11-01

The chemisorptions of methyl (CH 3), acetylide (H-CC), chlorine (Cl) and phosphorus trifluoride (PF 3) on ZnO(0001) and of Cl on ZnO(101¯0) have been examined employing semi-em- pirical quantum-chemical calculations (INDO/S) and neutral clusters of limited size (Zn 13O 13). CH 3, H-CC and Cl appear as strong electron acceptors when adsorbed on Zn sites of ZnO. The chemisorption bonds of these molecules are almost pure σ-bonds and are largely localized on the adsorption site. An increase in the work function of ZnO surfaces upon adsorption of CH 3, H-CC and Cl is predicted. The PF 3 molecule is a very weak acceptor of electrons when adsorbed on a-top sites of ZnO(0001). The bonding mechanism of CH 3, H-CC, Cl and PF 3 on the ZnO(0001) surface involves primarily the HOMO and LUMO of the adsorbate and the Zn(4s,4p) orbitals of the substrate. The effects of chemisorption on the C-H bonds of CH 3 and H-CC, the C-C bond of H-CC, and the P-F bonds of PF 3 are examined. On the basis of these INDO/S results, the possible UPS spectra for CH 3, H-CC and PF 3 adsorbed on ZnO(0001) are discussed and compared with results for adsorption on transition-metal surfaces. A general picture of the chemisorption bond of alkyls, acetylides, alkoxides, carboxylates and halogens on a-top sites of ZnO(0001) is obtained by comparing our results for adsorption of CH 3, H-CC and Cl with those previously reported for adsorption of methoxy, OH and formate.

SPRi-based biosensing platforms for detection of specific DNA sequences using thiolate and dithiocarbamate assemblies

NASA Astrophysics Data System (ADS)

Drozd, Marcin; Pietrzak, Mariusz D.; Malinowska, Elżbieta

2018-05-01

The framework of presented study covers the development and examination of the analytical performance of surface plasmon resonance-based (SPR) DNA biosensors dedicated for a detection of model target oligonucleotide sequence. For this aim, various strategies of immobilization of DNA probes on gold transducers were tested. Besides the typical approaches: chemisorption of thiolated ssDNA (DNA-thiol) and physisorption of non-functionalized oligonucleotides, relatively new method based on chemisorption of dithiocarbamate-functionalized ssDNA (DNA-DTC) was applied for the first time for preparation of DNA-based SPR biosensor. The special emphasis was put on the correlation between the method of DNA immobilization and the composition of obtained receptor layer. The carried out studies focused on the examination of the capability of developed receptors layers to interact with both target DNA and DNA-functionalized AuNPs. It was found, that the detection limit of target DNA sequence (27 nb length) depends on the strategy of probe immobilization and backfilling method, and in the best case it amounted to 0,66 nM. Moreover, the application of ssDNA-functionalized gold nanoparticles (AuNPs) as plasmonic labels for secondary enhancement of SPR response is presented. The influence of spatial organization and surface density of a receptor layer on the ability to interact with DNA-functionalized AuNPs is discussed. Due to the best compatibility of receptors immobilized via DTC chemisorption: 1.47 ± 0.4 ·1012 molecules • cm-2 (with the calculated area occupied by single nanoparticle label of 132.7 nm2), DNA chemisorption based on DTCs is pointed as especially promising for DNA biosensors utilizing indirect detection in competitive assays.

Nature of adsorption on TiC(111) investigated with density-functional calculations

NASA Astrophysics Data System (ADS)

Ruberto, Carlo; Lundqvist, Bengt I.

2007-06-01

Extensive density-functional calculations are performed for chemisorption of atoms in the three first periods (H, B, C, N, O, F, Al, Si, P, S, and Cl) on the polar TiC(111) surface. Calculations are also performed for O on TiC(001), for full O(1×1) monolayer on TiC(111), as well as for bulk TiC and for the clean TiC(111) and (001) surfaces. Detailed results concerning atomic structures, energetics, and electronic structures are presented. For the bulk and the clean surfaces, previous results are confirmed. In addition, detailed results are given on the presence of C-C bonds in the bulk and at the surface, as well as on the presence of a Ti-based surface resonance (TiSR) at the Fermi level and of C-based surface resonances (CSR’s) in the lower part of the surface upper valence band. For the adsorption, adsorption energies Eads and relaxed geometries are presented, showing great variations characterized by pyramid-shaped Eads trends within each period. An extraordinarily strong chemisorption is found for the O atom, 8.8eV /adatom. On the basis of the calculated electronic structures, a concerted-coupling model for the chemisorption is proposed, in which two different types of adatom-substrate interactions work together to provide the obtained strong chemisorption: (i) adatom-TiSR and (ii) adatom-CSR’s. This model is used to successfully describe the essential features of the calculated Eads trends. The fundamental nature of this model, based on the Newns-Anderson model, should make it apt for general application to transition-metal carbides and nitrides and for predictive purposes in technological applications, such as cutting-tool multilayer coatings and MAX phases.

SPRi-Based Biosensing Platforms for Detection of Specific DNA Sequences Using Thiolate and Dithiocarbamate Assemblies.

PubMed

Drozd, Marcin; Pietrzak, Mariusz D; Malinowska, Elżbieta

2018-01-01

The framework of presented study covers the development and examination of the analytical performance of surface plasmon resonance-based (SPR) DNA biosensors dedicated for a detection of model target oligonucleotide sequence. For this aim, various strategies of immobilization of DNA probes on gold transducers were tested. Besides the typical approaches: chemisorption of thiolated ssDNA (DNA-thiol) and physisorption of non-functionalized oligonucleotides, relatively new method based on chemisorption of dithiocarbamate-functionalized ssDNA (DNA-DTC) was applied for the first time for preparation of DNA-based SPR biosensor. The special emphasis was put on the correlation between the method of DNA immobilization and the composition of obtained receptor layer. The carried out studies focused on the examination of the capability of developed receptors layers to interact with both target DNA and DNA-functionalized AuNPs. It was found, that the detection limit of target DNA sequence (27 nb length) depends on the strategy of probe immobilization and backfilling method, and in the best case it amounted to 0.66 nM. Moreover, the application of ssDNA-functionalized gold nanoparticles (AuNPs) as plasmonic labels for secondary enhancement of SPR response is presented. The influence of spatial organization and surface density of a receptor layer on the ability to interact with DNA-functionalized AuNPs is discussed. Due to the best compatibility of receptors immobilized via DTC chemisorption: 1.47 ± 0.4 · 10 12 molecules · cm -2 (with the calculated area occupied by single nanoparticle label of ~132.7 nm 2 ), DNA chemisorption based on DTCs is pointed as especially promising for DNA biosensors utilizing indirect detection in competitive assays.

Tunneling electron induced chemisorption of copper phthalocyanine molecules on the Cu(111) surface

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

Stock, T.; Nogami, J.

2014-02-17

The adsorption of up to one monolayer (ML) of copper phthalocyanine (CuPc) molecules on a room temperature Cu(111) surface has been studied using scanning tunneling microscopy (STM). Below 1 ML the molecules are in a fluid state and are highly mobile on the surface. At 1 ML coverage the molecules coalesce into a highly ordered 2D crystal phase. At sub-ML coverages, chemisorption of individual CuPc molecules can be induced through exposure to tunneling electrons at a tunneling bias voltage exceeding a threshold value. This tunneling electron induced effect has been exploited to perform molecular STM lithography.

Recognizing Physisorption and Chemisorption in Carbon Nanotubes Gas Sensors by Double Exponential Fitting of the Response.

PubMed

Calvi, Andrea; Ferrari, Alberto; Sbuelz, Luca; Goldoni, Andrea; Modesti, Silvio

2016-05-19

Multi-walled carbon nanotubes (CNTs) have been grown in situ on a SiO 2 substrate and used as gas sensors. For this purpose, the voltage response of the CNTs as a function of time has been used to detect H 2 and CO 2 at various concentrations by supplying a constant current to the system. The analysis of both adsorptions and desorptions curves has revealed two different exponential behaviours for each curve. The study of the characteristic times, obtained from the fitting of the data, has allowed us to identify separately chemisorption and physisorption processes on the CNTs.

Rare isotope studies involving catalytic oxidation of CO over platinum-tin oxide

NASA Technical Reports Server (NTRS)

Upchurch, Billy T.; Wood, George M., Jr.; Hess, Robert V.; Hoyt, Ronald F.

1987-01-01

Results of studies utilizing normal and rare oxygen isotopes in the catalytic oxidation of carbon monoxide over a platinum-tin oxide catalyst substrate are presented. Chemisorption of labeled carbon monoxide on the catalyst followed by thermal desorption yielded a carbon dioxide product with an oxygen-18 composition consistent with the formation of a carbonate-like intermediate in the chemisorption process. The efficacy of a method developed for the oxygen-18 labeling of the platinum-tin oxide catalyst surface for use in closed cycle pulsed care isotope carbon dioxide lasers is demonstrated for the equivalent of 10 to the 6th power pulses at 10 pulses per second.

Feasibility demonstration for hydrogen chloride detection using a chemisorption technique and a quartz crystal microbalance

NASA Technical Reports Server (NTRS)

Jex, D. W.; Workman, G. L.

1975-01-01

A method of measuring concentrations of hydrogen chloride between 1 part per billion and 10 parts per million at standard temperature and pressure is presented. The feasibility of a low-cost device incorporating a chemisorption technique coupled with a quartz crystal microbalance was demonstrated in the field at the Viking B launch using a Titan-Centaur vehicle from Kennedy Space Center on August 20, 1975. Hydrogen chloride is a product of solid rocket combustion. The concentration level of hydrogen chloride for this particular launch was measured as approximately 0.2 parts per million at 4 km from the launch site.

The dissociative chemisorption of CO2 on Ni(100): A quantum dynamics study

NASA Astrophysics Data System (ADS)

Farjamnia, Azar; Jackson, Bret

2017-02-01

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of CO2 on Ni(100). The largest barrier to reaction corresponds to the formation of a bent anionic molecular precursor, bound to the surface by about 0.24 eV. The barrier to dissociation from this state is small. Our computed dissociative sticking probabilities on Ni(100) for molecules in the ground state are in very good agreement with available experimental data, reasonably reproducing the variation in reactivity with collision energy. Vibrational excitation of the incident CO2 can enhance reactivity, particularly for incident energies at or below threshold, and there is clear mode specific behavior. Both the vibrational enhancement and the increase in dissociative sticking with surface temperature are much weaker than that found in recent studies of methane and water dissociative chemisorption. The energetics for CO2 adsorption and dissociation on the stepped Ni(711) surface are found to be similar to that on Ni(100), except that the barrier to dissociation from the anionic precursor is even smaller on Ni(711). We predict that the dissociative sticking behavior is similar on the two surfaces.

The dissociative chemisorption of CO 2 on Ni(100): A quantum dynamics study

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

Farjamnia, Azar; Jackson, Bret

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of CO 2 on Ni(100). The largest barrier to reaction corresponds to the formation of a bent anionic molecular precursor, bound to the surface by about 0.24 eV. The barrier to dissociation from this state is small. In our computed dissociative sticking probabilities on Ni(100) for molecules, the ground states are in very good agreement with available experimental data, reasonably reproducing the variation in reactivity with collision energy. Vibrational excitation of the incident CO 2 can enhance reactivity, particularly for incident energiesmore » at or below threshold, and there is clear mode specific behavior. Both the vibrational enhancement and the increase in dissociative sticking with surface temperature are much weaker than that found in recent studies of methane and water dissociative chemisorption. The energetics for CO 2 adsorption and dissociation on the stepped Ni(711) surface are found to be similar to that on Ni(100), except that the barrier to dissociation from the anionic precursor is even smaller on Ni(711). Here, we predict that the dissociative sticking behavior is similar on the two surfaces.« less

The dissociative chemisorption of CO 2 on Ni(100): A quantum dynamics study

DOE PAGES

Farjamnia, Azar; Jackson, Bret

2017-02-21

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of CO 2 on Ni(100). The largest barrier to reaction corresponds to the formation of a bent anionic molecular precursor, bound to the surface by about 0.24 eV. The barrier to dissociation from this state is small. In our computed dissociative sticking probabilities on Ni(100) for molecules, the ground states are in very good agreement with available experimental data, reasonably reproducing the variation in reactivity with collision energy. Vibrational excitation of the incident CO 2 can enhance reactivity, particularly for incident energiesmore » at or below threshold, and there is clear mode specific behavior. Both the vibrational enhancement and the increase in dissociative sticking with surface temperature are much weaker than that found in recent studies of methane and water dissociative chemisorption. The energetics for CO 2 adsorption and dissociation on the stepped Ni(711) surface are found to be similar to that on Ni(100), except that the barrier to dissociation from the anionic precursor is even smaller on Ni(711). Here, we predict that the dissociative sticking behavior is similar on the two surfaces.« less

Analysis of the CO 2 Chemisorption in Li 5FeO 4, a New High Temperature CO 2 Captor Material. Effect of the CO 2 and O 2 Partial Pressures

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

Lara-García, Hugo A.; Sanchez-Camacho, Pedro; Duan, Yuhua

Pentalithium ferrite (Li 5FeO 4) was tested in this paper as possible CO 2 captor, both by theoretical calculations and experimental measurements. The pristine Li 5FeO 4 compound with orthorhombic structure was synthesized via solid-state reaction and it was structural and microstructurally characterized. Later, sample was heat-treated at temperatures from room temperature to 900 °C under different CO 2 or CO 2–O 2 atmospheres. Li 5FeO 4 exhibits excellent CO 2 chemisorption abilities with a capture capacity about 12.9 mmol/g, which is outstanding in comparison to other previously reported ceramic captors. This material is able to react with CO 2more » from 200 °C to approximately 715 °C showing a high kinetic of reaction even at CO 2 partial pressure values as low as 0.2. Finally and additionally, results suggest that oxygen addition does enhance the CO 2 chemisorption on Li 5FeO 4 at temperatures below 700 °C, although oxygen addition seems to favor the desorption process at higher temperatures.« less

Theoretical insight of adsorption thermodynamics of multifunctional molecules on metal surfaces

NASA Astrophysics Data System (ADS)

Loffreda, David

2006-05-01

Adsorption thermodynamics based on density functional theory (DFT) calculations are exposed for the interaction of several multifunctional molecules with Pt and Au(1 1 0)-(1 × 2) surfaces. The Gibbs free adsorption energy explicitly depends on the adsorption internal energy, which is derived from DFT adsorption energy, and the vibrational entropy change during the chemisorption process. Zero-point energy (ZPE) corrections have been systematically applied to the adsorption energy. Moreover the vibrational entropy change has been computed on the basis of DFT harmonic frequencies (gas and adsorbed phases, clean surfaces), which have been extended to all the adsorbate vibrations and the metallic surface phonons. The phase diagrams plotted in realistic conditions of temperature (from 100 to 400 K) and pressure (0.15 atm) show that the ZPE corrected adsorption energy is the main contribution. When strong chemisorption is considered on the Pt surface, the multifunctional molecules are adsorbed on the surface in the considered temperature range. In contrast for weak chemisorption on the Au surface, the thermodynamic results should be held cautiously. The systematic errors of the model (choice of the functional, configurational entropy and vibrational entropy) make difficult the prediction of the adsorption-desorption phase boundaries.

Analysis of the CO 2 Chemisorption in Li 5FeO 4, a New High Temperature CO 2 Captor Material. Effect of the CO 2 and O 2 Partial Pressures

DOE PAGES

Lara-García, Hugo A.; Sanchez-Camacho, Pedro; Duan, Yuhua; ...

2017-01-23

Pentalithium ferrite (Li 5FeO 4) was tested in this paper as possible CO 2 captor, both by theoretical calculations and experimental measurements. The pristine Li 5FeO 4 compound with orthorhombic structure was synthesized via solid-state reaction and it was structural and microstructurally characterized. Later, sample was heat-treated at temperatures from room temperature to 900 °C under different CO 2 or CO 2–O 2 atmospheres. Li 5FeO 4 exhibits excellent CO 2 chemisorption abilities with a capture capacity about 12.9 mmol/g, which is outstanding in comparison to other previously reported ceramic captors. This material is able to react with CO 2more » from 200 °C to approximately 715 °C showing a high kinetic of reaction even at CO 2 partial pressure values as low as 0.2. Finally and additionally, results suggest that oxygen addition does enhance the CO 2 chemisorption on Li 5FeO 4 at temperatures below 700 °C, although oxygen addition seems to favor the desorption process at higher temperatures.« less

Electrochemical generation of oxygen. 1: The effects of anions and cations on hydrogen chemisorption and anodic oxide film formation on platinum electrode. 2: The effects of anions and cations on oxygen generation on platinum electrode

NASA Technical Reports Server (NTRS)

Huang, C. J.; Yeager, E.; Ogrady, W. E.

1975-01-01

The effects were studied of anions and cations on hydrogen chemisorption and anodic oxide film formation on Pt by linear sweep voltammetry, and on oxygen generation on Pt by potentiostatic overpotential measurement. The hydrogen chemisorption and anodic oxide film formation regions are greatly influenced by anion adsorption. In acids, the strongly bound hydrogen occurs at more cathodic potential when chloride and sulfate are present. Sulfate affects the initial phase of oxide film formation by produced fine structure while chloride retards the oxide-film formation. In alkaline solutions, both strongly and weakly bound hydrogen are influenced by iodide, cyanide, and barium and calcium cations. These ions also influence the oxide film formation. Factors considered to explain these effects are discussed. The Tafel slope for oxygen generation was found to be independent on the oxide thickness and the presence of cations or anions. The catalytic activity indicated by the exchange current density was observed decreasing with increasing oxide layer thickness, only a minor dependence on the addition of certain cations and anions was found.

Evaluation of Fe-containing Li2CuO2 on CO2 capture performed at different physicochemical conditions.

PubMed

Yañez-Aulestia, Ana; Ovalle-Encinia, Oscar; Pfeiffer, Heriberto

2018-06-05

Li 2 CuO 2 and different iron-containing Li 2 CuO 2 samples were synthesized by solid state reaction. On iron-containing samples, atomic sites of copper are substituted by iron ions in the lattice (XRD and Rietveld analyses). Iron addition induces copper release from Li 2 CuO 2 , which produce cationic vacancies and CuO, due to copper (Cu 2+ ) and iron (Fe 3+ ) valence differences. Two different physicochemical conditions were used for analyzing CO 2 capture on these samples; (i) high temperature and (ii) low temperature in presence of water vapor. At high temperatures, iron addition increased CO 2 chemisorption, due to structural and chemical variations on Li 2 CuO 2 . Kinetic analysis performed by first order reaction and Eyring models evidenced that iron addition on Li 2 CuO 2 induced a faster CO 2 chemisorption but a higher thermal dependence. Conversely, CO 2 chemisorption at low temperature in water vapor presence practically did not vary by iron addition, although hydration and hydroxylation processes were enhanced. Moreover, under these physicochemical conditions the whole sorption process became slower on iron-containing samples, due to metal oxides presence.

The Role of Gas-Silicate Chemisorption Reactions in Modifying Planetary Crusts and Surfaces

NASA Astrophysics Data System (ADS)

King, P. L.; Henley, R. W.; Wykes, J. L.; Renggli, C.; Troitzsch, U.; Clark, D.; O'Neill, H. S.

2014-12-01

Evidence for gas-solid reactions is found throughout the solar system: for example, sulfidation reactions in some meteorites and secondary phases coating lunar pyroclastic glasses. On Earth, the products of gas-solid reactions are documented in volcanic systems, metalliferous mineral deposits, impact craters, and on dust or meteorites after passage through the atmosphere - such reactions are also likely on the surfaces of Mars and Venus. To understand the chemical dynamics of such gas-solid reactions, we are undertaking systematic experiments and thermochemical modelling. Experiments were conducted in a vertical gas-mixing furnace at 600 - 800 °C and 1 bar, using SO2and a range of Ca-bearing materials: labradorite, feldspar glass and anorthosite (rock). In each case, anhydrite formed rapidly. In shorter experiments with labradorite, isolated anhydrite is observed surrounded by 'moats' of Ca-depleted silicate. In longer experiments, anhydrite is found as clusters of crystals that, in some cases, extend from the substrate forming precarious 'towers' (Figure). Anhydrite fills cracks in porous samples. We propose that the nucleation and rapid growth of anhydrite on the surface of these Ca-rich phases occurs by chemisorption of SO2(g) molecules with slightly negatively charged oxygen onto available near-surface calcium with slight positive charge. Anhydrite growth is sustained by SO2(g) chemisorption and Ca migration through the reacting silicate lattice, accelerated by increased bond lengths at high temperature. Significantly, the chemisorption reaction indicates that SO2 disproportionates to form both oxidized sulfur (as anhydrite) and a reduced sulfur species (e.g., an S* radical ion). On Earth, in the presence of H2O, the predominant reduced sulfur species is H2S, through an overall reaction: 3CaAl2Si2O8 + 4 SO2(g)+ H2O(g) → 3CaSO4 + 3Al2SiO5 + 3SiO2 + H2S(g)The reduced sulfur may react with gas phase Fe, Ni, Zn and Cu cluster compounds to form metal sulfides. This is observed on the km-scale through co-existing anhydrite and sulphide in porphyry copper deposits on Earth. Chemisorption reactions with S-gases may also be responsible for sulfide coatings on lunar glass beads; sulfate minerals with volcanic rocks on Mars (e.g., Home Plate); and putative sulfate minerals on Venus and the early Earth.

Chemical surface modification of polycrystalline platinum thin-films to promote preferential chemisorption of n-hexane, piperidine, and cyclohexane

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

Thomas, V.; Schwank, J.; Gland, J.

In this study, hard/soft Lewis acid-base (HSAB) principles are used to modify a thin-polycrystalline platinum film to promote preferential chemisorption of molecules such as piperidine, n-hexane, and cyclohexane. Specifically, the particle size and electron density distribution of the platinum surface is modified using thermal treatment and co-adsorption of electro-positive and negative species. These studies are conducted in an ultra-high vacuum chamber. The platinum surface is characterized, before and after modification protocols, using a variety of in-situ and ex-situ techniques. These include temperature programmed desorption (TPD), both resistance change and work function measurements, and both X-ray photoelectron spectroscopy and diffraction.

Effect of Organic Cations on Hydrogen Oxidation Reaction of Carbon Supported Platinum

DOE PAGES

Chung, Hoon Taek; Choe, Yong-Kee; Martinez, Ulises; ...

2016-11-02

Effect of organic cations on hydrogen oxidation reaction (HOR) of carbon supported platinum (Pt/C) is investigated using three 0.1 M alkaline electrolytes, tetramethylammonium hydroxide (TMAOH), tetrabutylammonium hydroxide (TBAOH) and tetrabutylphosphonium hydroxide (TBPOH). Rotating disk electrode experiments indicate that the HOR of Pt/C is adversely impacted by time-dependent and potential-driven chemisorption of organic cations. In-situ infrared reflection adsorption spectroscopy experiments indicated that the specific chemisorption of organic cations drives the hydroxide co-adsorption on Pt surface. The co-adsorption of TMA + and hydroxide at 0.1 V vs. reversible hydrogen electrode is the strongest; consequently, complete removal of the co-adsorbed layer from Ptmore » surface is difficult even after exposure the Pt surface to 1.2 V. Conversely, the chemisorption of TBP+ is the weakest, yet notable decrease of HOR current density is still observed. The adsorption energies, ΔE, for TMA +, TBA +, and TBP + on Pt (111) surface from density functional theory are computed to be -2.79, -2.42 and -2.00 eV, respectively. The relatively low adsorption energy of TBP + is explained by the steric hindrance and electronic effect. This study emphasizes the importance of cationic group on HOR activity of alkaline anion exchange membrane fuel cells.« less

Electron-hole pair effects in methane dissociative chemisorption on Ni(111)

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

Luo, Xuan; Jiang, Bin, E-mail: bjiangch@ustc.edu.cn; Juaristi, J. Iñaki

The dissociative chemisorption of methane on metal surfaces has attracted much attention in recent years as a prototype of gas-surface reactions in understanding the mode specific and bond selective chemistry. In this work, we systematically investigate the influence of electron-hole pair excitations on the dissociative chemisorption of CH{sub 4}/CH{sub 3}D/CHD{sub 3} on Ni(111). The energy dissipation induced by surface electron-hole pair excitations is modeled as a friction force introduced in the generalized Langevin equation, in which the independent atomic friction coefficients are determined within the local-density friction approximation. Quasi-classical trajectory calculations for CH{sub 4}/CH{sub 3}D/CHD{sub 3} have been carried outmore » on a recently developed twelve-dimensional potential energy surface. Comparing the dissociation probabilities obtained with and without friction, our results clearly indicate that the electron-hole pair effects are generally small, both on absolute reactivity of each vibrational state and on the mode specificity and bond selectivity. Given similar observations in both water and methane dissociation processes, we conclude that electron-hole pair excitations would not play an important role as long as the reaction is direct and the interaction time between the molecule and metal electrons is relatively short.« less

Density functional theory study on the interactions of l-cysteine with graphene: adsorption stability and magnetism

NASA Astrophysics Data System (ADS)

Luo, Huijuan; Li, Hejun; Fu, Qiangang; Chu, Yanhui; Cao, Xiaoyu; Sun, Can; Yuan, Xiaoyan; Liu, Lei

2013-12-01

Understanding the interactions between graphene and biomolecules is of fundamental relevance to the area of nanobiotechnology. Herein, we take l-cysteine as the probe biomolecule and investigate its adsorption on pristine graphene and B-, N-, Al-, Ni-, Ga-, Pd-doped graphene using density functional theory calculations. Three kinds of upright adsorption configurations, via unprotonated functional groups (-SH, -NH2, -COOH), are considered. The calculations reveal pristine graphene physically adsorbs l-cysteine. N-doped graphene shows physisorption towards the S-end and N-end l-cysteine, and chemisorption towards the O-end radical. Strong chemisorption, with site-specific preference, occurs on Al-, Ni-, Ga- and Pd-doped graphene, accompanied by severe structural changes. Spin polarization with an unusual mirror symmetry on Ni- and Pd-doped graphene is induced by chemisorption of unprotonated l-cysteine, except for O-end adsorption on Pd-doped graphene. The magnetization arises mainly from spin polarization of the C 2pz orbital, with a minor magnetism located on Ni or Pd. The influence of van der Waals forces is also evaluated. A thorough analysis of the adsorption stability and magnetism of these systems would be beneficial to facilitate applications in graphene-based biosensing, biomolecule immobilization, magnetic bio-separation and other fields in bionanotechnology.

Methane dissociative chemisorption and detailed balance on Pt(111): Dynamical constraints and the modest influence of tunneling

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

Donald, S. B.; Navin, J. K.; Harrison, I., E-mail: harrison@virginia.edu

A dynamically biased (d-) precursor mediated microcanonical trapping (PMMT) model of the activated dissociative chemisorption of methane on Pt(111) is applied to a wide range of dissociative sticking experiments, and, by detailed balance, to the methane product state distributions from the thermal associative desorption of adsorbed hydrogen with coadsorbed methyl radicals. Tunneling pathways were incorporated into the d-PMMT model to better replicate the translational energy distribution of the desorbing methane product from the laser induced thermal reaction of coadsorbed hydrogen and methyl radicals occurring near T{sub s} = 395 K. Although tunneling is predicted to be inconsequential to the thermalmore » dissociative chemisorption of CH{sub 4} on Pt(111) at the high temperatures of catalytic interest, once the temperature drops to 395 K the tunneling fraction of the reactive thermal flux reaches 15%, and as temperatures drop below 275 K the tunneling fraction exceeds 50%. The d-PMMT model parameters of (E{sub 0} = 58.9 kJ/mol, s = 2, η{sub v} = 0.40) describe the apparent threshold energy for CH{sub 4}/Pt(111) dissociative chemisorption, the number of surface oscillators involved in the precursor complex, and the efficacy of molecular vibrational energy to promote reaction, relative to translational energy directed along the surface normal. Molecular translations parallel to the surface and rotations are treated as spectator degrees of freedom. Transition state vibrational frequencies are derived from generalized gradient approximation-density functional theory electronic structure calculations. The d-PMMT model replicates the diverse range of experimental data available with good fidelity, including some new effusive molecular beam and ambient gas dissociative sticking measurements. Nevertheless, there are some indications that closer agreement between theory and experiments could be achieved if a surface efficacy less than one was introduced into the modeling as an additional dynamical constraint.« less

Electron Spectroscopy Studies of Iron, Iron Sulfides and Supported Iron Surfaces: Chemisorption of Simple Gases.

NASA Astrophysics Data System (ADS)

Lee, Yiu Chung

EELS was used to investigate the chemisorption of oxygen and carbon on iron. The EELS spectra of oxidized iron show characteristic features with strong enhancement of the interband transitions involving the Fe 3d band (4.6 and 7.5 eV) and moderate enhancement of the M(,2,3) transition doublet (54.4 and 58.2 eV). The changes in the electron energy loss structures with an overlayer of graphitic or carbidic carbon were investigated. The adsorption and growth of iron on Ni(100) has been studied using the combined techniques of LEED and EELS. Initially iron grows by a layer-by-layer mechanism for the first few layers. High iron coverages result in the observation of complex LEED patterns with satellites around the main (1 x 1) diffraction sports. This is due to the formation of b.c.c. Fe(110) crystallites arranged in domains with different orientations. EELS studies show the presence of three stages in the growth of iron on Ni(100): low-coverage, film-like and bulk-like. Auger and EELS were used to study the iron sulfide (FeS(,2), Fe(,7)S(,8) and FeS) surfaces. A characteristic M(,2,3) VV Auger doublet with a separation of 5.0 eV was observed on the sulfides. An assignment of the electron energy loss peaks was made based on the energy dependence of the loss peaks and previous photoemission results. The effect of argon ion bombardment was studied. Peaks with strong iron and sulfur character were observed. Heating the damaged sulfides results in reconstruction of the sulfide surfaces. The reactions of the sulfides with simple gases, such as H(,2), CO, CH(,4), C(,2)H(,4), NH(,3) and O(,2) were also studied. Using XPS, the chemisorption of SO(,2) on CaO(100) has been studied. The chemical state of sulfur has been identified as that of sulfate. The kinetics of SO(,2) chemisorption on CaO are discussed. The binding states of Fe and Na on CaO were determined to be Fe('2+) and Na('+) respectively. At low Fe or Na coverages (< 0.5 ML), there is a large increase in the rate of sulfate formation at low SO(,2) exposures (< 3 L). This increase is explained by the 'activation' of SO(,2) chemisorption sites by Fe or Na adatoms.

Photocurrent generation in SnO2 thin film by surface charged chemisorption O ions

NASA Astrophysics Data System (ADS)

Lee, Po-Ming; Liao, Ching-Han; Lin, Chia-Hua; Liu, Cheng-Yi

2018-06-01

We report a photocurrent generation mechanism in the SnO2 thin film surface layer by the charged chemisorption O ions on the SnO2 thin film surface induced by O2-annealing. A critical build-in electric field in the SnO2 surface layer resulted from the charged O ions on SnO2 surface prolongs the lifetime and reduces the recombination probability of the photo-excited electron-hole pairs by UV-laser irradiation (266 nm) in the SnO2 surface layer, which is the key for the photocurrent generation in the SnO2 thin film surface layer. The critical lifetime of prolonged photo-excited electron-hole pair is calculated to be 8.3 ms.

Finite Size Effects in Submonolayer Catalysts Investigated by CO Electrosorption on PtsML/Pd(100).

PubMed

Yuan, Qiuyi; Doan, Hieu A; Grabow, Lars C; Brankovic, Stanko R

2017-10-04

A combination of scanning tunneling microscopy, subtractively normalized interfacial Fourier transform infrared spectroscopy (SNIFTIRS), and density functional theory (DFT) is used to quantify the local strain in 2D Pt clusters on the 100 facet of Pd and its effect on CO chemisorption. Good agreement between SNIFTIRS experiments and DFT simulations provide strong evidence that, in the absence of coherent strain between Pt and Pd, finite size effects introduce local compressive strain, which alters the chemisorption properties of the surface. Though this effect has been widely neglected in prior studies, our results suggest that accurate control over cluster sizes in submonolayer catalyst systems can be an effective approach to fine-tune their catalytic properties.

Communication: Energy transfer and reaction dynamics for DCl scattering on Au(111): An ab initio molecular dynamics study.

PubMed

Kolb, Brian; Guo, Hua

2016-07-07

Scattering and dissociative chemisorption of DCl on Au(111) are investigated using ab initio molecular dynamics with a slab model, in which the top two layers of Au are mobile. Substantial kinetic energy loss in the scattered DCl is found, but the amount of energy transfer is notably smaller than that observed in the experiment. On the other hand, the dissociative chemisorption probability reproduces the experimental trend with respect to the initial kinetic energy, but is about one order of magnitude larger than the reported initial sticking probability. While the theory-experiment agreement is significantly improved from the previous rigid surface model, the remaining discrepancies are still substantial, calling for further scrutiny in both theory and experiment.

CARBON DIOXIDE REDUCTION CONTACTORS IN SPACE VEHICLES AND OTHER ENCLOSED STRUCTURES,

DTIC Science & Technology

CONTROLLED ATMOSPHERES, CARBON DIOXIDE, REMOVAL, LIFE SUPPORT SYSTEMS, SPACE ENVIRONMENTS, CONFINED ENVIRONMENTS, OXYGEN CONSUMPTION, REGENERATION(ENGINEERING), CHEMISORPTION, MASS TRANSFER, FLUID MECHANICS, CENTRIFUGES .

Validity of the site-averaging approximation for modeling the dissociative chemisorption of H{sub 2} on Cu(111) surface: A quantum dynamics study on two potential energy surfaces

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

Liu, Tianhui; Fu, Bina, E-mail: bina@dicp.ac.cn, E-mail: zhangdh@dicp.ac.cn; Zhang, Dong H., E-mail: bina@dicp.ac.cn, E-mail: zhangdh@dicp.ac.cn

A new finding of the site-averaging approximation was recently reported on the dissociative chemisorption of the HCl/DCl+Au(111) surface reaction [T. Liu, B. Fu, and D. H. Zhang, J. Chem. Phys. 139, 184705 (2013); T. Liu, B. Fu, and D. H. Zhang, J. Chem. Phys. 140, 144701 (2014)]. Here, in order to investigate the dependence of new site-averaging approximation on the initial vibrational state of H{sub 2} as well as the PES for the dissociative chemisorption of H{sub 2} on Cu(111) surface at normal incidence, we carried out six-dimensional quantum dynamics calculations using the initial state-selected time-dependent wave packet approach, withmore » H{sub 2} initially in its ground vibrational state and the first vibrational excited state. The corresponding four-dimensional site-specific dissociation probabilities are also calculated with H{sub 2} fixed at bridge, center, and top sites. These calculations are all performed based on two different potential energy surfaces (PESs). It is found that the site-averaging dissociation probability over 15 fixed sites obtained from four-dimensional quantum dynamics calculations can accurately reproduce the six-dimensional dissociation probability for H{sub 2} (v = 0) and (v = 1) on the two PESs.« less

Tensile properties of ADI material in water and gaseous environments

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

Rajnovic, Dragan, E-mail: draganr@uns.ac.rs; Balos, Sebastian; Sidjanin, Leposava

2015-03-15

Austempered ductile iron (ADI) is an advanced type of heat treated ductile iron, having comparable mechanical properties as forged steels. However, it was found that in contact with water the mechanical properties of austempered ductile irons decrease, especially their ductility. Despite considerable scientific attention, the cause of this phenomenon remains unclear. Some authors suggested that hydrogen or small atom chemisorption causes the weakening of the surface atomic bonds. To get additional reliable data of that phenomenon, in this paper, two different types of austempered ductile irons were tensile tested in various environments, such as: argon, helium, hydrogen gas and water.more » It was found that only the hydrogen gas and water gave a statistically significant decrease in mechanical properties, i.e. cause embrittlement. Furthermore, the fracture surface analysis revealed that the morphology of the embrittled zone near the specimen surface shares similarities to the fatigue micro-containing striation-like lines, which indicates that the morphology of the brittle zone may be caused by cyclic local-chemisorption, micro-embrittlement and local-fracture. - Highlights: • In contact with water and other liquids the ADI suddenly exhibits embrittlement. • The embrittlement is more pronounced in water than in the gaseous hydrogen. • The hydrogen chemisorption into ADI surface causes the formation of a brittle zone. • The ADI austempered at lower temperatures (300 °C) is more resistant to embrittlement.« less

Quantum dynamics of water dissociative chemisorption on rigid Ni(111): An approximate nine-dimensional treatment

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

Jiang, Bin, E-mail: bjiangch@ustc.edu.cn, E-mail: hguo@unm.edu; Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131; Song, Hongwei

The quantum dynamics of water dissociative chemisorption on the rigid Ni(111) surface is investigated using a recently developed nine-dimensional potential energy surface. The quantum dynamical model includes explicitly seven degrees of freedom of D{sub 2}O at fixed surface sites, and the final results were obtained with a site-averaging model. The mode specificity in the site-specific results is reported and analyzed. Finally, the approximate sticking probabilities for various vibrationally excited states of D{sub 2}O are obtained considering surface lattice effects and formally all nine degrees of freedom. The comparison with experiment reveals the inaccuracy of the density functional theory and suggestsmore » the need to improve the potential energy surface.« less

Electronic levels and charge distribution near the interface of nickel

NASA Technical Reports Server (NTRS)

Waber, J. T.

1982-01-01

The energy levels in clusters of nickel atoms were investigated by means of a series of cluster calculations using both the multiple scattering and computational techniques (designated SSO) which avoids the muffin-tin approximation. The point group symmetry of the cluster has significant effect on the energy of levels nominally not occupied. This influences the electron transfer process during chemisorption. The SSO technique permits the approaching atom or molecule plus a small number of nickel atoms to be treated as a cluster. Specifically, molecular levels become more negative in the O atom, as well as in a CO molecule, as the metal atoms are approached. Thus, electron transfer from the nickel and bond formation is facilitated. This result is of importance in understanding chemisorption and catalytic processes.

Chemisorption on the (111) and (100) faces of platinum-tin bimetallic surfaces

NASA Astrophysics Data System (ADS)

Panja, Chameli

2000-10-01

Chemisorption and reaction of CH3OH (methanol), C2H 5OH (ethanol), and H2O (water) on Pt(111) and Sn/Pt(111) alloys, and CO (carbon monoxide), NO (nitric oxide), and C2D 2 (acetylene) on Pt(100) and Sn/Pt(100) have been studied under ultrahigh vacuum conditions using temperature programmed desorption (TPD), Auger electron spectroscopy (AES), low energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS) and high resolution electron energy loss spectroscopy (HREELS). Small organic molecules like CH3OH and C2H5OH are potential fuels for low-temperature hydrocarbon fuel cells and it is important to understand the role of tin as a promoter in electrooxidation of these molecules. Also, the catalytic reactions of CO, NO and C2H2 are of considerable interest for improving of automotive exhaust-gas catalytic converters and other heterogeneous catalysts. Ordered Pt-Sn alloys can be prepared by vapor deposition of Sn on Pt surfaces. A (2 x 2) structure (theta Sn = 0.25) and a (√3x√/3)R30° structure are formed on Pt(111), and a c(2 x 2) and (3√2x√2)R45° structures with theta Sn = 0.5 and 0.67, respectively, are formed on Pt(100). CH3OH, C2H5OH and H2O are all weakly bound and reversibly adsorbed on Pt(111) and both of the Sn/Pt(111) alloys under UHV conditions. Alloying Sn into the Pt(111) surface weakens the adsorption of these molecules from that on Pt(111) and leads to a lower reactivity as the surface concentration of Sn increases. TPD measurements reveal a reduction in the saturation coverage and chemisorption bond energy for CO, NO and C2HL chemisorption, on the two Sn/Pt(100)alloys compared to that on Pt(100). CO chemisorption is completely reversible on these two Sn/Pt(100) alloys. However, NO is partially reduced to form N2O on these alloys, so that N2O along with NO and O2 desorption was observed. We propose that dinitrosyl species, i.e., two NO molecules bound to one Pt atom, are intermediates in N2O formation from adsorbed NO on these Sn/Pt(100) surface alloys. Irreversible dissociative adsorption of acetylene was strongly suppressed (˜80--90%) on both of the two Sn/Pt(100) alloys. About 15% of the adsorbed acetylene monolayer was converted to benzene and desorbed during TPD on the (3√2x√2)R45°Sn/Pt(100) alloy, but no benzene was desorbed from the c(2x2) alloy.

Molecular simulation of CO chemisorption on Co(0001) in presence of supercritical fluid solvent: A potential of mean force study

NASA Astrophysics Data System (ADS)

Asiaee, Alireza; Benjamin, Kenneth M.

2016-08-01

For several decades, heterogeneous catalytic processes have been improved through utilizing supercritical fluids (SCFs) as solvents. While numerous experimental studies have been established across a range of chemistries, such as oxidation, pyrolysis, amination, and Fischer-Tropsch synthesis, still there is little fundamental, molecular-level information regarding the role of the SCF on elementary heterogeneous catalytic steps. In this study, the influence of hexane solvent on the adsorption of carbon monoxide on Co(0001), as the first step in the reaction mechanism of many processes involving syngas conversion, is probed. Simulations are performed at various bulk hexane densities, ranging from ideal gas conditions (no SCF hexane) to various near- and super-critical hexane densities. For this purpose, both density functional theory and molecular dynamics simulations are employed to determine the adsorption energy and free energy change during CO chemisorption. Potential of mean force calculations, utilizing umbrella sampling and the weighted histogram analysis method, provide the first commentary on SCF solvent effects on the energetic aspects of the chemisorption process. Simulation results indicate an enhanced stability of CO adsorption on the catalyst surface in the presence of supercritical hexane within the reduced pressure range of 1.0-1.5 at a constant temperature of 523 K. Furthermore, it is shown that the maximum stability of CO in the adsorbed state as a function of supercritical hexane density at 523 K nearly coincides with the maximum isothermal compressibility of bulk hexane at this temperature.

Permeability of two-dimensional graphene and hexagonal-boron nitride to hydrogen atom

NASA Astrophysics Data System (ADS)

Gupta, Varun; Kumar, Ankit; Ray, Nirat

2018-05-01

The permeability of atomic hydrogen in monolayer hexagonal Boron Nitride(h-BN) and graphene has been studied using first-principles density functional theory based simulations. For the specific cases of physisorption and chemisoroption, barrier heights are calculated using the nudged elastic band approach. We find that the barrier potential for physisorption through the ring is lower for graphene than h-BN. In the case of chemisorption, where the H atom passes through by making bonds with the atoms in the ring, the barrier potential for the graphene was found to be higher than that of h-BN. We conclude that the penetration of H atom with notable kinetic energy (<3eV) through physiosorption is more probable for graphene as compared to h-BN. Whereas through chemisorption, lower kinetic energy (>3eV) H-atoms have a higher chance to penetrate through h-BN than graphene.

On the behavior of Bronsted-Evans-Polanyi Relations for Transition Metal Oxides

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

Vojvodic, Aleksandra

2011-08-22

Versatile Broensted-Evans-Polanyi (BEP) relations are found from density functional theory for a wide range of transition metal oxides including rutiles and perovskites. For oxides, the relation depends on the type of oxide, the active site and the dissociating molecule. The slope of the BEP relation is strongly coupled to the adsorbate geometry in the transition state. If it is final state-like the dissociative chemisorption energy can be considered as a descriptor for the dissociation. If it is initial state-like, on the other hand, the dissociative chemisorption energy is not suitable as descriptor for the dissociation. Dissociation of molecules with strongmore » intramolecular bonds belong to the former and molecules with weak intramolecular bonds to the latter group. We show, for the prototype system La-perovskites, that there is a 'cyclic' behavior in the transition state characteristics upon change of the active transition metal of the oxide.« less

Adsorption and Dissociation of Molecular Oxygen on the (0001) Surface of Double Hexagonal Close Packed Americium

NASA Astrophysics Data System (ADS)

Dholabhai, Pratik; Atta-Fynn, Raymond; Ray, Asok

2008-03-01

Oxygen molecule adsorption on (0001) surface of double hexagonal packed americium has been studied in detail within the framework of density functional theory using a full-potential all-electron linearized augmented plane wave plus local orbitals method. The most stable configuration corresponded to molecular dissociation with the oxygen atoms occupying neighboring three-fold hollow h3 sites. Chemisorption energies and adsorption geometries for the adsorbed species, and change in work functions, magnetic moments, partial charges inside muffin-tins, difference charge density distributions and density of states for the bare Am slab and the Am slab after adsorption of the oxygen molecule will be discussed. The effects of chemisorption on Am 5f electron localization-delocalization in the vicinity of the Fermi level and the reaction barrier calculation for the dissociation of oxygen molecule to the most stable h3 sites will be discussed.

Nanoparticle chemisorption printing technique for conductive silver patterning with submicron resolution

PubMed Central

Yamada, Toshikazu; Fukuhara, Katsuo; Matsuoka, Ken; Minemawari, Hiromi; Tsutsumi, Jun'ya; Fukuda, Nobuko; Aoshima, Keisuke; Arai, Shunto; Makita, Yuichi; Kubo, Hitoshi; Enomoto, Takao; Togashi, Takanari; Kurihara, Masato; Hasegawa, Tatsuo

2016-01-01

Silver nanocolloid, a dense suspension of ligand-encapsulated silver nanoparticles, is an important material for printing-based device production technologies. However, printed conductive patterns of sufficiently high quality and resolution for industrial products have not yet been achieved, as the use of conventional printing techniques is severely limiting. Here we report a printing technique to manufacture ultrafine conductive patterns utilizing the exclusive chemisorption phenomenon of weakly encapsulated silver nanoparticles on a photoactivated surface. The process includes masked irradiation of vacuum ultraviolet light on an amorphous perfluorinated polymer layer to photoactivate the surface with pendant carboxylate groups, and subsequent coating of alkylamine-encapsulated silver nanocolloids, which causes amine–carboxylate conversion to trigger the spontaneous formation of a self-fused solid silver layer. The technique can produce silver patterns of submicron fineness adhered strongly to substrates, thus enabling manufacture of flexible transparent conductive sheets. This printing technique could replace conventional vacuum- and photolithography-based device processing. PMID:27091238

Universal energy relations and metal/ceramic interfaces

NASA Technical Reports Server (NTRS)

Smith, John R.; Schlosser, Herbert; Ferrante, John

1990-01-01

Known general relationships between pertinent variables are applied to investigate metal-ceramic interfaces. The adhesive energy is determined. The electronic exchange-correlation energy is found to be the dominant attractive term in the total energy. Results for the adhesive energy are obtained for junctions of all combinations of the low index surfaces of Al,Na, Mg, and Zn. This leads to a variety of curves, all with a single minimum of separation and equilibrium binding energy. Scaling results for 10 contacts fall closely onto a single curve, a universal energy relation for adhesion. The scaled chemisorption curves fall accurately on the same universal form that was found for adhesion. For the case of cohesion, all-first principle results are scaled and again all scaled curves for a variety of metals fall accurately on the universal form for adhesion and chemisorption. An intimate relationship between the energetics of solids and molecules is inferred.

Selective removal of mercury from aqueous solutions using thiolated cross-linked polyethylenimine

NASA Astrophysics Data System (ADS)

Saad, Dalia M.; Cukrowska, Ewa M.; Tutu, Hlanganani

2013-06-01

A successful approach to develop an insoluble form of polyethylenimine with a thiol-based functional group for selective removal of Hg(II) from aqueous solutions is reported. The selectivity of the modified polymer for Hg(II) as well as its ability to be regenerated for re-use has been studied. The synthesised polymer exhibited high selectivity for Hg(II) with high removal efficiency of up to 97 %, even in the presence of competing ions. The Freundlich isotherm was found to best fit and describe the experimental data. The pseudo-second-order equation explains the adsorption kinetics most effectively implying chemisorption. The thermodynamic study of the adsorption process revealed high activation energies >41 kJ mol-1, further confirming chemisorption as the mechanism of interaction between mercury ions and the polymer surface. The polymer exhibited good potential for re-use after many cycles of regeneration, giving good removal efficiency up to the fifth cycle.

The synthesis and the chemical and physical properties of non-aqueous silylamine solvents for carbon dioxide capture.

PubMed

Rohan, Amy L; Switzer, Jackson R; Flack, Kyle M; Hart, Ryan J; Sivaswamy, Swetha; Biddinger, Elizabeth J; Talreja, Manish; Verma, Manjusha; Faltermeier, Sean; Nielsen, Paul T; Pollet, Pamela; Schuette, George F; Eckert, Charles A; Liotta, Charles L

2012-11-01

Silylamine reversible ionic liquids were designed to achieve specific physical properties in order to address effective CO₂ capture. The reversible ionic liquid systems reported herein represent a class of switchable solvents where a relatively non-polar silylamine (molecular liquid) is reversibly transformed to a reversible ionic liquid (RevIL) by reaction with CO₂ (chemisorption). The RevILs can further capture additional CO₂ through physical absorption (physisorption). The effects of changes in structure on (1) the CO₂ capture capacity (chemisorption and physisorption), (2) the viscosity of the solvent systems at partial and total conversion to the ionic liquid state, (3) the energy required for reversing the CO₂ capture process, and (4) the ability to recycle the solvents systems are reported. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective depression behavior of guar gum on talc-type scheelite flotation

NASA Astrophysics Data System (ADS)

Zhang, Yong-zhong; Gu, Guo-hua; Wu, Xiang-bin; Zhao, Kai-le

2017-08-01

The depression behavior and mechanism of guar gum on talc-type scheelite flotation were systematically investigated by flotation experiments, adsorption tests, zeta-potential measurements, and infrared spectroscopic analyses. The flotation results for monominerals, mixed minerals, and actual mineral samples indicated that guar gum exhibited much higher selective depression for talc than for scheelite. Bench-scale closed-circuit tests showed that a tungsten concentrate with a WO3 grade of 51.43% and a WO3 recovery of 76.18% was obtained. Adsorption tests, zeta-potential measurements, and infrared spectral analyses confirmed that guar gum absorbed more strongly onto the talc surface than onto the scheelite surface because of chemisorption between guar gum and talc. This chemisorption is responsible for the guar gum's highly selective depression for talc and small depression for scheelite. The flotation results provide technical support for talc-type scheelite flotation.

Influence of preadsorbed oxygen on the sign and magnitude of the chemisorption-induced resistance change for H2 adsorption onto Fe films

NASA Technical Reports Server (NTRS)

Shanabarger, M. R.

1986-01-01

Measurements have been made of the chemisorption-induced resistance change for H2 adsorbed onto Fe film substrates predosed with fixed coverages of chemisorbed oxygen. The measurements were made at temperatures from 295 to 340 K and for estimated oxygen coverages of less than 0.1 monolayers. Two distinct resistance change components were observed in both the adsorption kinetics and the equilibrium isotherms: a positive component which is associated with the adsorption of H2 onto a clean Fe surface, and a negative component which was correlated with the presence of the chemisorbed oxygen. The resistance change isotherms can be fit with a model which assumes that each of the resistance change components result from dissociative chemisorbed hydrogen. Possible mechanisms for the chemisorbed-oxygen-induced negative resistance change are discussed.

Evaluation of the physi- and chemisorption of hydrogen in alkali (Na, Li) doped fullerenes

DOE PAGES

Ward, Patrick A.; Teprovich, Jr., Jospeph A.; Compton, Robert N.; ...

2015-01-11

Here, alkali doped fullerenes synthesized by two different solvent assisted mixing techniques are compared for their hydrogen uptake activity. In this study we investigated the interaction of hydrogen with alkali doped fullerenes via physisorption. In addition, we present the first mass spectrometric evidence for the formation of C 60H 60 via chemisorption. Hydrogen physisorption isotherms up to 1 atm at temperatures ranging from 77-303 K were measured demonstrating an increase in hydrogen uptake versus pure C 60 and increased isosteric heats of adsorption for the lithium doped fullerene Li 12C 60. However, despite these improvements the low amount of physisorbedmore » hydrogen at 1 atm and 77 K in these materials suggests that fullerenes do not possess enough accessible surface area to effectively store hydrogen due to their close packed crystalline nature.« less

Influence of preadsorbed oxygen on activated chemisorption of methane on Pd(110)

NASA Astrophysics Data System (ADS)

Valden, M.; Pere, J.; Xiang, N.; Pessa, M.

1996-07-01

Dissociative chemisorption of methane on clean and oxygen modified Pd(110) has been studied by using molecular beam surface scattering. The absolute dissociation probability of CH 4 ( Stot) is found to increase exponentially with the incident normal energy ( En) of CH 4 and with surface temperature ( TS) on clean Pd(110). The kinetic isotope effect is also found; namely, Stot of CD 4 is 4 to 5 times smaller than Stot of CH 4 throughout the entire range of En studied. These results are consistent with a direct dissociation mechanism. Measurements on preadsorbed oxygen on Pd(110) show that Stot of CH 4 decreases linearly, as oxygen coverage is increased from 0 to 0.4 ML in good agreement with the first-order Langmuir kinetics when approximately two active sites are blocked by one oxygen atom. No influence of the oxygen induced surface reconstructions on the dissociative adsorption kinetics of CH 4 is observed.

Understanding the role of thiol and disulfide self-assembled DNA receptor monolayers for biosensing applications.

PubMed

Carrascosa, Laura G; Martínez, Lidia; Huttel, Yves; Román, Elisa; Lechuga, Laura M

2010-09-01

A detailed study of the immobilization of three differently sulfur-modified DNA receptors for biosensing applications is presented. The three receptors are DNA-(CH)n-SH-, DNA-(CH)n-SS-(CH)n-DNA, and DNA-(CH)n-SS-DMTO. Nanomechanical and surface plasmon resonance biosensors and fluorescence and radiolabelling techniques were used for the experimental evaluation. The results highlight the critical role of sulfur linker type in DNA self-assembly, affecting the kinetic adsorption and spatial distribution of DNA chains within the monolayer and the extent of chemisorption and physisorption. A spacer (mercaptohexanol, MCH) is used to evaluate the relative efficiencies of chemisorption of the three receptors by analysing the extent to which MCH can remove physisorbed molecules from each type of monolayer. It is demonstrated that -SH derivatization is the most suitable for biosensing purposes as it results in densely packed monolayers with the lowest ratio of physisorbed probes.

A Hybrid Density Functional Study of Atomic Hydrogen and Oxygen Adsorptions on the (0001) Surface of Non-Magnetic DHCP Americium

NASA Astrophysics Data System (ADS)

Amdani-Moten, Shafaq; Atta-Fynn, Raymond; Ray, Asok

2010-03-01

As our group have recently shown^+, hybrid density functional theory (HDFT) which replaces a fraction (40%) of approximate DFT exchange with exact Hartree-Fock exchange yield structural, magnetic, and electronic properties for Americium-I that are in excellent agreement with experimental data. As a natural progression, ab initio calculations for atomic adsorptions on the (0001) surface of non-magnetic americium have been performed using HDFT. The americium surface is modeled by a seven-layer slab using inversion symmetry consisting of one atom per layer and non-magnetic ABAC stacking arrangement of these layers. Top, bridge, hcp and fcc chemisorption sites have been investigated with energies optimized with respect to the adatom distance from the surface. Details of the chemisorptions processes as well as comparisons of different sites will be presented. ^+ R. Atta-Fynn and A. K. Ray, Chemical Physics Letters, 482, 223-227 (2009).

Molecular simulation of CO chemisorption on Co(0001) in presence of supercritical fluid solvent: A potential of mean force study

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

Asiaee, Alireza; Benjamin, Kenneth M., E-mail: kenneth.benjamin@sdsmt.edu

2016-08-28

For several decades, heterogeneous catalytic processes have been improved through utilizing supercritical fluids (SCFs) as solvents. While numerous experimental studies have been established across a range of chemistries, such as oxidation, pyrolysis, amination, and Fischer-Tropsch synthesis, still there is little fundamental, molecular-level information regarding the role of the SCF on elementary heterogeneous catalytic steps. In this study, the influence of hexane solvent on the adsorption of carbon monoxide on Co(0001), as the first step in the reaction mechanism of many processes involving syngas conversion, is probed. Simulations are performed at various bulk hexane densities, ranging from ideal gas conditions (nomore » SCF hexane) to various near- and super-critical hexane densities. For this purpose, both density functional theory and molecular dynamics simulations are employed to determine the adsorption energy and free energy change during CO chemisorption. Potential of mean force calculations, utilizing umbrella sampling and the weighted histogram analysis method, provide the first commentary on SCF solvent effects on the energetic aspects of the chemisorption process. Simulation results indicate an enhanced stability of CO adsorption on the catalyst surface in the presence of supercritical hexane within the reduced pressure range of 1.0–1.5 at a constant temperature of 523 K. Furthermore, it is shown that the maximum stability of CO in the adsorbed state as a function of supercritical hexane density at 523 K nearly coincides with the maximum isothermal compressibility of bulk hexane at this temperature.« less

Adsorption Energies of Carbon, Nitrogen, and Oxygen Atoms on the Low-temperature Amorphous Water Ice: A Systematic Estimation from Quantum Chemistry Calculations

NASA Astrophysics Data System (ADS)

Shimonishi, Takashi; Nakatani, Naoki; Furuya, Kenji; Hama, Tetsuya

2018-03-01

We propose a new simple computational model to estimate the adsorption energies of atoms and molecules to low-temperature amorphous water ice, and we present the adsorption energies of carbon (3 P), nitrogen (4 S), and oxygen (3 P) atoms based on quantum chemistry calculations. The adsorption energies were estimated to be 14,100 ± 420 K for carbon, 400 ± 30 K for nitrogen, and 1440 ± 160 K for oxygen. The adsorption energy of oxygen is consistent with experimentally reported values. We found that the binding of a nitrogen atom is purely physisorption, while that of a carbon atom is chemisorption, in which a chemical bond to an O atom of a water molecule is formed. That of an oxygen atom has a dual character, with both physisorption and chemisorption. The chemisorption of atomic carbon also implies the possibility of further chemical reactions to produce molecules bearing a C–O bond, though this may hinder the formation of methane on water ice via sequential hydrogenation of carbon atoms. These properties would have a large impact on the chemical evolution of carbon species in interstellar environments. We also investigated the effects of newly calculated adsorption energies on the chemical compositions of cold dense molecular clouds with the aid of gas-ice astrochemical simulations. We found that abundances of major nitrogen-bearing molecules, such as N2 and NH3, are significantly altered by applying the calculated adsorption energy, because nitrogen atoms can thermally diffuse on surfaces, even at 10 K.

Removal of element mercury by medicine residue derived biochars in presence of various gas compositions.

PubMed

Li, Guoliang; Shen, Boxiong; Li, Yongwang; Zhao, Bin; Wang, Fumei; He, Chuan; Wang, Yinyin; Zhang, Min

2015-11-15

Pyrolyzed biochars from an industrial medicinal residue waste were modified by microwave activation and NH4Cl impregnation. Mercury adsorption of different modified biochars was investigated in a quartz fixed-bed reactor. The results indicated that both physisorption and chemisorption of Hg(0) occurred on the surface of M6WN5 which was modified both microwave and 5wt.% NH4Cl loading, and exothermic chemisorption process was a dominant route for Hg(0) removal. Microwave activation improved pore properties and NH4Cl impregnation introduced good active sites for biochars. The presence of NO and O2 increased Hg(0) adsorption whereas H2O inhibited Hg(0) adsorption greatly. A converse effect of SO2 was observed on Hg(0) removal, namely, low concentration of SO2 promoted Hg(0) removal obviously whereas high concentration of SO2 suppressed Hg(0) removal. The Hg(0) removal by M6WN5 was mainly due to the reaction of the C−Cl with Hg(0) to form HgCl2, and the active state of C−Cl(*) groups might be an intermediate group in this process. Thermodynamic analysis showed that mercury adsorption by the biochars was exothermic process and apparent adsorption energy was 43.3 kJ/mol in the range of chemisorption. In spite of low specific surface area, M6WN5 proved to be a promising Hg(0) sorbent in flue gas when compared with other sorbents. Copyright © 2015. Published by Elsevier B.V.

Silver-Loaded Aluminosilicate Aerogels As Iodine Sorbents

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

Riley, Brian J.; Kroll, Jared O.; Peterson, Jacob A.

This paper discusses the development of aluminosilicates aerogels as scaffolds for Ag0 nanoparticles used for chemisorption of I2(g). The starting materials for these scaffolds included both Na-Al-Si-O and Al-Si-O aerogels, both synthesized from metal alkoxides. The Ag0 particles are added by soaking the aerogels in AgNO3 followed by drying and flowing under H2/Ar to reduce Ag+ → Ag0. In some cases, samples were soaked in 3-(mercaptopropyl)trimethoxysilane under supercritical CO2 to add –SH tethers to the aerogel surfaces for more effective binding of Ag+. During the Ag+-impregnation steps, for the Na-Al-Si-O aerogels, Na was replaced with Ag, and for the Al-Si-Omore » aerogel, Si was replaced with Ag. The Ag-loading of thiolated versus non-thiolated Na-Al-Si-O aerogels was comparable at ~35 at% whereas the Ag-loading in unthiolated Al-Si-O aerogels was significantly lower at ~ 7 at% after identical treatment. Iodine loadings in both thiolated and unthiolated Ag0-functionalized Na-Al-Si-O aerogels were > 0.5 g g-1 showing almost complete utilization of the Ag through chemisorption to form AgI. Iodine loading in the thiolated Al-Si-O aerogel was 0.31 g g-1. The control of Ag uptake over solution residence time and [AgNO3] demonstrates the ability to customize the Ag-loading in the base sorbent to regulate the capacity of iodine chemisorption. Consolidation experimental results are also presented.« less

Surface-Electrochemical Sensor for the Measurement of Anti-Cholinesterase Activity

NASA Astrophysics Data System (ADS)

Matsuura, Hiroaki; Sato, Yukari; Yabuki, Soichi; Sawaguchi, Takahiro; Mizutani, Fumio

An organophosphorus pesticide, ethylthiometon (0.01-0.2 ppm) was determined by using a surface-electrochemical sensor system: the monolayer formation (chemisorption)-reductive desorption of thiocholine was applied to monitor the activity change of cholinesterase caused by the pesticide.

Understanding oxygen adsorption on 9.375 at. % Ga-stabilized δ-Pu (111) surface: A DFT study

DOE PAGES

Hernandez, Sarah C.; Wilkerson, Marianne P.; Huda, Muhammad N.

2015-08-30

Plutonium (Pu) metal reacts rapidly in the presence of oxygen (O), resulting in an oxide layer that will eventually have an olive green rust appearance over time. Recent experimental work suggested that the incorporation of gallium (Ga) as an alloying impurity to stabilize the highly symmetric high temperature δ-phase lattice may also provide resistance against corrosion/oxidation of plutonium. In this paper, we modeled a 9.375 at. % Ga stabilized δ-Pu (111) surface and investigated adsorption of atomic O using all-electron density functional theory. Key findings revealed that the O bonded strongly to a Pu-rich threefold hollow fcc site with amore » chemisorption energy of –5.06 eV. Migration of the O atom to a Pu-rich environment was also highly sensitive to the surface chemistry of the Pu–Ga surface; when the initial on-surface O adsorption site included a bond to a nearest neighboring Ga atom, the O atom relaxed to a Ga deficient environment, thus affirming the O preference for Pu. Only one calculated final on-surface O adsorption site included a Ga-O bond, but this chemisorption energy was energetically unfavorable. Chemisorption energies for interstitial adsorption sites that included a Pu or Pu-Ga environment suggested that over-coordination of the O atom was energetically unfavorable as well. Electronic structure properties of the on-surface sites, illustrated by the partial density of states, implied that the Ga 4p states indirectly but strongly influenced the Pu 6d states strongly to hybridize with the O 2p states, while also weakly influenced the Pu 5f states to hybridize with the O 2p states, even though Ga was not participating in bonding with O.« less

Influence of surface chemistry of carbon materials on their interactions with inorganic nitrogen contaminants in soil and water.

PubMed

Sumaraj; Padhye, Lokesh P

2017-10-01

Inorganic nitrogen contaminants (INC) (NH 4 + , NO 3 - , NO 2 - , NH 3 , NO, NO 2 , and N 2 O) pose a growing risk to the environment, and their remediation methods are highly sought after. Application of carbon materials (CM), such as biochar and activated carbon, to remediate INC from agricultural fields and wastewater treatment plants has gained a significant interest since past few years. Understanding the role of surface chemistry of CM in adsorption of various INC is highly critical to increase adsorption efficiency as well as to assess the long term impact of using these highly recalcitrant CM for remediation of INC. Critical reviews of adsorption studies related to INC have revealed that carbon surface chemistry (surface functional groups, pH, Eh, elemental composition, and mineral content) has significant influence on adsorption of INC. Compared to basic functional groups, oxygen containing surface functional groups have been found to be more influential for adsorption of INC. However, basic sites on carbon materials still play an important role in chemisorption of anionic INC. Apart from surface functional groups, pH, Eh and pH zpc of CM and elemental and mineral composition of its surface are important properties capable of altering INC interactions with CM. This review summarizes our current understanding of INC interactions with CM's surface through the known chemisorption mechanisms: electrostatic interaction, hydrogen bonding, electron donor-acceptor mechanism, hydrophobic and hydrophilic interaction, chemisorption aided by minerals, and interactions influenced by pH and elemental composition. Change in surface chemistry of CM in soil during aging is also discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Mechanistic understanding of crystal violet dye sorption by woody biochar: implications for wastewater treatment.

PubMed

Wathukarage, Awanthi; Herath, Indika; Iqbal, M C M; Vithanage, Meththika

2017-08-17

Dye-based industries, particularly small and medium scale, discharge their effluents into waterways without treatment due to cost considerations. We investigated the use of biochars produced from the woody tree Gliricidia sepium at 300 °C (GBC300) and 500 °C (GBC500) in the laboratory and at 700 °C from a dendro bioenergy industry (GBC700), to evaluate their potential for sorption of crystal violet (CV) dye. Experiments were conducted to assess the effect of pH reaction time and CV loading on the adsorption process. The equilibrium adsorption capacity was higher with GBC700 (7.9 mg g -1 ) than GBC500 (4.9 mg g -1 ) and GBC300 (4.4 mg g -1 ), at pH 8. The CV sorption process was dependent on the pH, surface area and pore volume of biochar (GBC). Both Freundlich and Hill isotherm models fitted best to the equilibrium isotherm data suggesting cooperative interactions via physisorption and chemisorption mechanisms for CV sorption. The highest Hill sorption capacity of 125.5 mg g -1 was given by GBC700 at pH 8. Kinetic data followed the pseudo-second-order model, suggesting that the sorption process is more inclined toward the chemisorption mechanism. Pore diffusion, π-π electron donor-acceptor interaction and H-bonding were postulated to be involved in physisorption, whereas electrostatic interactions of protonated amine group of CV and negatively charged GBC surface led to a chemisorption type of adsorption. Overall, GBC produced as a by-product of the dendro industry could be a promising remedy for CV removal from an aqueous environment.

Understanding oxygen adsorption on 9.375 at. % Ga-stabilized δ-Pu (111) surface: A DFT study

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

Hernandez, Sarah C.; Wilkerson, Marianne P.; Huda, Muhammad N.

Plutonium (Pu) metal reacts rapidly in the presence of oxygen (O), resulting in an oxide layer that will eventually have an olive green rust appearance over time. Recent experimental work suggested that the incorporation of gallium (Ga) as an alloying impurity to stabilize the highly symmetric high temperature δ-phase lattice may also provide resistance against corrosion/oxidation of plutonium. In this paper, we modeled a 9.375 at. % Ga stabilized δ-Pu (111) surface and investigated adsorption of atomic O using all-electron density functional theory. Key findings revealed that the O bonded strongly to a Pu-rich threefold hollow fcc site with amore » chemisorption energy of –5.06 eV. Migration of the O atom to a Pu-rich environment was also highly sensitive to the surface chemistry of the Pu–Ga surface; when the initial on-surface O adsorption site included a bond to a nearest neighboring Ga atom, the O atom relaxed to a Ga deficient environment, thus affirming the O preference for Pu. Only one calculated final on-surface O adsorption site included a Ga-O bond, but this chemisorption energy was energetically unfavorable. Chemisorption energies for interstitial adsorption sites that included a Pu or Pu-Ga environment suggested that over-coordination of the O atom was energetically unfavorable as well. Electronic structure properties of the on-surface sites, illustrated by the partial density of states, implied that the Ga 4p states indirectly but strongly influenced the Pu 6d states strongly to hybridize with the O 2p states, while also weakly influenced the Pu 5f states to hybridize with the O 2p states, even though Ga was not participating in bonding with O.« less

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

Calo, J.M.; Suuberg, E.M.; Hradil, G.

This project is concerned with the study of the nature and behavior of ''active sites'' in char gasification. The research strategy involves use of model chars produced from the phenol-formaldehyde family of resins. These materials have been chosen since they have structural features similar to those in coals, but are much ''cleaner'' in that the concentration of potentially catalytic impurities can be maintained at low levels. It should be borne in mind that the objective of this work is to study non-catalytic gasification processes. In the previous quarterly report, we presented evidence that low temperature oxygen chemisorption does not providemore » a site-specific titration of active sites in chars; the uptake of oxygen by a cleaned char surface was unquestionably shown to be a function of temperature and oxygen partial pressure, and the importance of these variables differs from char to char. The fact that ''active surface area'' (ASA) determined by various arbitrary methods does seem to generally correlate with reactivity, seems to suggest that reactivities under various gasification and chemisorption conditions are correlated but that mechanisitic inferences cannot necessarily be drawn from such data. In the present report, we have extended the study of low temperature oxidation of chars, considering mass loss as well as oxygen uptake, since the two processes are essentially inseparable under a wide range of conditions. This work represents more than a simple attempt at trying to learn more about the oxygen chemisorption technique; rather it offers the opportunity to study the mechanism of oxygen attack on char under conditions that allow for better understanding of the fundamental processes. For these reasons, this work was performed in the pyrogasifier reactor (developed for CO/sub 2/ gasification reactivity studies), and complements the ongoing work in the TGA apparatus. 6 refs., 9 figs., 1 tab.« less

Island morphology statistics and growth mechanism for oxidation of the Al(111) surface with thermal O2 and NO

NASA Astrophysics Data System (ADS)

Sexton, J. Z.; Kummel, A. C.

2004-10-01

Scanning tunneling microscopy (STM) was employed to study the mechanism for the oxidation of Al(111) with thermal O2 and NO in the 20%-40% monolayer coverage regime. Experiments show that the islands formed upon exposure to thermal O2 and NO have dramatically different shapes, which are ultimately dictated by the dynamics of the gas surface interaction. The circumference-to-area ratio and other island morphology statistics are used to quantify the average difference in the two island types. Ultrahigh-vacuum STM was employed to make the following observations: (1) Oxygen islands on the Al(111) surface, formed upon exposure to thermal oxygen, are elongated and noncompact. (2) Mixed O/N islands on the Al(111) surface, formed upon exposure to thermal nitric oxide (NO), are round and compact. (3) STM movies acquired during thermal O2 exposure indicate that a complex mechanism involving chemisorption initiated rearrangement of preexisting oxygen islands leads to the asymmetric and elongated island shapes. The overall mechanism for the oxidation of the Al(111) surface can be summarized in three regimes. Low coverage is dominated by widely isolated small oxygen features (<3 O atoms) where normal dissociative chemisorption and oxygen abstraction mechanisms are present. At 20%-40% monolayer coverage, additional oxygen chemisorption induces rearrangement of preexisting islands to form free-energy minimum island shapes. At greater than ˜40% monolayer coverage, the apparent surface oxygen coverage asymptotes corresponding to the conversion of the 2D islands to 3D Al2O3 surface crystallites. The rearrangement of oxygen islands on the surface to form the observed islands indicates that there is a short-range oxygen-oxygen attractive potential and a long-range oxygen-oxygen repulsive potential.

Fabrication and testing of low-temperature catalytically active washcoat materials for next-generation vehicle catalytic converters.

DOT National Transportation Integrated Search

2014-01-01

With funds from this grant, Youngstown State University has purchased a : Quantachrome iQ Chemisorption Analyzer and built a Chemical Reactor with Gas : Chromatographer for catalyst characterization. PI has been involved in the purchase and : install...

Surface composition of alloys

NASA Astrophysics Data System (ADS)

Sachtler, W. M. H.

1984-11-01

In equilibrium, the composition of the surface of an alloy will, in general, differ from that of the bulk. The broken-bond model is applicable to alloys with atoms of virtually equal size. If the heat of alloy formation is zero, the component of lower heat of atomization is found enriched in the surface. If both partners have equal heats of sublimination, the surface of a diluted alloy is enriched with the minority component. Size effects can enhance or weaken the electronic effects. In general, lattice strain can be relaxed by precipitating atoms of deviating size on the surface. Two-phase alloys are described by the "cherry model", i.e. one alloy phase, the "kernel" is surrounded by another alloy, the "flesh", and the surface of the outer phase, the "skin" displays a deviating surface composition as in monophasic alloys. In the presence of molecules capable of forming chemical bonds with individual metal atoms, "chemisorption induced surface segregation" can be observed at low temperatures, i.e. the surface becomes enriched with the metal forming the stronger chemisorption bonds.

Local resonances in STM manipulation of chlorobenzene on Si(111)-7×7: performance of different cluster models and density functionals

NASA Astrophysics Data System (ADS)

Utecht, Manuel; Klamroth, Tillmann

2018-07-01

Hot localised charge carriers on the Si(111)-7×7 surface are modelled by small charged clusters. Such resonances induce non-local desorption, i.e. more than 10 nm away from the injection site, of chlorobenzene in scanning tunnelling microscope experiments. We used such a cluster model to characterise resonance localisation and vibrational activation for positive and negative resonances recently. In this work, we investigate to which extent the model depends on details of the used cluster or quantum chemistry methods and try to identify the smallest possible cluster suitable for a description of the neutral surface and the ion resonances. Furthermore, a detailed analysis for different chemisorption orientations is performed. While some properties, as estimates of the resonance energy or absolute values for atomic changes, show such a dependency, the main findings are very robust with respect to changes in the model and/or the chemisorption geometry.

Facilitated Oxygen Chemisorption in Heteroatom-Doped Carbon for Improved Oxygen Reaction Activity in All-Solid-State Zinc-Air Batteries.

PubMed

Liu, Sisi; Wang, Mengfan; Sun, Xinyi; Xu, Na; Liu, Jie; Wang, Yuzhou; Qian, Tao; Yan, Chenglin

2018-01-01

Driven by the intensified demand for energy storage systems with high-power density and safety, all-solid-state zinc-air batteries have drawn extensive attention. However, the electrocatalyst active sites and the underlying mechanisms occurring in zinc-air batteries remain confusing due to the lack of in situ analytical techniques. In this work, the in situ observations, including X-ray diffraction and Raman spectroscopy, of a heteroatom-doped carbon air cathode are reported, in which the chemisorption of oxygen molecules and oxygen-containing intermediates on the carbon material can be facilitated by the electron deficiency caused by heteroatom doping, thus improving the oxygen reaction activity for zinc-air batteries. As expected, solid-state zinc-air batteries equipped with such air cathodes exhibit superior reversibility and durability. This work thus provides a profound understanding of the reaction principles of heteroatom-doped carbon materials in zinc-air batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improved sensitivity of polychlorinated-biphenyl-orientated porous-ZnO surface photovoltage sensors from chemisorption-formed ZnO-CuPc composites

PubMed Central

Li, Mingtao; Meng, Guowen; Huang, Qing; Zhang, Shile

2014-01-01

We report a new mechanism for the enhancement of porous-ZnO surface photovoltage (SPV) response to polychlorinated biphenyls (PCBs, a notorious class of persistent organic pollutants as global environmental hazard) based on copper phthalocyanine (CuPc) chemisorptive bonding on porous-ZnO. A new ZnO-CuPc composite is formed on the porous-ZnO surface due to the interaction between the surface ZnO and CuPc, with its valence band (VB) energy level being higher than that of the pristine porous-ZnO. So that the efficiency of the photogenerated-electron transfer from the composite VB to the adjacent ZnO's surface states is drastically increased due to the reduced energy gap between the transition states. As a result, the sensitivity of the PCB-orientated SPV sensor is much improved by showing amplified variation of the SPV-signals perturbed by PCBs adsorbed on the ZnO-CuPc@porous-ZnO sensitive material. PMID:24594662

Adsorptive removal of Congo red from aqueous solutions using crosslinked chitosan and crosslinked chitosan immobilized bentonite.

PubMed

Huang, Ruihua; Zhang, Lujie; Hu, Pan; Wang, Jing

2016-05-01

Batch experiments were executed to investigate the removal of Congo red (CR) from aqueous solutions using the crosslinked chitosan (CCS) and crosslinked chitosan immobilized bentonite (CCS/BT composite). The CCS and CCS/BT composite were characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) techniques. The removal of CR was examined as a function of pH value of CR solution, contact time, and inorganic sodium salt and ionic strength. The equilibrium data of CCS and CCS/BT composite agreed well with the Langmuir model. The adsorption capacities of CCS and CCS/BT composite at 298K and natural pH value were 405 and 500 mg/g, respectively. The kinetic data correlated well with the pseudo-second-order model. The adsorption of CR onto the CCS was mainly controlled by chemisorption while the adsorption of CR onto the CCS/BT composite was controlled by chemisorption and the electrostatic attraction. Copyright © 2016 Elsevier B.V. All rights reserved.

A comparative study of thermochemical and cold plasma treatment on lignin-based activated carbon for adsorbing Fe(III)

NASA Astrophysics Data System (ADS)

Shi, Shukai; Wang, Xin; Chen, Weimin; Chen, Minzhi; Zhou, Xiaoyan

2018-05-01

The as-prepared lignin-based activated carbon (LAC) was post-treated by urea and radio-frequency cold plasma separately. The obtained results demonstrated that the BET surface and total volumes of the LAC and plasma-treated LACs were greater than the urea-modified sample. The analysis of surface elemental composition showed that the nitrogen content of urea-modified LAC and nitrogen plasma-treated LAC are 3.79% and 2.62% higher than that of original LAC respectively, while the oxygen content of air plasma-treated LAC is 10.23% higher than that of original LAC. The Fe(III) ions adsorbed studies with pseudo-second order kinetic model revealed that urea-modified LAC had faster chemisorption rates while air plasma-treated LAC had larger adsorption capacity within 3 h. Moreover, the adsorption capacity and chemisorption rates of LAC post-treated by nitrogen plasma are inferior to the air plasma-treated LAC.

1,3,5-trinitro-1,3,5-triazine decomposition and chemisorption on Al(111) surface: first-principles molecular dynamics study.

PubMed

Umezawa, Naoto; Kalia, Rajiv K; Nakano, Aiichiro; Vashista, Priya; Shimojo, Fuyuki

2007-06-21

We have investigated the decomposition and chemisorption of a 1,3,5-trinitro-1,3,5-triazine (RDX) molecule on Al(111) surface using molecular dynamics simulations, in which interatomic forces are computed quantum mechanically in the framework of the density functional theory (DFT). The real-space DFT calculations are based on higher-order finite difference and norm-conserving pseudopotential methods. Strong attractive forces between oxygen and aluminum atoms break N-O and N-N bonds in the RDX and, subsequently, the dissociated oxygen atoms and NO molecules oxidize the Al surface. In addition to these Al surface-assisted decompositions, ring cleavage of the RDX molecule is also observed. These reactions occur spontaneously without potential barriers and result in the attachment of the rest of the RDX molecule to the surface. This opens up the possibility of coating Al nanoparticles with RDX molecules to avoid the detrimental effect of oxidation in high energy density material applications.

Interaction of hydrogen with palladium clusters deposited on graphene

NASA Astrophysics Data System (ADS)

Alonso, Julio A.; Granja, Alejandra; Cabria, Iván; López, María J.

2015-12-01

Hydrogen adsorption on nanoporous carbon materials is a promising technology for hydrogen storage. However, pure carbon materials do not meet the technological requirements due to the week binding of hydrogen to the pore walls. Experimental work has shown that doping with Pd atoms and clusters enhances the storage capacity of porous carbons. Therefore, we have investigated the role played by the Pd dopant on the enhancement mechanisms. By performing density functional calculations, we have found that hydrogen adsorbs on Pd clusters deposited on graphene following two channels, molecular adsorption and dissociative chemisorption. However, desorption of Pd-H complexes competes with desorption of hydrogen, and consequently desorption of Pd-H complexes would spoil the beneficial effect of the dopant. As a way to overcome this difficulty, Pd atoms and clusters can be anchored to defects of the graphene layer, like graphene vacancies. The competition between molecular adsorption and dissociative chemisorption of H2 on Pd6 anchored on a graphene vacancy has been studied in detail.

Chemical trends of Schottky barrier behavior on monolayer hexagonal B, Al, and Ga nitrides

NASA Astrophysics Data System (ADS)

Lu, Haichang; Guo, Yuzheng; Robertson, John

2016-08-01

The Schottky Barrier Heights (SBH) of metal layers on top of monolayer hexagonal X-nitrides (X = B, Al, Ga, and h-XN) are calculated using supercells and density functional theory so as to understand the chemical trends of contact formation on graphene and the 2D layered semiconductors such as the transition metal dichalcogenides. The Fermi level pinning factor S of SBHs on h-BN is calculated to be nearly 1, indicating no pinning. For h-AlN and h-GaN, the calculated pinning factor is about 0.63, less than for h-BN. We attribute this to the formation of stronger, chemisorptive bonds between the nitrides and the contact metal layer. Generally, the h-BN layer remains in a planar sp2 geometry and has weak physisorptive bonds to the metals, whereas h-AlN and h-GaN buckle out of their planar geometry which enables them to form the chemisorptive bonds to the metals.

PREPARATION, CHARACTERIZATION AND ACTIVITY OF AL2O3-SUPPORTED V2O5 CATALYSTS

EPA Science Inventory

A series of activated alumina supported vanadium oxide catalysts with various V2O5 loadings ranging from 5 to 25 wt% has been prepared by wet impregnation technique. A combination of various physico-chemical techniques such as BET surface areas, oxygen chemisorption, X-ray diffra...

Investigation of catalytic reduction and filter techniques for simultaneous measurements of NO, NO2, and HNO3 in the stratosphere

NASA Technical Reports Server (NTRS)

Wendt, J.; Fabian, Peter; Flentje, G.; Kourtidis, K.

1994-01-01

A concept for measuring stratospheric NOy-species is presented which utilizes the catalytic reduction of NO2 and HNO3 over heated metal catalysts and the chemisorption of HNO3 on Nylon. Using the Max Planck Institute for Aeronomy (MPAE) chemiluminescent balloon-borne sonde, stratospheric NO and NO2 profiles have been measured since 1983. NO is detected by chemiluminescence produced in reaction with O3 while NO2 needs first to be converted to NO over a heated stainless steel catalyst. To improve this technique for simultaneously measuring HNO3, the catalytic reduction of NO2 and HNO3 over several metal catalysts and the chemisorption of NO2 and HNO3 on Nylon have been investigated in laboratory tests. The results of these tests under simulated stratospheric conditions are presented in detail in this paper. They demonstrate that the simultaneous measurement of NO, NO2 and HNO3 is indeed possible with the combination of stainless steel or Au as a catalyst and a nylon filter.

Electrophilic surface sites as precondition for the chemisorption of pyrrole on GaAs(001) surfaces

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

Bruhn, Thomas; Leibniz-Institut für Analytische Wissenschaften - ISAS - e.V., Albert-Einstein-Str.9, 12489 Berlin; Fimland, Bjørn-Ove

We report how the presence of electrophilic surface sites influences the adsorption mechanism of pyrrole on GaAs(001) surfaces. For this purpose, we have investigated the adsorption behavior of pyrrole on different GaAs(001) reconstructions with different stoichiometries and thus different surface chemistries. The interfaces were characterized by x-ray photoelectron spectroscopy, scanning tunneling microscopy, and by reflectance anisotropy spectroscopy in a spectral range between 1.5 and 5 eV. On the As-rich c(4 × 4) reconstruction that exhibits only nucleophilic surface sites, pyrrole was found to physisorb on the surface without any significant modification of the structural and electronic properties of the surface. Onmore » the Ga-rich GaAs(001)-(4 × 2)/(6 × 6) reconstructions which exhibit nucleophilic as well as electrophilic surface sites, pyrrole was found to form stable covalent bonds mainly to the electrophilic (charge deficient) Ga atoms of the surface. These results clearly demonstrate that the existence of electrophilic surface sites is a crucial precondition for the chemisorption of pyrrole on GaAs(001) surfaces.« less

A quantum chemistry study on surface reactivity of pristine and carbon-substituted AlN nanotubes

NASA Astrophysics Data System (ADS)

Mahdaviani, Amir; Esrafili, Mehdi D.; Esrafili, Ali; Behzadi, Hadi

2013-09-01

A density functional theory investigation was performed to predict the surface reactivity of pristine and carbon-substituted (6,0) single-walled aluminum nitride nanotubes (AlNNTs). The properties determined include the electrostatic potentials VS(r) and average local ionization energies ĪS(r) on the surfaces of the investigated tubes. According to computed VS(r) results, the Al/N atoms in edge or cap regions show a different reactivity pattern than those at the middle portion of the tubes. Due to the carbon-substitution at the either Al or N sites of the tubes, the negative regions associated with nitrogen atoms are stronger than before. The prediction of surface reactivity and regioselectivity using average local ionization energies has been verified by atomic hydrogen chemisorption energies calculated for AlNNTs at the B3LYP/6-31 G* level. There is an acceptable correlation between the minima of ĪS(r) and the atomic hydrogen chemisorption energies, demonstrating that ĪS(r) provides an effective means for rapidly and economically assessing the relative reactivities of finite sized AlNNTs.

Photocatalytic oxidation mechanism of alkanes in contact with titanium dioxide

NASA Technical Reports Server (NTRS)

Formenti, M.; Juillet, F.; Teichner, S. J.

1977-01-01

Isobutane was photooxidized on titanium dioxide between -16 and +180 C in tertiary butanol and acetone. The formation of tertiary butanol preceded the formation of acetone. Above 20 C the latter compound became clearly predominant. The reaction kinetics obeyed a steady state model of oxygen chemisorption with the involvement of isobutane in the physisorbed phase.

Recent Studies of Chemical Interactions on Surfaces Using Molecular Beams

DTIC Science & Technology

1976-01-26

going to the mobile chemisorbed state. Procop and Volter report an entropy increase of about 20 cal/mole OK for hydrogen chemisorption on platinum, for...31. I) 35. A. George Stoll, Jr., Ph.D. Thsis, Depam t of Chmial Nagineering, U.C.B. 36. it. P. eiurr-., private commication. 0 37. N. Procop and J

Deposition on disordered substrates with precursor layer diffusion

NASA Astrophysics Data System (ADS)

Filipe, J. A. N.; Rodgers, G. J.; Tavassoli, Z.

1998-09-01

Recently we introduced a one-dimensional accelerated random sequential adsorption process as a model for chemisorption with precursor layer diffusion. In this paper we consider this deposition process on disordered or impure substrates. The problem is solved exactly on both the lattice and continuum and for various impurity distributions. The results are compared with those from the standard random sequential adsorption model.

Phosphorous removal from aqueous solution can be enhanced through the calcination of lime sludge.

PubMed

Bal Krishna, K C; Niaz, Mohamed R; Sarker, Dipok C; Jansen, Troy

2017-09-15

Water treatment plants generate an enormous amount of the sludge which is normally treated as waste. In the recent past, many investigations have been focused on developing an economical adsorbent using water treatment sludge to remove phosphorous (P) from aqueous solutions. However, the great extents of the studies have been limited in the use of alum- and iron-based sludges. This study, therefore, investigated the P removal performance of the calcined lime sludge. Calcined lime sludge at 700 °C significantly enhanced the P removal efficiency whereas marginal improvement was noted when the sludge calcined at 400 °C was tested. With increase P removal efficiency, final pH values of the solution also significantly increased. P removal efficiency of the calcined sludge decreased with increasing the initial P concentrations. However, the removal efficiency could be improved by increasing the weight of the sludge. Further analysis demonstrated that P removal trend followed both pseudo-second order and diffusion-chemisorption kinetics signifying the P removal is potentially due to a multi-mechanistic reaction in which, the process is controlled by intra-particle diffusion followed by chemisorptions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Alkali Metal CO2 Sorbents and the Resulting Metal Carbonates: Potential for Process Intensification of Sorption-Enhanced Steam Reforming.

PubMed

Memon, Muhammad Zaki; Zhao, Xiao; Sikarwar, Vineet Singh; Vuppaladadiyam, Arun K; Milne, Steven J; Brown, Andy P; Li, Jinhui; Zhao, Ming

2017-01-03

Sorption-enhanced steam reforming (SESR) is an energy and cost efficient approach to produce hydrogen with high purity. SESR makes it economically feasible to use a wide range of feedstocks for hydrogen production such as methane, ethanol, and biomass. Selection of catalysts and sorbents plays a vital role in SESR. This article reviews the recent research aimed at process intensification by the integration of catalysis and chemisorption functions into a single material. Alkali metal ceramic powders, including Li 2 ZrO 3 , Li 4 SiO 4 and Na 2 ZrO 3 display characteristics suitable for capturing CO 2 at low concentrations (<15% CO 2 ) and high temperatures (>500 °C), and thus are applicable to precombustion technologies such as SESR, as well as postcombustion capture of CO 2 from flue gases. This paper reviews the progress made in improving the operational performance of alkali metal ceramics under conditions that simulate power plant and SESR operation, by adopting new methods of sorbent synthesis and doping with additional elements. The paper also discusses the role of carbonates formed after in situ CO 2 chemisorption during a steam reforming process in respect of catalysts for tar cracking.

Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH 4 on Pt(111)

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

Guo, Han; Jackson, Bret

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore CH 4 dissociation on Pt(111). Computed sticking probabilities for molecules in the ground, 1v 3 and 2v 3, states are in very good agreement with the available experimental data, reproducing the variation in reactivity with collision energy and vibrational state. As was found in similar studies on Ni(100) and Ni(111), exciting the 1v 1 symmetric stretch of CH 4 is more effective at promoting the dissociative chemisorption of CH 4 than exciting the 1v 3 antisymmetric stretch. This behavior is explained in terms of symmetry,more » mode-softening, and nonadiabatic transitions between vibrationally adiabatic states. We find that the efficacies of the bending modes for promoting reaction are reasonably large, and similar to the 1v 3 state. The vibrational efficacies for promoting reaction on Ni(111) are larger than for reaction on Pt(111), due to the larger nonadiabatic couplings. As a result, our computed sticking probabilities are in good agreement with results from recent ab initio molecular dynamics and reactive force field studies.« less

Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH{sub 4} on Pt(111)

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

Guo, Han; Jackson, Bret, E-mail: jackson@chem.umass.edu

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore CH{sub 4} dissociation on Pt(111). Computed sticking probabilities for molecules in the ground, 1v{sub 3} and 2v{sub 3}, states are in very good agreement with the available experimental data, reproducing the variation in reactivity with collision energy and vibrational state. As was found in similar studies on Ni(100) and Ni(111), exciting the 1v{sub 1} symmetric stretch of CH{sub 4} is more effective at promoting the dissociative chemisorption of CH{sub 4} than exciting the 1v{sub 3} antisymmetric stretch. This behavior is explained in terms of symmetry,more » mode-softening, and nonadiabatic transitions between vibrationally adiabatic states. We find that the efficacies of the bending modes for promoting reaction are reasonably large, and similar to the 1v{sub 3} state. The vibrational efficacies for promoting reaction on Ni(111) are larger than for reaction on Pt(111), due to the larger nonadiabatic couplings. Our computed sticking probabilities are in good agreement with results from recent ab initio molecular dynamics and reactive force field studies.« less

Low Temperature ABC-Type Ru Atomic Layer Deposition through Consecutive Dissociative Chemisorption, Combustion, and Reduction Steps

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

Lu, Junling; Elam, Jeffrey W.

Thermal atomic layer deposition (ALD) of noble metals is frequently performed using molecular oxygen as the nonmetal precursor to effect a combustion-type chemistry at relatively high temperatures of 300 °C. Bis(ethylcyclopentadienyl)ruthenium (Ru(EtCp)2) is one of the common used metal precursors for Ru ALD. Using Ru(EtCp)2 and oxygen as reactants, Ru ALD was acheived at near 300 °C. Here, we demonstrate that Ru ALD can proceed at as low as 150 °C by using successive exposures to oxygen and hydrogen as the co-reactants. In situ quartz crystal microbalance (QCM) and quadrupole mass spectroscopy (QMS) measurements both suggest that this ABC-type ALDmore » occurs through dissociative chemisorption, combustion, and reduction for the Ru(EtCp)2, oxygen and hydrogen steps, respectively, in a similar manner to processes using ozone and hydrogen as co-reactants reported previously. Moreover, we believe this molecular O2 and H2 based ABC-type ALD could be exploited for the ALD of other noble metals to decrease the deposition temperature and reduce oxygen impurities.« less

Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH 4 on Pt(111)

DOE PAGES

Guo, Han; Jackson, Bret

2016-05-13

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore CH 4 dissociation on Pt(111). Computed sticking probabilities for molecules in the ground, 1v 3 and 2v 3, states are in very good agreement with the available experimental data, reproducing the variation in reactivity with collision energy and vibrational state. As was found in similar studies on Ni(100) and Ni(111), exciting the 1v 1 symmetric stretch of CH 4 is more effective at promoting the dissociative chemisorption of CH 4 than exciting the 1v 3 antisymmetric stretch. This behavior is explained in terms of symmetry,more » mode-softening, and nonadiabatic transitions between vibrationally adiabatic states. We find that the efficacies of the bending modes for promoting reaction are reasonably large, and similar to the 1v 3 state. The vibrational efficacies for promoting reaction on Ni(111) are larger than for reaction on Pt(111), due to the larger nonadiabatic couplings. As a result, our computed sticking probabilities are in good agreement with results from recent ab initio molecular dynamics and reactive force field studies.« less

Modified energetics and growth kinetics on H-terminated GaAs (110)

NASA Astrophysics Data System (ADS)

Galiana, B.; Benedicto, M.; Díez-Merino, L.; Lorbek, S.; Hlawacek, G.; Teichert, C.; Tejedor, P.

2013-10-01

Atomic hydrogen modification of the surface energy of GaAs (110) epilayers, grown at high temperatures from molecular beams of Ga and As4, has been investigated by friction force microscopy (FFM). The reduction of the friction force observed with longer exposures to the H beam has been correlated with the lowering of the surface energy originated by the progressive de-relaxation of the GaAs (110) surface occurring upon H chemisorption. Our results indicate that the H-terminated GaAs (110) epilayers are more stable than the As-stabilized ones, with the minimum surface energy value of 31 meV/Å2 measured for the fully hydrogenated surface. A significant reduction of the Ga diffusion length on the H-terminated surface irrespective of H coverage has been calculated from the FFM data, consistent with the layer-by-layer growth mode and the greater As incorporation coefficient determined from real-time reflection high-energy electron diffraction studies. Arsenic incorporation through direct dissociative chemisorption of single As4 molecules mediated by H on the GaAs (110) surface has been proposed as the most likely explanation for the changes in surface kinetics observed.

DFT Study of PH3 Physisorption and Chemisorptions on Boron Nitride Nanotubes

NASA Astrophysics Data System (ADS)

Rakhshi, Mahdi; Mohsennia, Mohsen; Rasa, Hossein

2018-03-01

The adsorption of PH3 molecules on the NiB,N-doped(4,4) and (5,5) BNNTS surfaces has been investigated using density functional theory (DFT). The adsorption energies, geometric and electronic structures of the adsorbed systems were studied to judge the possible application of NiB,N-doped BNNTS in PH3 monitoring systems. Our calculated results showed that NiB,N-doped BNNTS had much higher adsorption energy and shorter binding distances than pure BNNTS owning to chemisorptions of the PH3 molecule. The obtained density of states (DOS) and frontier orbitals demonstrated that the orbital hybridization was obvious between the PH3 molecule and NiB,N-doped BNNTS. However, due to weak physisorption according to the total electron density maps, there was no evidence for hybridization between PH3 molecule and pure BNNTS. It was shown that after doping of Ni atom, the primary symmetry of BNNTS decreased which enhanced the chemical activity of BNNTS towards PH3 molecules. According to the obtained results, we highlight the high potential application of NiB,N-doped BNNTS in the design and fabrication of PH3 sensing devices.

Making Activated Carbon for Storing Gas

NASA Technical Reports Server (NTRS)

Wojtowicz, Marek A.; Serio, Michael A.; Suuberg, Eric M.

2005-01-01

Solid disks of microporous activated carbon, produced by a method that enables optimization of pore structure, have been investigated as means of storing gas (especially hydrogen for use as a fuel) at relatively low pressure through adsorption on pore surfaces. For hydrogen and other gases of practical interest, a narrow distribution of pore sizes <2 nm is preferable. The present method is a variant of a previously patented method of cyclic chemisorption and desorption in which a piece of carbon is alternately (1) heated to the lower of two elevated temperatures in air or other oxidizing gas, causing the formation of stable carbon/oxygen surface complexes; then (2) heated to the higher of the two elevated temperatures in flowing helium or other inert gas, causing the desorption of the surface complexes in the form of carbon monoxide. In the present method, pore structure is optimized partly by heating to a temperature of 1,100 C during carbonization. Another aspect of the method exploits the finding that for each gas-storage pressure, gas-storage capacity can be maximized by burning off a specific proportion (typically between 10 and 20 weight percent) of the carbon during the cyclic chemisorption/desorption process.

Evidence for Redox Mechanisms in Organometallic Chemisorption and Reactivity on Sulfated Metal Oxides

DOE PAGES

Klet, Rachel C.; Kaphan, David M.; Liu, Cong; ...

2018-04-09

The chemical and electronic interactions of organometallic species with metal oxide support materials are of fundamental importance for the development of new classes of catalytic materials. Chemisorption of Cp*(PMe 3)IrMe 2 on sulfated alumina (SA) and sulfated zirconia (SZ) led to an unexpected redox mechanism for deuteration of the ancillary Cp* ligand. Evidence for this oxidative mechanism was provided by studying the analogous homogeneous reactivity of the organometallic precursors toward trityl cation ([Ph 3C] +), a Lewis acid known to effect formal hydride abstraction by one-electron oxidation followed by hydrogen abstraction. Organometallic deuterium incorporation was found to be correlated withmore » surface sulfate concentration as well as the extent of dehydration under thermal activation conditions of SA and SZ supports. Surface sulfate concentration dependence, in conjunction with a computational study of surface electron affinity, indicates an electron-deficient pyrosulfate species as the redox-active moiety. Furthermore, these results provide further evidence for the ability of sulfated metal oxides to participate in redox chemistry not only toward organometallic complexes but also in the larger context of their application as catalysts for the transformation of light alkanes.« less

Evidence for Redox Mechanisms in Organometallic Chemisorption and Reactivity on Sulfated Metal Oxides

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

Klet, Rachel C.; Kaphan, David M.; Liu, Cong

The chemical and electronic interactions of organometallic species with metal oxide support materials are of fundamental importance for the development of new classes of catalytic materials. Chemisorption of Cp*(PMe 3)IrMe 2 on sulfated alumina (SA) and sulfated zirconia (SZ) led to an unexpected redox mechanism for deuteration of the ancillary Cp* ligand. Evidence for this oxidative mechanism was provided by studying the analogous homogeneous reactivity of the organometallic precursors toward trityl cation ([Ph 3C] +), a Lewis acid known to effect formal hydride abstraction by one-electron oxidation followed by hydrogen abstraction. Organometallic deuterium incorporation was found to be correlated withmore » surface sulfate concentration as well as the extent of dehydration under thermal activation conditions of SA and SZ supports. Surface sulfate concentration dependence, in conjunction with a computational study of surface electron affinity, indicates an electron-deficient pyrosulfate species as the redox-active moiety. Furthermore, these results provide further evidence for the ability of sulfated metal oxides to participate in redox chemistry not only toward organometallic complexes but also in the larger context of their application as catalysts for the transformation of light alkanes.« less

Gearing.

DTIC Science & Technology

1985-12-01

trichloroethyl phosphite and a phosphate ester containing a pentachlorphenyl radical. Most of the Asperity heights phosphorous compounds in gear oils...108) found that phosphorous compounds chemisorption. These boundary films can be thinner than ( 1 0 u ts n 0.025 pm (I in ) or several microinches thick...Pinion 1 .. dibutylxanthic acid disulfide. Ŗ %- Lead soaps have been used in lubricants for many 02 years. They resist the wiping and sliding action in

Environmental applications using graphene composites: water remediation and gas adsorption.

PubMed

Kemp, K Christian; Seema, Humaira; Saleh, Muhammad; Le, Nhien H; Mahesh, Kandula; Chandra, Vimlesh; Kim, Kwang S

2013-04-21

This review deals with wide-ranging environmental studies of graphene-based materials on the adsorption of hazardous materials and photocatalytic degradation of pollutants for water remediation and the physisorption, chemisorption, reactive adsorption, and separation for gas storage. The environmental and biological toxicity of graphene, which is an important issue if graphene composites are to be applied in environmental remediation, is also addressed.

The structure, energetics, and nature of the chemical bonding of phenylthiol adsorbed on the Au(111) surface: implications for density-functional calculations of molecular-electronic conduction.

PubMed

Bilić, Ante; Reimers, Jeffrey R; Hush, Noel S

2005-03-01

The adsorption of phenylthiol on the Au(111) surface is modeled using Perdew and Wang density-functional calculations. Both direct molecular physisorption and dissociative chemisorption via S-H bond cleavage are considered as well as dimerization to form disulfides. For the major observed product, the chemisorbed thiol, an extensive potential-energy surface is produced as a function of both the azimuthal orientation of the adsorbate and the linear translation of the adsorbate through the key fcc, hcp, bridge, and top binding sites. Key structures are characterized, the lowest-energy one being a broad minimum of tilted orientation ranging from the bridge structure halfway towards the fcc one. The vertically oriented threefold binding sites, often assumed to dominate molecular electronics measurements, are identified as transition states at low coverage but become favored in dense monolayers. A similar surface is also produced for chemisorption of phenylthiol on Ag(111); this displays significant qualitative differences, consistent with the qualitatively different observed structures for thiol chemisorption on Ag and Au. Full contours of the minimum potential energy as a function of sulfur translation over the crystal face are described, from which the barrier to diffusion is deduced to be 5.8 kcal mol(-1), indicating that the potential-energy surface has low corrugation. The calculated bond lengths, adsorbate charge and spin density, and the density of electronic states all indicate that, at all sulfur locations, the adsorbate can be regarded as a thiyl species that forms a net single covalent bond to the surface of strength 31 kcal mol(-1). No detectable thiolate character is predicted, however, contrary to experimental results for alkyl thiols that indicate up to 20%-30% thiolate involvement. This effect is attributed to the asymptotic-potential error of all modern density functionals that becomes manifest through a 3-4 eV error in the lineup of the adsorbate and substrate bands. Significant implications are described for density-functional calculations of through-molecule electron transport in molecular electronics.

Dispersion Forces of Solids under Stress. Chemisorption under Stress.

DTIC Science & Technology

1984-08-01

The objective of the research summerized here was to determine the stress ce dependence of the chemical potential of atoms chemisorbed to metal...received by the scientific- engineering community. In- terest was shown to carry out the experiments suggested in our paper and we hope that this phase...out several benchmark theoretical investi- gations on our chemostress effect. These papers were well received by both .* scientific and engineering

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

Not Available

The following are reported: theoretical calculations (configuration interaction, relativistic effective core potentials, polyatomics, CASSCF); proposed theoretical studies (clusters of Cu, Ag, Au, Ni, Pt, Pd, Rh, Ir, Os, Ru; transition metal cluster ions; transition metal carbide clusters; bimetallic mixed transition metal clusters); reactivity studies on transition metal clusters (reactivity with H{sub 2}, C{sub 2}H{sub 4}, hydrocarbons; NO and CO chemisorption on surfaces). Computer facilities and codes to be used, are described. 192 refs, 13 figs.

Sputtering in mercury ion thrusters

NASA Technical Reports Server (NTRS)

Mantenieks, M. A.; Rawlin, V. K.

1979-01-01

A model, which assumes that chemisorption is the dominant mechanism, is applied to the sputtering rate measurements of the screen grid of a 30 cm thruster in the presence of nitrogen. The model utilizes inputs from a variety of experimental and analytical sources. The model of environmental effects on sputtering was applied to thruster conditions of low discharge voltage and a discussion of the comparison of theory and experiment is presented.

Amidoxime Polymers for Uranium Adsorption: Influence of Comonomers and Temperature

DOE PAGES

Ladshaw, Austin P.; Wiechert, Alexander I.; Das, Sadananda; ...

2017-11-04

Recovering uranium from seawater has been the subject of many studies for decades, and has recently seen significant progress in materials development since the U.S. Department of Energy (DOE) has become involved. With DOE direction, the uranium uptake for amidoxime-based polymer adsorbents has more than tripled in capacity. In an effort to better understand how these new adsorbent materials behave under different environmental stimuli, several experimental and modeling based studies have been employed to investigate impacts of competing ions, salinity, pH, and other factors on uranium uptake. For this study, the effect of temperature and type of comonomer on uraniummore » adsorption by three different amidoxime adsorbents (AF1, 38H, AI8) was examined. Experimental measurements of uranium uptake were taken in 1–L batch reactors from 10 to 40 °C. A chemisorption model was developed and applied in order to estimate unknown system parameters through optimization. Experimental results demonstrated that the overall uranium chemisorption process for all three materials is endothermic, which was also mirrored in the model results. Model simulations show very good agreement with the data and were able to predict the temperature effect on uranium adsorption as experimental conditions changed. Here, this model may be used for predicting uranium uptake by other amidoxime materials.« less

Amidoxime Polymers for Uranium Adsorption: Influence of Comonomers and Temperature

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

Ladshaw, Austin P.; Wiechert, Alexander I.; Das, Sadananda

Recovering uranium from seawater has been the subject of many studies for decades, and has recently seen significant progress in materials development since the U.S. Department of Energy (DOE) has become involved. With DOE direction, the uranium uptake for amidoxime-based polymer adsorbents has more than tripled in capacity. In an effort to better understand how these new adsorbent materials behave under different environmental stimuli, several experimental and modeling based studies have been employed to investigate impacts of competing ions, salinity, pH, and other factors on uranium uptake. For this study, the effect of temperature and type of comonomer on uraniummore » adsorption by three different amidoxime adsorbents (AF1, 38H, AI8) was examined. Experimental measurements of uranium uptake were taken in 1–L batch reactors from 10 to 40 °C. A chemisorption model was developed and applied in order to estimate unknown system parameters through optimization. Experimental results demonstrated that the overall uranium chemisorption process for all three materials is endothermic, which was also mirrored in the model results. Model simulations show very good agreement with the data and were able to predict the temperature effect on uranium adsorption as experimental conditions changed. Here, this model may be used for predicting uranium uptake by other amidoxime materials.« less

Atomic imaging of the irreversible sensing mechanism of NO2 adsorption on copper phthalocyanine.

PubMed

Park, Jun Hong; Royer, James E; Chagarov, Evgeniy; Kaufman-Osborn, Tobin; Edmonds, Mary; Kent, Tyler; Lee, Sangyeob; Trogler, William C; Kummel, Andrew C

2013-10-02

Ambient NO2 adsorption onto copper(II) phthalocyanine (CuPc) monolayers is observed using ultrahigh vacuum (UHV) scanning tunneling microscopy (STM) to elucidate the molecular sensing mechanism in CuPc chemical vapor sensors. For low doses (1 ppm for 5 min) of NO2 at ambient temperatures, isolated chemisorption sites on the CuPc metal centers are observed in STM images. These chemisorbates almost completely desorb from the CuPc monolayer after annealing at 100 °C for 30 min. Conversely, for high NO2 doses (10 ppm for 5 min), the NO2 induces a fracture of the CuPc domains. This domain fracture can only be reversed by annealing above 150 °C, which is consistent with dissociative chemisorption into NO and atomic O accompanied by surface restructuring. This high stability implies that the domain fracture results from tightly bound adsorbates, such as atomic O. Existence of atomic O on or under the CuPc layer, which results in domain fracture, is revealed by XPS analysis and ozone-dosing experiments. The observed CuPc domain fracturing is consistent with a mechanism for the dosimetric sensing of NO2 and other reactive gases by CuPc organic thin film transistors (OTFTs).

Defects and oxidation of group-III monochalcogenide monolayers

NASA Astrophysics Data System (ADS)

Guo, Yu; Zhou, Si; Bai, Yizhen; Zhao, Jijun

2017-09-01

Among various two-dimensional (2D) materials, monolayer group-III monochalcogenides (GaS, GaSe, InS, and InSe) stand out owing to their potential applications in microelectronics and optoelectronics. Devices made of these novel 2D materials are sensitive to environmental gases, especially O2 molecules. To address this critical issue, here we systematically investigate the oxidization behaviors of perfect and defective group-III monochalcogenide monolayers by first-principles calculations. The perfect monolayers show superior oxidation resistance with large barriers of 3.02-3.20 eV for the dissociation and chemisorption of O2 molecules. In contrast, the defective monolayers with single chalcogen vacancy are vulnerable to O2, showing small barriers of only 0.26-0.36 eV for the chemisorption of an O2 molecule. Interestingly, filling an O2 molecule to the chalcogen vacancy of group-III monochalcogenide monolayers could preserve the electronic band structure of the perfect system—the bandgaps are almost intact and the carrier effective masses are only moderately disturbed. On the other hand, the defective monolayers with single vacancies of group-III atoms carry local magnetic moments of 1-2 μB. These results help experimental design and synthesis of group-III monochalcogenides based 2D devices with high performance and stability.

Internal stress induced natural self-chemisorption of ZnO nanostructured films

PubMed Central

Chi, Po-Wei; Su, Chih-Wei; Wei, Da-Hua

2017-01-01

The energetic particles bombardment can produce large internal stress in the zinc oxide (ZnO) thin film, and it can be used to intentionally modify the surface characteristics of ZnO films. In this article, we observed that the internal stress increased from −1.62 GPa to −0.33 GPa, and the naturally wettability of the textured ZnO nanostructured films changed from hydrophobicity to hydrophilicity. According to analysis of surface chemical states, the naturally controllable wetting behavior can be attributed to hydrocarbon adsorbates on the nanostructured film surface, which is caused by tunable internal stress. On the other hand, the interfacial water molecules near the surface of ZnO nanostructured films have been identified as hydrophobic hydrogen structure by Fourier transform infrared/attenuated total reflection. Moreover, a remarkable near-band-edge emission peak shifting also can be observed in PL spectra due to the transition of internal stress state. Furthermore, our present ZnO nanostructured films also exhibited excellent transparency over 80% with a wise surface wetting switched from hydrophobic to hydrophilic states after exposing in ultraviolet (UV) surroundings. Our work demonstrated that the internal stress of the thin film not only induced natural wettability transition of ZnO nanostructured films, but also in turn affected the surface properties such as surface chemisorption. PMID:28233827

Internal stress induced natural self-chemisorption of ZnO nanostructured films

NASA Astrophysics Data System (ADS)

Chi, Po-Wei; Su, Chih-Wei; Wei, Da-Hua

2017-02-01

The energetic particles bombardment can produce large internal stress in the zinc oxide (ZnO) thin film, and it can be used to intentionally modify the surface characteristics of ZnO films. In this article, we observed that the internal stress increased from -1.62 GPa to -0.33 GPa, and the naturally wettability of the textured ZnO nanostructured films changed from hydrophobicity to hydrophilicity. According to analysis of surface chemical states, the naturally controllable wetting behavior can be attributed to hydrocarbon adsorbates on the nanostructured film surface, which is caused by tunable internal stress. On the other hand, the interfacial water molecules near the surface of ZnO nanostructured films have been identified as hydrophobic hydrogen structure by Fourier transform infrared/attenuated total reflection. Moreover, a remarkable near-band-edge emission peak shifting also can be observed in PL spectra due to the transition of internal stress state. Furthermore, our present ZnO nanostructured films also exhibited excellent transparency over 80% with a wise surface wetting switched from hydrophobic to hydrophilic states after exposing in ultraviolet (UV) surroundings. Our work demonstrated that the internal stress of the thin film not only induced natural wettability transition of ZnO nanostructured films, but also in turn affected the surface properties such as surface chemisorption.

Internal stress induced natural self-chemisorption of ZnO nanostructured films.

PubMed

Chi, Po-Wei; Su, Chih-Wei; Wei, Da-Hua

2017-02-24

The energetic particles bombardment can produce large internal stress in the zinc oxide (ZnO) thin film, and it can be used to intentionally modify the surface characteristics of ZnO films. In this article, we observed that the internal stress increased from -1.62 GPa to -0.33 GPa, and the naturally wettability of the textured ZnO nanostructured films changed from hydrophobicity to hydrophilicity. According to analysis of surface chemical states, the naturally controllable wetting behavior can be attributed to hydrocarbon adsorbates on the nanostructured film surface, which is caused by tunable internal stress. On the other hand, the interfacial water molecules near the surface of ZnO nanostructured films have been identified as hydrophobic hydrogen structure by Fourier transform infrared/attenuated total reflection. Moreover, a remarkable near-band-edge emission peak shifting also can be observed in PL spectra due to the transition of internal stress state. Furthermore, our present ZnO nanostructured films also exhibited excellent transparency over 80% with a wise surface wetting switched from hydrophobic to hydrophilic states after exposing in ultraviolet (UV) surroundings. Our work demonstrated that the internal stress of the thin film not only induced natural wettability transition of ZnO nanostructured films, but also in turn affected the surface properties such as surface chemisorption.

Stereo-selective binding of chlorobenzene on Si(111)-7×7

NASA Astrophysics Data System (ADS)

Cao, Y.; Deng, J. F.; Xu, G. Q.

2000-03-01

The adsorption and binding of chlorobenzene (C6H5Cl) on clean and D-modified Si(111)-7×7 surfaces have been investigated using high resolution electron energy loss spectroscopy (HREELS) and thermal desorption spectroscopy (TDS). On a clean surface, both chemisorbed and physisorbed C6H5Cl are observed at an adsorption temperature of 110 K. The HREEL spectra show direct evidence for the presence of both sp2 and sp3 carbon atoms in chemisorbed C6H5Cl molecules on Si(111)-7×7. Upon D-modification, the chemisorption of C6H5Cl decreases rapidly with increasing D-coverage (θD). At θD=1/3 ML, only physisorbed chlorobenzene is detected, which strongly suggests the involvement of rest-atoms in the chemisorption of C6H5Cl. Combined with the scanning tunneling microscopy (STM) results by Chen et al. [Surf. Sci. 340, 224 (1995)] showing the participation of adatoms in the binding, we propose that the 2,5-carbon atoms in C6H5Cl are stereo-selectively di-σ bonded to a pair of adjacent adatom and rest-atom on the Si(111)-7×7 surface, yielding a 2,5-chlorocyclohexadienelike surface adduct.

Carbon Dioxide Absorption by the Imidazolium-Amino Acid Ionic Liquids, Kinetics, and Mechanism Approach.

PubMed

Rezaeian, Mojtaba; Izadyar, Mohammad; Nakhaei Pour, Ali

2018-06-25

The kinetics and mechanism of CO 2 absorption by ionic liquids (ILs) were studied, theoretically. The studied ILs are composed of 1-ethyl-3-methylimidazolium [Emim] + as the cation with a general formula of the [Emim][X] (X = Gly - , Ala - , Lys - , Arg - ). To investigate the alkyl chain length and the number of the amine group effects on the CO 2 absorption, different amino acid anions were chosen. On the basis of the enthalpy changes during CO 2 capture, a chemisorption nature is confirmed. An increase in the number of amine (-NH 2 ) groups in the ILs structures, facilitates the CO 2 absorption. According to kinetic results, the rate of CO 2 absorption by [Emim][Gly] is higher than that of [Emim][Ala]. This can be interpreted by a higher steric hindrance in [Emim][Ala] due to an additional methyl group in the amino acid chain. Donor-acceptor interactions and C-N bond formation were investigated by natural bond orbital analysis. Moreover, topological studies show a covalent nature for the C-N bond critical point that showing CO 2 capture is a chemisorption process. Finally, on the basis of kinetic energy results, donor-acceptor interaction and topological analysis, [Emim][Arg] is proposed as the best candidate for CO 2 absorption from the kinetic and thermodynamic viewpoints.

Amidoxime Polymers for Uranium Adsorption: Influence of Comonomers and Temperature

PubMed Central

Wiechert, Alexander I.; Das, Sadananda; Yiacoumi, Sotira

2017-01-01

Recovering uranium from seawater has been the subject of many studies for decades, and has recently seen significant progress in materials development since the U.S. Department of Energy (DOE) has become involved. With DOE direction, the uranium uptake for amidoxime-based polymer adsorbents has more than tripled in capacity. In an effort to better understand how these new adsorbent materials behave under different environmental stimuli, several experimental and modeling based studies have been employed to investigate impacts of competing ions, salinity, pH, and other factors on uranium uptake. For this study, the effect of temperature and type of comonomer on uranium adsorption by three different amidoxime adsorbents (AF1, 38H, AI8) was examined. Experimental measurements of uranium uptake were taken in 1−L batch reactors from 10 to 40 °C. A chemisorption model was developed and applied in order to estimate unknown system parameters through optimization. Experimental results demonstrated that the overall uranium chemisorption process for all three materials is endothermic, which was also mirrored in the model results. Model simulations show very good agreement with the data and were able to predict the temperature effect on uranium adsorption as experimental conditions changed. This model may be used for predicting uranium uptake by other amidoxime materials. PMID:29113060

Calorimetry, activity, and micro-FTIR analysis of CO chemisorption, titration, and oxidation on supported Pt

NASA Technical Reports Server (NTRS)

Sermon, Paul A.; Self, Valerie A.; Vong, Mariana S. W.; Wurie, Alpha T.

1990-01-01

The value of in situ analysis on CO chemisorption, titration and oxidation over supported Pt catalysts using calorimetry, catalytic and micro-FTIR methods is illustrated using silica- and titania-supported samples. Isothermal CO-O and O2-CO titrations have not been widely used on metal surfaces and may be complicated if some oxide supports are reduced by CO titrant. However, they can illuminate the kinetics of CO oxidation on metal/oxide catalysts since during such titrations all O and CO coverages are scanned as a function of time. There are clear advantages in following the rates of the catalyzed CO oxidation via calorimetry and gc-ms simultaneously. At lower temperatures the evidence they provide is complementary. CO oxidation and its catalysis of CO oxidation have been extensively studied with hysteresis and oscillations apparent, and the present results suggest the benefits of a combined approach. Silica support porosity may be important in defining activity-temperature hysteresis. FTIR microspectroscopy reveals the chemical heterogeneity of the catalytic surfaces used; it is interesting that the evidence with regard to the dominant CO surface species and their reactivities with regard to surface oxygen for present oxide-supported Pt are different from those seen on graphite-supported Pt.

A relativistic density functional study of the role of 5f electrons in atomic and molecular adsorptions on actinide surfaces

NASA Astrophysics Data System (ADS)

Huda, Muhammad Nurul

Atomic and molecular adsorptions of oxygen and hydrogen on actinide surfaces have been studied within the generalized gradient approximations to density functional theory (GGA-DFT). The primary goal of this work is to understand the details of the adsorption processes, such as chemisorption sites, energies, adsorption configurations and activation energies for dissociation of molecules; and the signature role of the plutonium 5f electrons. The localization of the 5f electrons remains one of central questions in actinides and one objective here is to understand the extent to which localizations plays a role in adsorption on actinide surfaces. We also investigated the magnetism of the plutonium surfaces, given the fact that magnetism in bulk plutonium is a highly controversial issue, and the surface magnetism of it is not a well explored territory. Both the non-spin-polarized and spin-polarized calculations have been performed to arrive at our conclusions. We have studied both the atomic and molecular hydrogen and oxygen adsorptions on plutonium (100) and (111) surfaces. We have also investigated the oxygen molecule adsorptions on uranium (100) surface. Comparing the adsorption on uranium and plutonium (100) surfaces, we have seen that O2 chemisorption energy for the most favorable adsorption site on uranium surface has higher chemisorption energy, 9.492 eV, than the corresponding plutonium site, 8.787 eV. Also degree of localization of 5f electrons is less for uranium surface. In almost all of the cases, the most favorable adsorption sites are found where the coordination numbers are higher. For example, we found center sites are the most favorable sites for atomic adsorptions. In general oxygen reacts more strongly with plutonium surface than hydrogen. We found that atomic oxygen adsorption energy on (100) surface is 3.613 eV more than that of the hydrogen adsorptions, considering only the most favorable site. This is also true for molecular adsorptions, as the oxygen molecules on both (100) and (111) plutonium surfaces dissociate almost spontaneously, whereas hydrogen needs some activation energy to dissociate. From spin-polarized calculations we found both (100) and (111) surfaces have the layer by layer alternating spin-magnetic behavior. In general adsorption of H2 and O2 do not change this behavior.

SrNb2O6 nanoplates as efficient photocatalysts for the preferential reduction of CO2 in the presence of H2O.

PubMed

Xie, Shunji; Wang, Yu; Zhang, Qinghong; Deng, Weiping; Wang, Ye

2015-02-25

We successfully synthesized SrNb2O6 with nanoplate morphology by a facile hydrothermal method. The SrNb2O6 nanoplate without any promoters or co-catalysts exhibited promising photocatalytic performance for the preferential reduction of CO2 with H2O vapour to CO and CH4 due to its high electron-hole separation and high CO2 chemisorption abilities.

An investigation of the effect of surface impurities on the adsorption kinetics of hydrogen chemisorbed onto iron

NASA Technical Reports Server (NTRS)

Shanabarger, Mickey R.

1994-01-01

The goal of this program has been to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. During the present program, the interaction of hydrogen with the surfaces of alpha-2 (Ti3Al) titanium aluminide, gamma (TiAl) titanium aluminide, and beryllium were studied. The interaction of low pressure hydrogen with gamma titanium aluminide and beryllium was found to be relatively weak. Weak in the sense that adsorption leads to a low surface concentration of dissociated hydrogen, i.e., the chemisorption process is reversible at room temperature (300 K) for gamma titanium aluminide and the sticking coefficient for chemisorption is extremely small for beryllium. Hydrogen was found to interact readily with alpha-2 titanium aluminide to form a stable surface hydride at 300 K. These results correlate well with other recent studies which show that the mechanical properties for alpha-2 titanium aluminide are readily degraded in hydrogen while gamma titanium aluminide exhibits less degradation and beryllium essentially no degradation. The interaction of oxygen with the surface of several of these materials was studied. More recently, preliminary hydrogen permeation studies were completed for three high temperature alloys, Incoloy 909, Mo-47.5Re (wt. %), and this past year, Haynes 188.

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

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

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

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

Strong Capillarity, Chemisorption, and Electrocatalytic Capability of Crisscrossed Nanostraws Enabled Flexible, High-Rate, and Long-Cycling Lithium-Sulfur Batteries.

PubMed

Ma, Lianbo; Zhang, Wenjun; Wang, Lei; Hu, Yi; Zhu, Guoyin; Wang, Yanrong; Chen, Renpeng; Chen, Tao; Tie, Zuoxiu; Liu, Jie; Jin, Zhong

2018-05-22

The development of flexible lithium-sulfur (Li-S) batteries with high energy density and long cycling life are very appealing for the emerging flexible, portable, and wearable electronics. However, the progress on flexible Li-S batteries was limited by the poor flexibility and serious performance decay of existing sulfur composite cathodes. Herein, we report a freestanding and highly flexible sulfur host that can simultaneously meet the flexibility, stability, and capacity requirements of flexible Li-S batteries. The host consists of a crisscrossed network of carbon nanotubes reinforced CoS nanostraws (CNTs/CoS-NSs). The CNTs/CoS-NSs with large inner space and high conductivity enable high loading and efficient utilization of sulfur. The strong capillarity effect and chemisorption of CNTs/CoS-NSs to sulfur species were verified, which can efficiently suppress the shuttle effect and promote the redox kinetics of polysulfides. The sulfur-encapsulated CNTs/CoS-NSs (S@CNTs/CoS-NSs) cathode in Li-S batteries exhibits superior performance, including high discharge capacity, rate capability (1045 mAh g -1 at 0.5 C and 573 mAh g -1 at 5.0 C), and cycling stability. Intriguingly, the soft-packed Li-S batteries based on S@CNTs/CoS-NSs cathode show good flexibility and stability upon bending.

The adsorption of oleate on powellite and fluorapatite: A joint experimental and theoretical simulation study

NASA Astrophysics Data System (ADS)

Zhen, Wang

2017-07-01

Flotation and adsorption performance of sodium oleate(NaOl)on powellite and fluorapatite were investigated in this work through micro-flotation tests, work of adhesion calculations, molecular dynamics simulation, micro-topography studies and FTIR measurements. The micro-flotation results show a similar flotation behaviors of powellite and fluorapatite under alkaline conditions, but a considerable difference in mineral recoveries in the pH range 2-7, which demonstrates the possibilities for separating powillite from fluorapatite under acidic conditions. The great difference in mineral recovery displays a good accordance with the obvious difference in the work of adhesion of powellite and fluorapatite at NaOl dosage range of 40-80 mg/L, obtained from flotation and contact angle measurements, respectively. The more negative interaction energy (ΔE) between NaOl and powellite/water interface from molecular dynamics simulation reveals a more easily adsorption of NaOl onto powellite than onto fluorapatite, which excellently matches with the results of flotation and work of adhesion. The results of micro-topography study shows that the adsorption of NaOl on powellite is mainly ascribed to the chemisorption of oleate ions with Ca2+ on powellite lattice or the precipitation of calcium dioleate agglomerates on powellite surface when it was in the solution without or with Ca2+, respectively. The FTIR measurements further confirm the chemisorption of oleate ions with Ca2+ active sites on powellite surface.

The electrooxidation mechanism of formic acid on platinum and on lead ad-atoms modified platinum studied with the kinetic isotope effect

NASA Astrophysics Data System (ADS)

Bełtowska-Brzezinska, M.; Łuczak, T.; Stelmach, J.; Holze, R.

2014-04-01

Kinetics and mechanism of formic acid (FA) oxidation on platinum and upd-lead ad-atoms modified platinum electrodes have been studied using unlabelled and deuterated compounds. Poisoning of the electrode surface by CO-like species was prevented by suppression of dissociative chemisorption of FA due to a fast competitive underpotential deposition of lead ad-atoms on the Pt surface from an acidic solution containing Pb2+ cations. Modification of the Pt electrode with upd lead induced a catalytic effect in the direct electrooxidation of physisorbed FA to CO2. With increasing degree of H/D substitution, the rate of this reaction decreased in the order: HCOOH > DCOOH ≥ HCOOD > DCOOD. HCOOH was oxidized 8.5-times faster on a Pt/Pb electrode than DCOOD. This primary kinetic isotope effect proves that the C-H- and O-H-bonds are simultaneously cleaved in the rate determining step. A secondary kinetic isotope effect was found in the dissociative chemisorption of FA in the hydrogen adsorption-desorption range on a bare Pt electrode after H/D exchange in the C-H bond, wherein the influence of deuterium substitution in the O-H group was negligibly small. Thus the C-H bond cleavage is accompanied by the C-OH and not the O-H bond split in the FA decomposition, producing CO-like species on the Pt surface sites.

DFT study of benzyl alcohol/TiO2 interfacial surface complex: reaction pathway and mechanism of visible light absorption.

PubMed

Zhao, Lei; Gu, Feng Long; Kim, Minjae; Miao, Maosheng; Zhang, Rui-Qin

2017-09-24

We propose a new pathway for the adsorption of benzyl alcohol on the surface of TiO 2 and the formation of interfacial surface complex (ISC). The reaction free energies and reaction kinetics were thoroughly investigated by density functional calculations. The TiO 2 surfaces were modeled by clusters consisting of 4 Ti atoms and 18 O atoms passivated by H, OH group and H 2 O molecules. Compared with solid-state calculations utilizing the periodicity of the materials, such cluster modeling allows inclusion of the high-order correlation effects that seem to be essential for the adsorption of organic molecules onto solid surfaces. The effects of both acidity and solvation are included in our calculations, which demonstrate that the new pathway is competitive with a previous pathway. The electronic structure calculations based on the relaxed ISC structures reveal that the chemisorption of benzyl alcohol on the TiO 2 surface greatly alters the nature of the frontier molecular orbitals. The resulted reduced energy gap in ISC matches the energy of visible light, showing how the adsorption of benzyl alcohol sensitizes the TiO 2 surface. Graphical Abstract The chemisorption of benzyl alcohol on TiO 2 surface greatly alters the nature of the frontier molecular orbitals and the formed interfacial surface complex can be sensitized by visible light.

Pentacene on Au(1 1 1), Ag(1 1 1) and Cu(1 1 1): From physisorption to chemisorption.

PubMed

Lu, Meng-Chao; Wang, Rong-Bin; Yang, Ao; Duhm, Steffen

2016-03-09

We measured the electronic and the molecular surface structure of pentacene deposited on the (1 1 1)-surfaces of coinage metals by means of ultraviolet photoelectron spectroscopy (UPS) and low-energy electron diffraction (LEED). Pentacene is almost flat-lying in monolayers on all three substrates and highly ordered on Au(1 1 1) and on Cu(1 1 1). On Ag(1 1 1), however, weak chemisorption leads to almost disordered monolayers, both, at room temperature and at 78 K. On Cu(1 1 1) pentacene is strongly chemisorbed and the lowest unoccupied molecular orbital becomes observable in UPS by a charge transfer from the substrate. On Ag(1 1 1) and Cu(1 1 1) multilayers adopt a tilted orientation and a high degree of crystallinity. On Au(1 1 1), most likely, also in multilayers the molecular short and long axes are parallel to the substrate, leading to a distinctively different electronic structure than on Ag(1 1 1) and Cu(1 1 1). Overall, it could be demonstrated that the substrate not only determines the geometric and electronic characteristics of molecular monolayer films but also plays a crucial role for multilayer film growth.

The role of beaded activated carbon's surface oxygen groups on irreversible adsorption of organic vapors.

PubMed

Jahandar Lashaki, Masoud; Atkinson, John D; Hashisho, Zaher; Phillips, John H; Anderson, James E; Nichols, Mark

2016-11-05

The objective of this study is to determine the contribution of surface oxygen groups to irreversible adsorption (aka heel formation) during cyclic adsorption/regeneration of organic vapors commonly found in industrial systems, including vehicle-painting operations. For this purpose, three chemically modified activated carbon samples, including two oxygen-deficient (hydrogen-treated and heat-treated) and one oxygen-rich sample (nitric acid-treated) were prepared. The samples were tested for 5 adsorption/regeneration cycles using a mixture of nine organic compounds. For the different samples, mass balance cumulative heel was 14 and 20% higher for oxygen functionalized and hydrogen-treated samples, respectively, relative to heat-treated sample. Thermal analysis results showed heel formation due to physisorption for the oxygen-deficient samples, and weakened physisorption combined with chemisorption for the oxygen-rich sample. Chemisorption was attributed to consumption of surface oxygen groups by adsorbed species, resulting in formation of high boiling point oxidation byproducts or bonding between the adsorbates and the surface groups. Pore size distributions indicated that different pore sizes contributed to heel formation - narrow micropores (<7Å) in the oxygen-deficient samples and midsize micropores (7-12Å) in the oxygen-rich sample. The results from this study help explain the heel formation mechanism and how it relates to chemically tailored adsorbent materials. Copyright © 2016 Elsevier B.V. All rights reserved.

Recent advances in self-assembled monolayers based biomolecular electronic devices.

PubMed

Arya, Sunil K; Solanki, Pratima R; Datta, Monika; Malhotra, Bansi D

2009-05-15

Self-assembled monolayers (SAMs) have aroused much interest due to their potential applications in biosensors, biomolecular electronics and nanotechnology. This has been largely attributed to their inherent ordered arrangement and controllable properties. SAMs can be formed by chemisorption of organic molecules containing groups like thiols, disulphides, amines, acids or silanes, on desired surfaces and can be used to fabricate biomolecular electronic devices. We focus on recent applications of organosulphur compounds (thiols) based SAMs to biomolecular electronic devices in the last about 3 years.

Phase Transitions on Surfaces. An International Conference. Abstracts and Program, 3-7 August 1981, Orono, Maine.

DTIC Science & Technology

1982-04-16

P. J. Estrup Chemisorption-Induced Phase Transitions and Adatom Interactions on GaAs(110) P. Skeath, C. Y. Su, P. W. Chye , I. Lindau and W. E. Spicer...Transitions and Adatom Interactions on GaAs(ll0)* Perry Skeath, C. Y. Su, P. W. Chye , I Lindau, and W. E. Spicer Stanford Electronics Labs Stanford...ORDER PHASE TRANSITIONS* P. KLEBAN and CHIN -KUN HU, Department of Physics and Astronomy and Laboratory for Surface Science and Technology University of

Model of gas adsorption on magnetic surfaces

NASA Astrophysics Data System (ADS)

Pick, S.˛te˛´n.; D´, Hugues

1997-12-01

The semi-empirical self-consistent tight-binding model of gas (C, N, O) chemisorption is suggested to study its influence on surface magnetism. For the strongly ferromagnetic Fe(001), we find that the adsorbates are not effective in magnetism reduction. For the hypothetical magnetic V(001) surface, the magnetization is very sensitive to the vanadium d-band occupation used in the calculation. Supposing that the magnetization is weak, it can be essentially suppressed by the gas contamination. The effect is explained by the Stoner criterion.

X-Ray Photoelectron Spectroscopy Study of the Chemisorption of Lead Naphthenate to Nucleophilic Surfaces.

DTIC Science & Technology

1980-09-10

naphthenic acid is 1-methylcyclopentane- carboxylic acid . Lead naphthenate is not one unique compound but a mixture of several naphthenates with various alkane...chain lengths and an average molecu- lar weight of 662 g/mol. It contains no free naphthenic acid . Solutions of 1% by weight lead naphthenate in...particularly on surface acidity . The influence of the pH of the pretreatment bath used for the substrate on the existence of chemi- sorbed lead naphthenate

Coalescence of 3-phenyl-propynenitrile on Cu(111) into interlocking pinwheel chains

NASA Astrophysics Data System (ADS)

Luo, Miaomiao; Lu, Wenhao; Kim, Daeho; Chu, Eric; Wyrick, Jon; Holzke, Connor; Salib, Daniel; Cohen, Kamelia D.; Cheng, Zhihai; Sun, Dezheng; Zhu, Yeming; Einstein, T. L.; Bartels, Ludwig

2011-10-01

3-phenyl-propynenitrile (PPN) adsorbs on Cu(111) in a hexagonal network of molecular trimers formed through intermolecular interaction of the cyano group of one molecule with the aromatic ring of its neighbor. Heptamers of trimers coalesce into interlocking pinwheel-shaped structures that, by percolating across islands of the original trimer coverage, create the appearance of gear chains. Density functional theory aids in identifying substrate stress associated with the chemisorption of PPN's acetylene group as the cause of this transition.

SFG experiment and ab initio study of the chemisorption of CN - on low-index platinum surfaces

NASA Astrophysics Data System (ADS)

Tadjeddine, M.; Flament, J.-P.; Le Rille, A.; Tadjeddine, A.

2006-05-01

A dual analysis is proposed in order to have a better understanding of the adsorption of the cyanide ions on a platinum electrode. The SFG (Sum Frequency Generation) spectroscopy allows the in situ vibrational study and the SFG spectra of the CN - species adsorbed on single crystal Pt electrode allow a systematic study of the low-index platinum surfaces. This experimental work is supported by ab initio calculations using density functional theory and cluster models. For each surface orientation and each geometry, a cluster model of 20-30 Pt atoms has been built in order to interpret the chemisorption of the CN - ions through four kinds of adsorption geometry: on-top or bridge site, bonding via C or N atoms. Geometries have been optimized and adsorption energies, electronic properties and vibrational frequencies have been computed. From the electronic properties, we can propose an analysis of the bonding mechanism for each studied kind of adsorption. The SFG spectra of the CN -/Pt(1 1 1) system present an unique resonance owing to the top C adsorption. It is mainly the same for the CN -/Pt(1 0 0) system. It is also the case for the SFG spectra of the CN -/Pt(1 1 0) system recorded at negative electrochemical voltage; at more positive voltage, a second resonance appears at a lower frequency, owing to the top N adsorption. Experimental and theoretical values of the C-N stretching frequencies are in excellent agreement.

Correlation between Fischer-Tropsch catalytic activity and composition of catalysts

PubMed Central

2011-01-01

This paper presents the synthesis and characterization of monometallic and bimetallic cobalt and iron nanoparticles supported on alumina. The catalysts were prepared by a wet impregnation method. Samples were characterized using temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), CO-chemisorption, transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM-EDX) and N2-adsorption analysis. Fischer-Tropsch synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H2/CO = 2 v/v and space velocity, SV = 12L/g.h. The physicochemical properties and the FTS activity of the bimetallic catalysts were analyzed and compared with those of monometallic cobalt and iron catalysts at similar operating conditions. H2-TPR analysis of cobalt catalyst indicated three temperature regions at 506°C (low), 650°C (medium) and 731°C (high). The incorporation of iron up to 30% into cobalt catalysts increased the reduction, CO chemisorption and number of cobalt active sites of the catalyst while an opposite trend was observed for the iron-riched bimetallic catalysts. The CO conversion was 6.3% and 4.6%, over the monometallic cobalt and iron catalysts, respectively. Bimetallic catalysts enhanced the CO conversion. Amongst the catalysts studied, bimetallic catalyst with the composition of 70Co30Fe showed the highest CO conversion (8.1%) while exhibiting the same product selectivity as that of monometallic Co catalyst. Monometallic iron catalyst showed the lowest selectivity for C5+ hydrocarbons (1.6%). PMID:22047220

Label-free detection of 3-nitro-l-tyrosine with nickel-doped graphene localized surface plasmon resonance biosensor.

PubMed

Ng, Siu Pang; Qiu, Guangyu; Ding, Ning; Lu, Xiaoqing; Wu, Chi-Man Lawrence

2017-03-15

3-nitro-l-tyrosine (3-NT) is believed to be a biomarker of neurodegenerative diseases and metal doped graphene possess exceptionally high binding energy of 3-NT with metal-nitro chemisorption. Here we report a novel label-free detection scheme of 3-NT via nickel-doped graphene (NDG) as the functionalized receptor on our phase detecting localized surface plasmon resonance (LSPR) biosensor. When compared with reported 3-NT immunoassay with enzyme-linked immunosorbent assay (ELISA), our NDG-LSPR platform offers two advantages i.e. 1) label-free and 2) capture of 3-NT by direct chemisorption. Our limit of detection for 3-NT in PBS was found to be 0.13pg/ml and the linear dynamic range of response was from 0.5pg/ml to 1ng/ml, i.e. four orders of magnitude. The specificity of our NDG receptor to 3-NT was also verified with l-tyrosine of equivalent concentrations in PBS and diluted human serum, for which the NDG receptor shows negligible responses. In addition, the adsorption of 3-NT and l-tyrosine to the NDG receptor were also investigated by atomic force microscopy and further verified by surface enhanced Raman spectroscopy. Therefore, our NDG-LSPR biosensor competes favorably against ELISA and we believe it should be an attractive and economical solution to early diagnostic of 3-NT related disorders for clinical applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Study on the adsorption properties of O{sub 3}, SO{sub 2}, and SO{sub 3} on B-doped graphene using DFT calculations

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

Rad, Ali Shokuhi, E-mail: a.shokuhi@gmail.com; Shabestari, Sahand Sadeghi; Mohseni, Soheil

2016-05-15

We investigated the structure, adsorption, electronic states, and charge transfer of O{sub 3}, SO{sub 2} and SO{sub 3} molecules on the surface of a B-doped graphene using density functional theory (DFT). We found weak physisorption of SO{sub 2} (−10.9 kJ/mole, using B3LYP-D) and SO{sub 3} (−15.7 kJ/mole, using B3LYP-D) on the surface of B-doped graphene while there is strong chemisorption for O{sub 3} (−96.3 kJ/mole, using B3LYP-D ) on this surface. Our results suggest the potential of B-doped graphene as a selective sensor/adsorbent for O{sub 3} molecule. We noticed some change in hybridizing of boron from sp{sup 2} to sp{supmore » 3} upon adsorption of O{sub 3} which cases transformation of the adsorbent from 2D to 3D. - Graphical abstract: The electronic property of B-doped graphene is responsible to highly adsorption of O{sub 3} molecules while the adsorption of SO{sub 2} and SO{sub 3} molecules on this surface exhibits only a weak interaction. - Highlights: • B-doped graphene clearly is n-type semiconductor. • High negatively charge of C-atoms neighboring the boron dopant. • Chemisorption of O{sub 3} and physisorption of SO{sub 2} and SO{sub 3} on the surface of B-doped graphene.« less

Dissociative chemisorption of methane on metal surfaces: Tests of dynamical assumptions using quantum models and ab initio molecular dynamics

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

Jackson, Bret, E-mail: jackson@chem.umass.edu; Nattino, Francesco; Kroes, Geert-Jan

The dissociative chemisorption of methane on metal surfaces is of great practical and fundamental importance. Not only is it the rate-limiting step in the steam reforming of natural gas, the reaction exhibits interesting mode-selective behavior and a strong dependence on the temperature of the metal. We present a quantum model for this reaction on Ni(100) and Ni(111) surfaces based on the reaction path Hamiltonian. The dissociative sticking probabilities computed using this model agree well with available experimental data with regard to variation with incident energy, substrate temperature, and the vibrational state of the incident molecule. We significantly expand the vibrationalmore » basis set relative to earlier studies, which allows reaction probabilities to be calculated for doubly excited initial vibrational states, though it does not lead to appreciable changes in the reaction probabilities for singly excited initial states. Sudden models used to treat the center of mass motion parallel to the surface are compared with results from ab initio molecular dynamics and found to be reasonable. Similar comparisons for molecular rotation suggest that our rotationally adiabatic model is incorrect, and that sudden behavior is closer to reality. Such a model is proposed and tested. A model for predicting mode-selective behavior is tested, with mixed results, though we find it is consistent with experimental studies of normal vs. total (kinetic) energy scaling. Models for energy transfer into lattice vibrations are also examined.« less

Adsorption of a novel reagent scheme on scheelite and calcite causing an effective flotation separation.

PubMed

Gao, Yuesheng; Gao, Zhiyong; Sun, Wei; Yin, Zhigang; Wang, Jianjun; Hu, Yuehua

2018-02-15

The efficient separation of scheelite from calcium-bearing minerals, especially calcite, remains a challenge in practice. In this work, a novel reagent scheme incorporating a depressant of sodium hexametaphosphate (SHMP) and a collector mixture of octyl hydroxamic acid (HXMA-8) and sodium oleate (NaOl) was employed in both single and mixed binary mineral flotation, and it proved to be highly effective for the separation. Furthermore, the role of the pH value in the separation was evaluated. Additionally, the mechanism of the selective separation was investigated systemically via zeta potential measurements, fourier transform infrared (FTIR) spectroscopy analysis, X-ray photoelectron (XPS) spectroscopy analysis and crystal chemistry calculations. It turns out that the selective chemisorption of SHMP on calcite (in the form of complexation between H 2 PO 4 - /HPO 4 2- and Ca 2+ ) over scheelite is ascribed to the stronger reactivity and higher density of Ca ions on the commonly exposed surfaces of calcite minerals. The intense adsorption of HXMA-8 on scheelite over calcite due to the match of the OO distances in WO 4 2- of scheelite and CONHOH of HXMA-8 holds the key to the successful separation. We were also interested in warranting the previous claim that NaOl is readily adsorbed on both minerals via chemisorption. Our results provided valuable insights into the application of mixed collectors and an effective depressant for flotation separation. Copyright © 2017 Elsevier Inc. All rights reserved.

Understanding the adsorptive interactions of arsenate-iron nanoparticles with curved fullerene-like sheets in activated carbon using a quantum mechanics/molecular mechanics computational approach.

PubMed

Ha, Nguyen Ngoc; Cam, Le Minh; Ha, Nguyen Thi Thu; Goh, Bee-Min; Saunders, Martin; Jiang, Zhong-Tao; Altarawneh, Mohammednoor; Dlugogorski, Bogdan Z; El-Harbawi, Mohanad; Yin, Chun-Yang

2017-06-07

The prevalence of global arsenic groundwater contamination has driven widespread research on developing effective treatment systems including adsorption using various sorbents. The uptake of arsenic-based contaminants onto established sorbents such as activated carbon (AC) can be effectively enhanced via immobilization/impregnation of iron-based elements on the porous AC surface. Recent suggestions that AC pores structurally consist of an eclectic mix of curved fullerene-like sheets may affect the arsenic adsorption dynamics within the AC pores and is further complicated by the presence of nano-sized iron-based elements. We have therefore, attempted to shed light on the adsorptive interactions of arsenate-iron nanoparticles with curved fullerene-like sheets by using hybridized quantum mechanics/molecular mechanics (QMMM) calculations and microscopy characterization. It is found that, subsequent to optimization, chemisorption between HAsO 4 2- and the AC carbon sheet (endothermic process) is virtually non-existent - this observation is supported by experimental results. Conversely, the incorporation of iron nanoparticles (FeNPs) into the AC carbon sheet greatly facilitates chemisorption of HAsO 4 2- . Our calculation implies that iron carbide is formed at the junction between the iron and the AC interface and this tightly chemosorbed layer prevents detachment of the FeNPs on the AC surface. Other aspects including electronic structure/properties, carbon arrangement defects and rate of adsorptive interaction, which are determined using the Climbing-Image NEB method, are also discussed.

Aging Oxidation Reactions on Atmospheric Black Carbon by OH Radicals. A Theoretical Modeling Study.

PubMed

Rojas, Laura; Peraza, Alexander; Ruette, Fernando

2015-12-31

Aging processes of black carbon (BC) particles require knowledge of their chemical reactivities, which have impact on cloud condensation nuclei (CCN) activities, radiant properties and health problems related to air pollutions. In the present work, interactions between several OH radicals with BC (modeled with a coronene molecule) were calculated by using DFT and PM6 codes as described by Mysak et al. Water interaction with BC was also included. Results show that OH radical adsorption is preferred on border sites, independent of the theoretical method employed. Potential energy curves using DFT(TPSS-D3) approach for OH chemisorption showed small-energy barriers, as reported in previous work with PM6. A dipole moment has been created, and the hydrophobic coronene surface is transformed to hydrophilic after the first OH chemisorption. Several stages were found in the BC aging by OH radicals, thus (a) Hydroxylation of coronene by several OH radical would lead to H abstractions directly from the substrate. (b) Abstraction of H from adsorbed OH (at the border sites) drives a C-C bond breaking and the formation of carboxyl groups. (c) Hydrogen abstraction from carboxyl group produces decarboxylation (CO2 plus water) as experimentally obtained. Potential energy curves of one of the reactive path were calculated with the PM6 method. The formation of products was confirmed using DFT. Coronene interaction with O2 was also considered to have a realistic atmospheric environment.

Normal Mode Analysis in Zeolites: Toward an Efficient Calculation of Adsorption Entropies.

PubMed

De Moor, Bart A; Ghysels, An; Reyniers, Marie-Françoise; Van Speybroeck, Veronique; Waroquier, Michel; Marin, Guy B

2011-04-12

An efficient procedure for normal-mode analysis of extended systems, such as zeolites, is developed and illustrated for the physisorption and chemisorption of n-octane and isobutene in H-ZSM-22 and H-FAU using periodic DFT calculations employing the Vienna Ab Initio Simulation Package. Physisorption and chemisorption entropies resulting from partial Hessian vibrational analysis (PHVA) differ at most 10 J mol(-1) K(-1) from those resulting from full Hessian vibrational analysis, even for PHVA schemes in which only a very limited number of atoms are considered free. To acquire a well-conditioned Hessian, much tighter optimization criteria than commonly used for electronic energy calculations in zeolites are required, i.e., at least an energy cutoff of 400 eV, maximum force of 0.02 eV/Å, and self-consistent field loop convergence criteria of 10(-8) eV. For loosely bonded complexes the mobile adsorbate method is applied, in which frequency contributions originating from translational or rotational motions of the adsorbate are removed from the total partition function and replaced by free translational and/or rotational contributions. The frequencies corresponding with these translational and rotational modes can be selected unambiguously based on a mobile block Hessian-PHVA calculation, allowing the prediction of physisorption entropies within an accuracy of 10-15 J mol(-1) K(-1) as compared to experimental values. The approach presented in this study is useful for studies on other extended catalytic systems.

Investigation of formaldehyde interaction with carbon nanotubes and quartz sand

NASA Astrophysics Data System (ADS)

Georgopoulou, Maria P.; Chrysikopoulos, Constantinos V.

2017-04-01

Assessment of the potential impact of synthetic carbon nanotubes on the fate and transport of common chemical contaminants (pesticides, pharmaceuticals, etc.) in groundwater systems is considered to be an increasingly important aspect of environmental research. This study investigates the interaction of formaldehyde with multi-walled carbon nanotubes (MWCNTs) and quartz sand under static and dynamic conditions. Due to polarity, formaldehyde, is expected to develop strong adsorptive interactions with carbon nanotubes. Several batch adsorption experiments were conducted in test tubes, under controlled conditions. Various initial formaldehyde solution concentration (2, 5, 8 ppm), contact times, and temperatures (8, 18, 25 °C) were considered. Supernatant liquid samples were collected at regular intervals, and centrifuged. Subsequently, the formaldehyde concentration in the supernatant was quantified indirectly, by derivatization with Nash reagent and subsequent measurement of the resulting complex using spectrophotometry in the visible spectral range. Experimental results suggested that formaldehyde has a low affinity for quartz sand, but an enhanced potential for adsorption onto carbon nanotubes. Formaldehyde adsorption onto both absorbents (quartz sand and MWCNTs) was more pronounced under dynamic than static conditions, probably, because agitation improves the mixing of the absorbent within the solution. Also, it was shown that the adsorption data were adequately described by the pseudo-second order kinetic model, suggesting that the primary adsorption mechanism was chemisorption, where two or more (sequential or parallel) processes (e.g. surface chemisorption, intraparticle diffusion) were taking place. Therefore, MWCNTs could be promising adsorbent materials for groundwater remediation.

Chemisorption studies of Pt/SnO2 catalysts

NASA Technical Reports Server (NTRS)

Brown, Kenneth G.; Ohorodnik, Susan K.; Vannorman, John D.; Schryer, Jacqueline; Upchurch, Billy T.; Schryer, David R.

1990-01-01

The low temperature CO oxidation catalysts that are being developed and tested at NASA-Langley are fairly unique in their ability to efficiently oxidize CO at low temperatures (approx. 303 K). The bulk of the reaction data that has been collected in the laboratory has been determined using plug flow reactors with a low mass of Pt/SnO2/SiO2 catalyst (approx. 0.1 g) and a modest flow rate (5 to 10 sc sm). The researchers have previously characterized the surface solely in terms of N2 BET surface areas. These surface areas have not been that indicative of reaction rate. Indeed, some of the formulations with high BET surface area have yielded lower reaction rates than those with lower BET surface areas. As a result researchers began a program of determining the chemisorption of the various species involved in the reaction; CO, O2 and CO2. Such a determination of will lead to a better understanding of the mechanism and overall kinetics of the reaction. The pulsed-reactor technique, initially described by Freel, is used to determine the amount of a particular molecule that is adsorbed on the catalyst. Since there is some reaction of CO with the surface to produce CO2, the pulsed reactor had to be coupled with a gas chromatograph in order to distinguish between the loss of CO that is due to adsorption by the surface and the loss that is due to reaction with the surface.

Vacancy Mediated Mechanism of Nitrogen Substitution in Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Srivastava, Deepak; Menon, Madhu; Sadanadan, Bindu; Rao, Apparao M.

2003-01-01

Nitrogen substitution reaction in a graphene sheet and carbon nanotubes of different diameter are investigated using the generalized tight-binding molecular dynamics method. The formation of a vacancy in curved graphene sheet or a carbon nanotube is found to cause a curvature dependent local reconstruction of the surface. Our simulations and analysis show that vacancy mediated N substitution (rather than N chemisorption) is favored on the surface of nanotubes with diameter larger than 8 nm. This predicted value of the critical minimum diameter for N incorporation is confirmed by experimental results presented.

Oxidation of Sn doped Cu cluster: A first principle study

NASA Astrophysics Data System (ADS)

Parida, Ganesh; Majumder, Chiranjib

2017-05-01

Bimetallic clusters have immense potential to exhibit tunable properties in the emerging field of nano catalysis. Using plane wave based pseudopotential approach we have investigated the oxidation behavior of pure and Sn doped Cu13 clusters. The results showed significant modification of the cluster geometry upon interaction with oxygen molecule. The interaction of oxygen with Cu13, Cu12Sn1 and Cu11Sn2 clusters show dissociative chemisorption is more favorable than molecular adsorption. In addition, the adsorption energy is found to decrease with the increase in Sn concentration.

Proof of Principle: Immobilisation of Robust CuII3 TbIII -Macrocycles on Small, Suitably Pre-functionalised Gold Nanoparticles.

PubMed

Feltham, Humphrey L C; Dumas, Christophe; Mannini, Matteo; Otero, Edwige; Sainctavit, Philippe; Sessoli, Roberta; Meledandri, Carla J; Brooker, Sally

2017-02-21

In a proof-of-principle study, a soluble macrocyclic single-molecule magnet (SMM) containing a Cu II 3 Tb III magnetic core was covalently grafted onto small gold nanoparticles pre-functionalised with carboxylate-terminated tethers. A modified microemulsion method allowed production of the small and monodisperse nanoparticles (approximately 3.5 nm in diameter) for the chemisorption of a large amount of intact macrocyclic complexes in the hybrid system. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sensitivity of BN nano-cages to caffeine and nicotine molecules

NASA Astrophysics Data System (ADS)

Soltani, Alireza; Baei, Mohammad T.; Tazikeh Lemeski, E.; Shahini, Malihe

2014-12-01

Adsorption of caffeine and nicotine molecules over B12N12 and B16N16 nano-cages were investigated by using first-principles calculations to define whether BN nano-cages are applicable for filtering or sensing caffeine and nicotine molecules. The chemisorption energy of nicotine molecule on BN nano-cages is very stronger than caffeine molecule. Upon the adsorption of caffeine and nicotine molecules, the electronic properties of the BN nano-cages can be significantly changed, being too much sensitized on the caffeine and nicotine adsorptions.

Photoassisted Kelvin probe force microscopy at GaN surfaces: The role of polarity

NASA Astrophysics Data System (ADS)

Wei, J. D.; Li, S. F.; Atamuratov, A.; Wehmann, H.-H.; Waag, A.

2010-10-01

The behavior of GaN surfaces during photoassisted Kelvin probe force microscopy is demonstrated to be strongly dependant on surface polarity. The surface photovoltage of GaN surfaces illuminated with above-band gap light is analyzed as a function of time and light intensity. Distinct differences between Ga-polar and N-polar surfaces could be identified, attributed to photoinduced chemisorption of oxygen during illumination. These differences can be used for a contactless, nondestructive, and easy-performable analysis of the polarity of GaN surfaces.

A quantitative method to discriminate between non-specific and specific lectin-glycan interactions on silicon-modified surfaces.

PubMed

Yang, Jie; Siriwardena, Aloysius; Boukherroub, Rabah; Ozanam, François; Szunerits, Sabine; Gouget-Laemmel, Anne Chantal

2016-02-15

Essential to the success of any surface-based carbohydrate biochip technology is that interactions of the particular interface with the target protein be reliable and reproducible and not susceptible to unwanted nonspecific adsorption events. This condition is particularly important when the technology is intended for the evaluation of low-affinity interactions such as those typically encountered between lectins and their monomeric glycan ligands. In this paper, we describe the fabrication of glycan (mannoside and lactoside) monolayers immobilized on hydrogenated crystalline silicon (111) surfaces. An efficient conjugation protocol featuring a key "click"-based coupling step has been developed which ensures the obtention of interfaces with controlled glycan density. The adsorption behavior of these newly developed interfaces with the lectins, Lens culinaris and Peanut agglutinin, has been probed using quantitative IR-ATR and the data interpreted using various isothermal models. The analysis reveals that protein physisorption to the interface is more prevalent than specific chemisorption for the majority of washing protocols investigated. Physisorption can be greatly suppressed through application of a strong surfactinated rinse. The coexistence of chemisorption and physisorption processes is further demonstrated by quantification of the amounts of adsorbed proteins distributed on the surface, in correlation with the results obtained by atomic force microscopy (AFM). Taken together, the data demonstrates that the nonspecific adsorption of proteins to these glycan-terminated surfaces can be effectively eliminated through the proper control of the chemical structure of the surface monolayer combined with the implementation of an appropriate surface-rinse protocol. Copyright © 2015 Elsevier Inc. All rights reserved.

Reactivity and Catalytic Activity of Hydrogen Atom Chemisorbed Silver Clusters.

PubMed

Manzoor, Dar; Pal, Sourav

2015-06-18

Metal clusters of silver have attracted recent interest of researchers as a result of their potential in different catalytic applications and low cost. However, due to the completely filled d orbital and very high first ionization potential of the silver atom, the silver-based catalysts interact very weakly with the reacting molecules. In the current work, density functional theory calculations were carried out to investigate the effect of hydrogen atom chemisorption on the reactivity and catalytic properties of inert silver clusters. Our results affirm that the hydrogen atom chemisorption leads to enhancement in the binding energy of the adsorbed O2 molecule on the inert silver clusters. The increase in the binding energy is also characterized by the decrease in the Ag-O and increase in the O-O bond lengths in the case of the AgnH silver clusters. Pertinent to the increase in the O-O bond length, a significant red shift in the O-O stretching frequency is also noted in the case of the AgnH silver clusters. Moreover, the hydrogen atom chemisorbed silver clusters show low reaction barriers and high heat of formation of the final products for the environmentally important CO oxidation reaction as compared to the parent catalytically inactive clusters. The obtained results were compared with those of the corresponding gold and hydrogen atom chemisorbed gold clusters obtained at the same level of theory. It is expected the current computational study will provide key insights for future advances in the design of efficient nanosilver-based catalysts through the adsorption of a small atom or a ligand.

Ion-enhanced oxidation of aluminum as a fundamental surface process during target poisoning in reactive magnetron sputtering

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

Kuschel, Thomas; Keudell, Achim von

2010-05-15

Plasma deposition of aluminum oxide by reactive magnetron sputtering (RMS) using an aluminum target and argon and oxygen as working gases is an important technological process. The undesired oxidation of the target itself, however, causes the so-called target poisoning, which leads to strong hysteresis effects during RMS operation. The oxidation occurs by chemisorption of oxygen atoms and molecules with a simultaneous ion bombardment being present. This heterogenous surface reaction is studied in a quantified particle beam experiment employing beams of oxygen molecules and argon ions impinging onto an aluminum-coated quartz microbalance. The oxidation and/or sputtering rates are measured with thismore » microbalance and the resulting oxide layers are analyzed by x-ray photoelectron spectroscopy. The sticking coefficient of oxygen molecules is determined to 0.015 in the zero coverage limit. The sputtering yields of pure aluminum by argon ions are determined to 0.4, 0.62, and 0.8 at 200, 300, and 400 eV. The variation in the effective sticking coefficient and sputtering yield during the combined impact of argon ions and oxygen molecules is modeled with a set of rate equations. A good agreement is achieved if one postulates an ion-induced surface activation process, which facilitates oxygen chemisorption. This process may be identified with knock-on implantation of surface-bonded oxygen, with an electric-field-driven in-diffusion of oxygen or with an ion-enhanced surface activation process. Based on these fundamental processes, a robust set of balance equations is proposed to describe target poisoning effects in RMS.« less

Theoretical studies of chemisorption and dimer model systems: Moller-Plesset and configuration interaction calculations on PdH, PdC, PdO, PdF, Pd sub 2 , and PdCO

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

Schwerdtfeger, P.; McFeaters, J.S.; Moore, J.J.

1991-01-01

Ab initio SCF studies have been performed to study the molecular properties of several single-bonded palladium compounds, PdH, PdC, PdO, PdF, Pd{sub 2}, and PdCO, which are important in surface and materials science. Electron correlation effects were evaluated by a second- and third-order Moller-Plesset (MP) perturbation theory and a size-consistency-corrected configuration interaction with single and double substitutions (CISC). Relativistic effects were investigated for PdH and PdF. The ground state of PdC has been calculated at the CISC level to be a {sup 3}{Pi} state which is only 0.26 eV below the {sup 3}{Sigma}{sup {minus}} state (previously assigned ground state) andmore » 0.51 eV below the {sup 1}{Sigma}{sup +} state. PdC is predicted to be stable in the gas phase, and the possibility of preparing this compound is investigated. The bonding in CO chemisorbed on palladium is studied by using the model Pd-CO system. The effect of d{sub {pi}}-{pi}{sup *} back-bonding, discussed at the Hartree-Fock and CI level, is compared with results from multiple-scattering {Chi}{alpha} calculations. The C-O stretching frequency shift for CO on palladium was analyzed at various levels of theory, and the results indicated that the decrease in the CO force constant associated with chemisorption is not solely the result of d{sub {pi}}-{pi}{sup *} back-bonding.« less

Energetics of CO2 and H2O adsorption on zinc oxide.

PubMed

Gouvêa, Douglas; Ushakov, Sergey V; Navrotsky, Alexandra

2014-08-05

Adsorption of H2O and CO2 on zinc oxide surfaces was studied by gas adsorption calorimetry on nanocrystalline samples prepared by laser evaporation in oxygen to minimize surface impurities and degassed at 450 °C. Differential enthalpies of H2O and CO2 chemisorption are in the range -150 ±10 kJ/mol and -110 ±10 kJ/mol up to a coverage of 2 molecules per nm(2). Integral enthalpy of chemisorption for H2O is -96.8 ±2.5 kJ/mol at 5.6 H2O/nm(2) when enthalpy of water condensation is reached, and for CO2 is -96.6 ±2.5 kJ/mol at 2.6 CO2/nm(2) when adsorption ceases. These values are consistent with those reported for ZnO prepared by other methods after similar degas conditions. The similar energetics suggests possible competition of CO2 and H2O for binding to ZnO surfaces. Exposure of bulk and nanocrystalline ZnO with preadsorbed CO2 to water vapor results in partial displacement of CO2 by H2O. In contrast, temperature-programmed desorption (TPD) indicates that a small fraction of CO2 is retained on ZnO surfaces up to 800 °C, under conditions where all H2O is desorbed, with adsorption energies near -200 kJ/mol. Although molecular mechanisms of adsorption were not studied, the thermodynamic data are consistent with dissociative adsorption of H2O at low coverage and with several different modes of CO2 binding.

Rethinking chemisorption: New insights into the factors controlling the binding energy

NASA Astrophysics Data System (ADS)

Alcantara Ortigoza, Marisol; Stolbov, Sergey

2015-03-01

Chemisorption of atomic and molecular species on a substrate induces electronic charge redistribution upon which substrate nuclei respond by adjusting their positions. This lattice distortion has been linked to the binding energy EB of the adsorbed species and attached to the so-called surface relaxation energy, Erx. We have found, however, that for transition metals the energy associated with the mere charge redistribution Eelec is much larger than Erx and thus both contributions must be considered [1]. In this work, we quantify the electronic and structural perturbation energy EP brought by various adsorbates on surfaces to understand anomalous adsorbate binding energies, i.e., those in which EP strongly influences the magnitude of EB. For example, for O adsorption on Au(111), while Erx is only 0.25 eV, the overall perturbation energy EP affecting EB(O) is ~ 1 eV [1]. This indicates that EP cannot be ignored but also that local bonds may not be as weak as portrayed by EB, even though EB is significantly reduced. We expose cases in which EP is really dominated by the lattice distortion energy, as well as a rationale for its trends as a function of the substrate and adsorbate. We discuss the implications of the fact that EB is not always predominately controlled by the bond-strength on heterogeneous catalysis, as well as the applications of the same fact. M. Alcántara Ortigoza and S. Stolbov; ``The Perturbation Energy: The missing key to understand gold `nobleness.' '' Submitted in October 2014 This work was supported the NSF under Grant CBET-1249134.

Effects of H ₂SO₄ and O ₂ on Hg⁰ uptake capacity and reversibility of sulfur-impregnated activated carbon under dynamic conditions.

PubMed

Wei, Yuanyang; Yu, Danqing; Tong, Shitang; Jia, Charles Q

2015-02-03

Powder activated carbon (AC) injection is widely considered as the most viable technology for removing gaseous elemental mercury (Hg(0)) in flue gases of coal-fired power plants. However, sulfuric acid (H2SO4) can form on the external and internal surfaces of AC particles due to the presence of sulfur oxides, nitrogen oxides, oxygen, and moisture in flue gases. This work focuses on the effects of H2SO4 and O2 on the Hg(0) uptake capacity and reversibility of sulfur impregnated activated carbon (SIAC) under dynamic conditions. Experiments were conducted with 25 μg-Hg(0)/m(3) of nitrogen or air, using a semicontinuous flow fixed-bed reactor kept at 120 or 180 °C. H2SO4 had a profound hindering effect on Hg(0) uptake due to pore blockage. O2 significantly enhanced Hg(0) uptake and its reversibility, via the oxidation of Hg(0) which facilitated chemisorption and the subsequent physisorption onto chemically adsorbed Hg. Absorption of Hg in H2SO4 was unlikely a significant contributor, when Hg(0) concentrations were at levels of typical power plants (tens of ppb). The reversibility of and relative contributions of physisorption and chemisorption to Hg(0) uptake would change with Hg(0) concentrations in flue gases. These findings could be significant in developing a complete solution for Hg capture where the handling of spent sorbent materials and the possible secondary pollution need to be considered.

The selective hydrogenation of crotonaldehyde over bimetallic catalysts

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

Schoeb, Ann M.

1997-10-17

The selective hydrogenation of crotonaldehyde has been investigated over a monometallic Pt/SiO 2 catalyst and platinum bimetallic catalysts where the second metal was either silver, copper, or tin. The effects of addition of a second metal to the Pt/SiO 2 system on the selectivity to crotyl alcohol were investigated. The Pt-Sn bimetallic catalysts were characterized by hydrogen chemisorption, 1H NMR and microcalorimetry. The Pt-Ag/SiO 2 and Pt-Cu/SiO 2 catalysts were characterized by hydrogen chemisorption. Pt-Sn/SiO 2 catalysts selectively hydrogenated crotonaldehyde to crotyl alcohol and the method of preparation of these catalysts affected the selectivity. The most selective Pt-Sn/SiO 2 catalystsmore » for the hydrogenation of crotonaldehyde to crotyl alcohol were those in which the Sn precursor was dissolved in a HCl solution. Sn increased both the rate of formation of butyraldehyde and the rate of formation of crotyl alcohol. The Pt/SiO 2, Pt-Ag/SiO 2 and Pt-Cu/SiO 2 catalysts produced only butyraldehyde. Initial heats of adsorption (~90 kJ/mol) measured using microcalorimetry were not affected by the presence of Sn on Pt. We can conclude that there is no through metal electronic interaction between Pt and Sn at least with respect to hydrogen surface bonds since the Pt and Pt-Sn at least with respect to hydrogen surface bonds since the Pt and Pt-Sn had similar initial heats of adsorption coupled with the invariance of the 1H NMR Knight shift.« less

Enhancing the Properties of Carbon and Gold Substrates by Surface Modification

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

Harnisch, Jennifer Anne

2001-01-01

The properties of both carbon and gold substrates are easily affected by the judicious choice of a surface modification protocol. Several such processes for altering surface composition have been published in literature. The research presented in this thesis primarily focuses on the development of on-column methods to modify carbon stationary phases used in electrochemically modulated liquid chromatography (EMLC). To this end, both porous graphitic carbon (PGC) and glassy carbon (GC) particles have been modified on-column by the electroreduction of arenediazonium salts and the oxidation of arylacetate anions (the Kolbe reaction). Once modified, the carbon stationary phases show enhanced chromatographic performancemore » both in conventional liquid chromatographic columns and EMLC columns. Additionally, one may also exploit the creation of aryl films to by electroreduction of arenediazonium salts in the creation of nanostructured materials. The formation of mercaptobenzene film on the surface of a GC electrode provides a linking platform for the chemisorption of gold nanoparticles. After deposition of nanoparticles, the surface chemistry of the gold can be further altered by self-assembled monolayer (SAM) formation via the chemisorption of a second thiol species. Finally, the properties of gold films can be altered such that they display carbon-like behavior through the formation of benzenehexathiol (BHT) SAMs. BHT chemisorbs to the gold surface in a previously unprecedented planar fashion. Carbon and gold substrates can be chemically altered by several methodologies resulting in new surface properties. The development of modification protocols and their application in the analytical arena is considered herein.« less

Influence of Alumina Binder Content on Catalytic Performance of Ni/HZSM-5 for Hydrodeoxygenation of Cyclohexanone

PubMed Central

Kong, Xiangjin; Liu, Junhai

2014-01-01

The influence of the amount of alumina binders on the catalytic performance of Ni/HZSM-5 for hydrodeoxygenation of cyclohexanone was investigated in a fixed-bed reactor. N2 sorption, X-ray diffraction, H2-chemisorption and temperature-programmed desorption of ammonia were used to characterize the catalysts. It can be observed that the Ni/HZSM-5 catalyst bound with 30 wt.% alumina binder exhibited the best catalytic performance. The high catalytic performance may be due to relatively good Ni metal dispersion, moderate mesoporosity, and proper acidity of the catalyst. PMID:25009974

Influence of alumina binder content on catalytic performance of Ni/HZSM-5 for hydrodeoxygenation of cyclohexanone.

PubMed

Kong, Xiangjin; Liu, Junhai

2014-01-01

The influence of the amount of alumina binders on the catalytic performance of Ni/HZSM-5 for hydrodeoxygenation of cyclohexanone was investigated in a fixed-bed reactor. N2 sorption, X-ray diffraction, H2-chemisorption and temperature-programmed desorption of ammonia were used to characterize the catalysts. It can be observed that the Ni/HZSM-5 catalyst bound with 30 wt.% alumina binder exhibited the best catalytic performance. The high catalytic performance may be due to relatively good Ni metal dispersion, moderate mesoporosity, and proper acidity of the catalyst.

Relative impact of H 2 O and O 2 in the oxidation of UO 2 powders from 50 to 300 °C

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

Donald, Scott B.; Davisson, M. Lee; Dai, Zurong

Here, we studied the reaction of water and molecular oxygen with stoichiometric uranium dioxide (i.e. UO 2) powder at elevated temperature by high-resolution x-ray photoelectron spectroscopy (XPS), infrared (IR) spectroscopy, powder x-ray diffraction (XRD), and scanning electron microscopy (SEM). We observed and quatified oxidation resulting from the dissociative chemisorption of the adsorbing molecules and subsequent incorporation into the oxide lattice. Molecular oxygen was found to be a stronger oxidation agent than water at elevated temperatures but not at ambient.

Size-dependent surface-enhanced Raman scattering of sodium benzoate on Silver nanoparticles

NASA Astrophysics Data System (ADS)

Badr, Y.; Mahmoud, M. A.

2005-07-01

The absorption spectrum of silver nanoparticles (Ag NPs) with different size and the transmission electron microscopy (TEM) was recorded. Surface-enhanced Raman scattering (SERS) spectra of Sodium Benzoate (SB) adsorbed on Ag NPs with different particle size were studied. The carboxylic group bands were enhanced as the particle size decreases due to the chemisorption of SB on the Ag NPs through it in which the carboxyl group was perpendicular to the surface and the benzene ring parallel to the surface; the SB bands were enhanced as the coverage density of Ag NPs increased.

Sorption J-T refrigeration utilizing manganese nitride chemisorption

NASA Technical Reports Server (NTRS)

Jones, Jack; Lund, Alan

1990-01-01

The equilibrium pressures and compositions have been measured for a system of finely powdered manganese nitride and nitrogen gas at 650, 700, 800, and 850 C for various nitrogen loadings. Pressures ranged from less than 0.02 MPa at 650 C to 6.38 MPa at 850 C. Analysis of the test results has shown that under certain conditions Mn(x)N(y) could potentially be used in a triple regenerative sorption compressor refrigeration system, but the potential power savings are small compared to the increased complexity and reliability problems associated with very high temperature (above 950 C) pressurized systems.

Scattering, Adsorption, and Langmuir-Hinshelwood Desorption Models for Physisorptive and Chemisorptive Gas-Surface Systems

DTIC Science & Technology

2013-09-01

respectively, and ΦQw is the reflected flux of Q at complete accommodation. Typical properties of Q are tangential momentum mct , normal mo- mentum mcn, and...that σt ≡ mct −mc′t mct −mcw = ct − c′t ct , (9) 23 where c′t is the post-collisional tangential speed, and cw is the speed of the wall, which in this...was measured within an experimental error of ±0.02, and the coverage θ noise level was about 0.01 ML. 35 MKS simulations are compared with data in

Relative impact of H2O and O2 in the oxidation of UO2 powders from 50 to 300 °C

NASA Astrophysics Data System (ADS)

Donald, Scott B.; Davisson, M. Lee; Dai, Zurong; Roberts, Sarah K.; Nelson, Art J.

2017-12-01

The reaction of water and molecular oxygen with stoichiometric uranium dioxide (i.e. UO2) powder at elevated temperature was studied by high-resolution x-ray photoelectron spectroscopy (XPS), infrared (IR) spectroscopy, powder x-ray diffraction (XRD), and scanning electron microscopy (SEM). Oxidation resulting from the dissociative chemisorption of the adsorbing molecules and subsequent incorporation into the oxide lattice was observed and quantified. Molecular oxygen was found to be a stronger oxidation agent than water at elevated temperatures but not at ambient.

Coloration of tyrosine by organic-semiconductor interfacial charge-transfer transitions

NASA Astrophysics Data System (ADS)

Fujisawa, Jun-ichi; Kikuchi, Natsumi; Hanaya, Minoru

2016-11-01

L-tyrosine (Tyr) plays a crucial role as a proteinogenic amino acid and also as a precursor to several neurotransmitters and hormones. Here we demonstrate coloration of Tyr based on organic-semiconductor interfacial charge-transfer (ICT) transitions. The ICT transitions from Tyr to TiO2 are induced by the chemisorption of Tyr on TiO2 surfaces via the hydroxy group of the phenol moiety. Because other amino acids possess no chemical group to induce ICT transitions, this coloration method enables to detect Tyr selectively without drastic structural change in contrast to the conventional coloration methods.

Chlorination of alumina in kaolinitic clay

NASA Astrophysics Data System (ADS)

Grob, B.; Richarz, W.

1984-09-01

The chlorination of alumina in kaolinitic clay with Cl2 and CO gas mixtures was studied gravimetrically. The effects of the calcination method and of NaCl addition on the reactivity of the clay were examined. Fast reaction rates were achieved only with samples previously exposed to a sulfating treatment. Optimum conditions, with maximum yield and selectivity to A1C13 and minimum SiO2 conversion, were found between 770 and 970 K. At higher temperatures the SiCl4 formed poisons the reactive alumina surface by selective chemisorption with a marked decrease of the reaction rate.

Adsorptive removal of 2-chlorophenol by low-cost coir pith carbon.

PubMed

Namasivayam, C; Kavitha, D

2003-03-17

Adsorption of 2-chlorophenol (2-CP) by coir pith carbon was carried out by varying the parameters such as agitation time, 2-CP concentration, adsorbent dose, pH and temperature. Adsorption equilibrium reached at 40, 60, 80 and 100 min for 2-CP concentration of 10, 20, 30 and 40 mg/l, respectively. Adsorption followed second-order kinetics. The adsorption equilibrium data obeyed Freundlich isotherm. Acidic pH was favorable for the adsorption of 2-CP. Desorption studies showed that chemisorption plays a major role in the adsorption process. Copyright 2003 Elsevier Science B.V.

Evidence for a novel chemisorption bond: Formate (HCO/sub 2/) on Cu(100)

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

Stoehr, J.; Outka, D.A.; Madix, R.J.

1985-03-25

Surface extended-x-ray-absorption fine-structure measurements reveal that formate (HCO/sub 2/) groups on Cu(100) chemisorb via the two oxygen atoms in adjacent fourfold hollow sites with an average O-Cu nearest-neighbor bond length of 2.38 +- 0.03 A. This distance is sig- nificantly (approx.0.4 A) longer than typical O-Cu bonds in bulk compounds and all known surface complexes. The unusually large O-Cu distance is attributed to a steric effect involving the C atom in HCO/sub 2/ and the nearest-neighbor Cu surface atoms.

Relative impact of H 2 O and O 2 in the oxidation of UO 2 powders from 50 to 300 °C

DOE PAGES

Donald, Scott B.; Davisson, M. Lee; Dai, Zurong; ...

2017-10-04

Here, we studied the reaction of water and molecular oxygen with stoichiometric uranium dioxide (i.e. UO 2) powder at elevated temperature by high-resolution x-ray photoelectron spectroscopy (XPS), infrared (IR) spectroscopy, powder x-ray diffraction (XRD), and scanning electron microscopy (SEM). We observed and quatified oxidation resulting from the dissociative chemisorption of the adsorbing molecules and subsequent incorporation into the oxide lattice. Molecular oxygen was found to be a stronger oxidation agent than water at elevated temperatures but not at ambient.

Infrared spectroscopic study of radiation-induced adsorption of n-hexane on a beryllium surface

NASA Astrophysics Data System (ADS)

Gadzhieva, N. N.

2017-07-01

Radiation-stimulated adsorption on a beryllium surface is studied by IR reflection-absorption spectroscopy. It is found that γ-irradiation at room temperature leads to the appearance of n-hexane adsorption centers on a beryllium surface according to molecular and dissociation mechanisms. The kinetics of n-hexane adsorption in a Be- n-hexane system is studied; activated dissociative chemisorption accompanied by formation of beryllium alkyls and surface hydrides is observed at absorbed doses 15 kGy ≤ Vγ ≤ 35 kGy. A possible mechanism of this process is suggested.

Thermoelectric properties of nano-granular indium-tin-oxide within modified electron filtering model with chemisorption-type potential barriers

NASA Astrophysics Data System (ADS)

Brinzari, V.; Nika, D. L.; Damaskin, I.; Cho, B. K.; Korotcenkov, G.

2016-07-01

In this work, an approach to the numerical study of the thermoelectric parameters of nanoscale indium tin oxide (ITO, Sn content<10 at%) based on an electron filtering model (EFM) was developed. Potential barriers at grain boundaries were assumed to be responsible for a filtering effect. In the case of the dominant inelastic scattering of electrons, the maximal distance between potential barriers was limited in this modified model. The algorithm for such characteristic length calculation was proposed, and its value was evaluated for ITO. In addition, the contributions of different scattering mechanisms (SMs) in electron transport were examined. It was confirmed that in bulk ITO, the scattering on polar optical phonons (POPs) and ionized impurities dominates, limiting electron transport. In the framework of the filtering model, the basic thermoelectric parameters (i.e., electrical conductivity, mobility, Seebeck coefficient, and power factor (PF)) were calculated for ITO in the temperature range of 100-500 °C as a function of potential barrier height. The results demonstrated a sufficient rise of the Seebeck coefficient with an increase in barrier height and specific behavior of PF. It was found that PF is very sensitive to barrier height, and at its optimal value for granular ITO, it may exceed the PF for bulk ITO by 3-5 times. The PF maximum was achieved by band bending, slightly exceeding Fermi energy. The nature of surface potential barriers in nano-granular ITO with specific grains is due to the oxygen chemisorption effect, and this can be observed despite of the degeneracy of the conduction band (CB). This hypothesis and the corresponding calculations are in good agreement with recent experimental studies [Brinzari et al. Thin Solid Films 552 (2014) 225].

Nanostructure-directed physisorption vs chemisorption at semiconductor interfaces: the inverse of the HSAB concept.

PubMed

Gole, James L; Ozdemir, Serdar

2010-08-23

A concept, complementary to that of hard and soft acid-base interactions (HSAB-dominant chemisorption) and consistent with dominant physisorption to a semiconductor interface, is presented. We create a matrix of sensitivities and interactions with several basic gases. The concept, based on the reversible interaction of hard-acid surfaces with soft bases, hard-base surfaces with soft acids, or vice versa, corresponds 1) to the inverse of the HSAB concept and 2) to the selection of a combination of semiconductor interface and analyte materials, which can be used to direct a physisorbed vs chemisorbed interaction. The technology, implemented on nanopore coated porous silicon micropores, results in the coupling of acid-base chemistry with the depletion or enhancement of majority carriers in an extrinsic semiconductor. Using the inverse-HSAB (IHSAB) concept, significant and predictable changes in interface sensitivity for a variety of gases can be implemented. Nanostructured metal oxide particle depositions provide selectivity and complement a highly efficient electrical contact to a porous silicon nanopore covered microporous interface. The application of small quantities (much less than a monolayer) of nanostructured metals, metal oxides, and catalysts which focus the physisorbtive and chemisorbtive interactions of the interface, can be made to create a range of notably higher sensitivities for reversible physisorption. This is exemplified by an approach to reversible, sensitive, and selective interface responses. Nanostructured metal oxides developed from electroless gold (Au(x)O), tin (SnO(2)), copper (Cu(x)O), and nickel (NiO) depositions, nanoalumina, and nanotitania are used to demonstrate the IHSAB concept and provide for the detection of gases, including NH(3), PH(3), CO, NO, and H(2)S, in an array-based format to the sub-ppm level.

Influence of lanthanum on the surface structure and CO hydrogenation activity of supported cobalt catalysts

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

Ledford, J.S.; Houalla, M.; Proctor, A.

1989-09-07

X-ray photoelectron spectroscopy (ESCA or XPS), X-ray diffraction (XRD), Raman spectroscopy, H{sub 2} chemisorption, and gravimetric analysis have been used to characterize three series of La/Al{sub 3}O{sub 3} and CoLa/Al{sub 2}O{sub 3} catalysts. CoLa/Al{sub 2}O{sub 3} catalysts were prepared by two methods: impregnation of La first followed by Co (designated CoLay) and impregnation of Co first followed by La (designated LayCo). The information obtained from surface and bulk characterization has been compared with CO hydrogenation activity and selectivity of the supported Co/Al{sub 2}O{sub 3} catalysts. For CoLay catalysts with low La loadings (La/Al atomic ratio {le} 0.026), the presence ofmore » La had little effect on the structure or CO hydrogenation activity. However, the selectivity to higher hydrocarbons and olefinic products increased with increasing La content. For CoLay catalysts with higher La loadings, Co{sub 3}O{sub 4} is suppressed in favor of an amorphous dispersed La-Co mixed oxide. ESCA and H{sub 2} chemisorption indicated higher dispersion of the metallic cobalt phase for high La loadings. The turnover frequency (TOF) for CO hydrogenation decreased dramatically for high La loadings. This has been correlated to the decrease in the amount of Co{sub 3}O{sub 4} present in the La-rich catalysts. Catalysts prepared by reverse impregnation (LayCo) showed little evidence of La-Co interaction. No significant variation in reducibility or cobalt metal dispersion was observed. Lanthanum addition had little effect on the TOF for CO hydrogenation or the selectivity to olefinic products and higher hydrocarbons.« less

Theory of the reaction dynamics of small molecules on metal surfaces

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

Jackson, Bret

The objective of this project has been to develop realistic theoretical models for gas-surface interactions, with a focus on processes important in heterogeneous catalysis. The dissociative chemisorption of a molecule on a metal is a key step in many catalyzed reactions, and is often the rate-limiting step. We have explored the dissociative chemisorption of H 2, H 2O and CH 4 on a variety of metal surfaces. Most recently, our extensive studies of methane dissociation on Ni and Pt surfaces have fully elucidated its dependence on translational energy, vibrational state and surface temperature, providing the first accurate comparisons with experimentalmore » data. We have explored Eley-Rideal and hot atom reactions of H atoms with H- and C-covered metal surfaces. H atom interactions with graphite have also been explored, including both sticking and Eley-Rideal recombination processes. Again, our methods made it possible to explain several experiments studying these reactions. The sticking of atoms on metal surfaces has also been studied. To help elucidate the experiments that study these processes, we examine how the reaction dynamics depend upon the nature of the molecule-metal interaction, as well as experimental variables such as substrate temperature, beam energy, angle of impact, and the internal states of the molecules. Electronic structure methods based on Density Functional Theory are used to compute each molecule-metal potential energy surface. Both time-dependent quantum scattering techniques and quasi-classical methods are used to examine the reaction or scattering dynamics. Much of our effort has been directed towards developing improved quantum methods that can accurately describe reactions, as well as include the effects of substrate temperature (lattice vibration).« less

A quantum mechanical study of water adsorption on the (110) surfaces of rutile SnO₂ and TiO₂: investigating the effects of intermolecular interactions using hybrid-exchange density functional theory.

PubMed

Patel, M; Sanches, F F; Mallia, G; Harrison, N M

2014-10-21

Periodic hybrid-exchange density functional theory calculations are used to explore the first layer of water at model oxide surfaces, which is an important step for understanding the photocatalytic reactions involved in solar water splitting. By comparing the structure and properties of SnO2(110) and TiO2(110) surfaces in contact with water, the effects of structural and electronic differences on the water chemistry are examined. The dissociative adsorption mode at low coverage (1/7 ML) up to monolayer coverage (1 ML) on both SnO2 and TiO2(110) surfaces is analysed. To investigate further the intermolecular interactions between adjacent adsorbates, monolayer adsorption on each surface is explored in terms of binding energies and bond lengths. Analysis of the water adsorption geometry and energetics shows that the relative stability of water adsorption on SnO2(110) is governed largely by the strength of the chemisorption and hydrogen bonds at the surface of the adsorbate-substrate system. However on TiO2(110), a more complicated scenario of the first layer of water on its surface arises in which there is an interplay between chemisorption, hydrogen bonding and adsorbate-induced atomic displacements in the surface. Furthermore the projected density of states of each surface in contact with a mixture of adsorbed water molecules and adsorbed hydroxyls is presented and sheds some light on the nature of the crystalline chemical bonds as well as on why adsorbed water has often been reported to be unstable on rutile SnO2(110).

Reaction rate kinetics for in situ combustion retorting of Michigan Antrim oil shale

USGS Publications Warehouse

Rostam-Abadi, M.; Mickelson, R.W.

1984-01-01

The intrinsic reaction rate kinetics for the pyrolysis of Michigan Antrim oil shale and the oxidation of the carbonaceous residue of this shale have been determined using a thermogravimetric analysis method. The kinetics of the pyrolysis reaction were evaluated from both isothermal and nonisothermal rate data. The reaction was found to be second-order with an activation energy of 252.2 kJ/mole, and with a frequency factor of 9.25 ?? 1015 sec-1. Pyrolysis kinetics were not affected by heating rates between 0.01 to 0.67??K/s. No evidence of any reactions among the oil shale mineral constituents was observed at temperatures below 1173??K. However, it was found that the presence of pyrite in oil shale reduces the primary devolatilization rate of kerogen and increases the amount of residual char in the spent shale. Carbonaceous residues which were prepared by heating the oil shale at a rate of 0.166??K/s to temperatures between 923??K and 1073??K, had the highest reactivities when oxidized at 0.166??K/s in a gas having 21 volume percent oxygen. Oxygen chemisorption was found to be the initial precursor to the oxidation process. The kinetics governing oxygen chemisorption is (Equation Presented) where X is the fractional coverage. The oxidation of the carbonaceous residue was found also to be second-order. The activation energy and the frequency factor determined from isothermal experiments were 147 kJ/mole and 9.18??107 sec-1 respectively, while the values of these parameters obtained from a nonisothermal experiment were 212 kJ/mole and 1.5??1013 sec-1. The variation in the rate constants is attributed to the fact that isothermal and nonisothermal analyses represent two different aspects of the combustion process.

Disilane chemisorption on Si(x)Ge(1-x)(100)-(2 x 1): molecular mechanisms and implications for film growth rates.

PubMed

Ng, Rachel Qiao-Ming; Tok, E S; Kang, H Chuan

2009-07-28

At low temperatures, hydrogen desorption is known to be the rate-limiting process in silicon germanium film growth via chemical vapor deposition. Since surface germanium lowers the hydrogen desorption barrier, Si(x)Ge((1-x)) film growth rate increases with the surface germanium fraction. At high temperatures, however, the molecular mechanisms determining the epitaxial growth rate are not well established despite much experimental work. We investigate these mechanisms in the context of disilane adsorption because disilane is an important precursor used in film growth. In particular, we want to understand the molecular steps that lead, in the high temperature regime, to a decrease in growth rate as the surface germanium increases. In addition, there is a need to consider the issue of whether disilane adsorbs via silicon-silicon bond dissociation or via silicon-hydrogen bond dissociation. It is usually assumed that disilane adsorption occurs via silicon-silicon bond dissociation, but in recent work we provided theoretical evidence that silicon-hydrogen bond dissociation is more important. In order to address these issues, we calculate the chemisorption barriers for disilane on silicon germanium using first-principles density functional theory methods. We use the calculated barriers to estimate film growth rates that are then critically compared to the experimental data. This enables us to establish a connection between the dependence of the film growth rate on the surface germanium content and the kinetics of the initial adsorption step. We show that the generally accepted mechanism where disilane chemisorbs via silicon-silicon bond dissociation is not consistent with the data for film growth kinetics. Silicon-hydrogen bond dissociation paths have to be included in order to give good agreement with the experimental data for high temperature film growth rate.

Characterizing water-metal interfaces and machine learning potential energy surfaces

NASA Astrophysics Data System (ADS)

Ryczko, Kevin

In this thesis, we first discuss the fundamentals of ab initio electronic structure theory and density functional theory (DFT). We also discuss statistics related to computing thermodynamic averages of molecular dynamics (MD). We then use this theory to analyze and compare the structural, dynamical, and electronic properties of liquid water next to prototypical metals including platinum, graphite, and graphene. Our results are built on Born-Oppenheimer molecular dynamics (BOMD) generated using density functional theory (DFT) which explicitly include van der Waals (vdW) interactions within a first principles approach. All calculations reported use large simulation cells, allowing for an accurate treatment of the water-electrode interfaces. We have included vdW interactions through the use of the optB86b-vdW exchange correlation functional. Comparisons with the Perdew-Burke-Ernzerhof (PBE) exchange correlation functional are also shown. We find an initial peak, due to chemisorption, in the density profile of the liquid water-Pt interface not seen in the liquid water-graphite interface, liquid watergraphene interface, nor interfaces studied previously. To further investigate this chemisorption peak, we also report differences in the electronic structure of single water molecules on both Pt and graphite surfaces. We find that a covalent bond forms between the single water molecule and the platinum surface, but not between the single water molecule and the graphite surface. We also discuss the effects that defects and dopants in the graphite and graphene surfaces have on the structure and dynamics of liquid water. Lastly, we introduce artificial neural networks (ANNs), and demonstrate how they can be used to machine learn electronic structure calculations. As a proof of principle, we show the success of an ANN potential energy surfaces for a dimer molecule with a Lennard-Jones potential.

Low-Dimensional Materials for Optoelectronic and Bioelectronic Applications

NASA Astrophysics Data System (ADS)

Hong, Tu

In this thesis, we first discuss the fundamentals of ab initio electronic structure theory and density functional theory (DFT). We also discuss statistics related to computing thermodynamic averages of molecular dynamics (MD). We then use this theory to analyze and compare the structural, dynamical, and electronic properties of liquid water next to prototypical metals including platinum, graphite, and graphene. Our results are built on Born-Oppenheimer molecular dynamics (BOMD) generated using density functional theory (DFT) which explicitly include van der Waals (vdW) interactions within a first principles approach. All calculations reported use large simulation cells, allowing for an accurate treatment of the water-electrode interfaces. We have included vdW interactions through the use of the optB86b-vdW exchange correlation functional. Comparisons with the Perdew-Burke-Ernzerhof (PBE) exchange correlation functional are also shown. We find an initial peak, due to chemisorption, in the density profile of the liquid water-Pt interface not seen in the liquid water-graphite interface, liquid watergraphene interface, nor interfaces studied previously. To further investigate this chemisorption peak, we also report differences in the electronic structure of single water molecules on both Pt and graphite surfaces. We find that a covalent bond forms between the single water molecule and the platinum surface, but not between the single water molecule and the graphite surface. We also discuss the effects that defects and dopants in the graphite and graphene surfaces have on the structure and dynamics of liquid water. Lastly, we introduce artificial neural networks (ANNs), and demonstrate how they can be used to machine learn electronic structure calculations. As a proof of principle, we show the success of an ANN potential energy surfaces for a dimer molecule with a Lennard-Jones potential.

Novel nitrogen doped carbon dots for corrosion inhibition of carbon steel in 1 M HCl solution

NASA Astrophysics Data System (ADS)

Cui, Mingjun; Ren, Siming; Zhao, Haichao; Wang, Liping; Xue, Qunji

2018-06-01

Nitrogen doped carbon dots (NCDs) were synthesized and used for inhibiting the corrosion of Q235 carbon steel in hydrochloric acid (HCl) solution. Inhibition effectiveness in short- and long-term immersion was examined using electrochemical measurements, weight loss and surface analysis. Results revealed the inhibition efficiency was improved significantly after adding NCDs and strongly dependent on the concentration of NCDs. SVET results showed that the sample immersed in HCl solution with NCDs showed lower anodic current density mapping than that in blank HCl solution. According to the data extracted from the Langmuir adsorption, the absorption of NCDs involved both chemisorption and physisorption.

Energy storage device including a redox-enhanced electrolyte

DOEpatents

Stucky, Galen; Evanko, Brian; Parker, Nicholas; Vonlanthen, David; Auston, David; Boettcher, Shannon; Chun, Sang-Eun; Ji, Xiulei; Wang, Bao; Wang, Xingfeng; Chandrabose, Raghu Subash

2017-08-08

An electrical double layer capacitor (EDLC) energy storage device is provided that includes at least two electrodes and a redox-enhanced electrolyte including two redox couples such that there is a different one of the redox couples for each of the electrodes. When charged, the charge is stored in Faradaic reactions with the at least two redox couples in the electrolyte and in a double-layer capacitance of a porous carbon material that comprises at least one of the electrodes, and a self-discharge of the energy storage device is mitigated by at least one of electrostatic attraction, adsorption, physisorption, and chemisorption of a redox couple onto the porous carbon material.

Synthesis and Hydrodeoxygenation Properties of Ruthenium Phosphide Catalysts

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

Bowker, Richard H.; Smith, Mica C.; Pease, Melissa

2011-07-01

Ru2P/SiO2 and RuP/SiO2 catalysts were prepared by the temperature-programmed reduction (TPR) of uncalcined precursors containing hypophosphite ion (H2PO2-) as the phosphorus source. The Ru2P/SiO2 and RuP/SiO2 catalysts had small average particle sizes (~4 nm) and high CO chemisorption capacities (90-110 umol/g). The Ru phosphide catalysts exhibited similar or higher furan (C4H4O) hydrodeoxygenation (HDO) activities than did a Ru/SiO2 catalyst, and the phosphide catalysts favored C4 hydrocarbon products while the Ru metal catalyst produced primarily C3 hydrocarbons.

Influence of Mechanical Stretching on Adsorption Properties of Nitrogen-Doped Graphene

NASA Astrophysics Data System (ADS)

Dolinskii, I. Yu.; Katin, K. P.; Grishakov, K. S.; Prudkovskii, V. S.; Kargin, N. I.; Maslov, M. M.

2018-04-01

This paper presents the results of quantum chemical modeling of chemisorption of atomic hydrogen and epoxy, carboxyl, and hydroxyl functional groups on nitrogen-doped graphene. It is shown that the substitutional nitrogen atom does not bind to adsorbing groups directly, but significantly increases the adsorption activity of neighboring carbon atoms. Mechanical stretching of doped graphene reduces the adsorption energy of all the aforementioned radicals. This reduction is significantly greater for the epoxy group than for the other functional groups. The results obtained confirm that, upon a sufficient stretching of a nitrogen-doped graphene sheet, the dissociation of molecular hydrogen and oxygen with subsequent precipitation of the resulting radicals onto graphene can be energetically favorable.

Characterization of recycled rubber media for hydrogen sulphide (H2S) control.

PubMed

Wang, Ning; Park, Jaeyoung; Evans, Eric A; Ellis, Timothy G

2014-01-01

Hydrogen sulphide (H2S) adsorption capacities on recycled rubber media, tyre-derived rubber particle (TDRP), and other rubber material (ORM) have been evaluated. As part of the research, densities, moisture contents, and surface properties of TDRP and ORM have been determined. The research team findings show that TDRP and ORM are more particulate in nature and not highly porous-like activated carbon. The characteristics of surface area, pore size, and moisture content support chemisorption on the macrosurface rather than physical adsorption in micropores. For example, moisture content is essential for H2S adsorption on ORM, and an increase in moisture content results in an increase in adsorption capacity.

Kinetic Characteristics of Hydrogen Transfer Through Palladium-Modified Membrane

NASA Astrophysics Data System (ADS)

Petriev, I. S.; Frolov, V. Yu.; Bolotin, S. N.; Baryshev, M. G.; Kopytov, G. F.

2018-01-01

The paper deals with hydrogen transfer through Pd-23%Ag alloy membrane, the surface of which is modified by the electrolytic deposition of highly dispersed palladium. The dependence between the density of hydrogen flow and its excess pressure on the input surface of membrane is well approximated by the first-order curve. This fact indicates that the process of hydrogen permeability is defined by its dissociation on the input surface. Activation energy of this process is 47.9 kJ/mol which considerably exceeds that of the process of hydrogen transfer through palladium (22-30 kJ/mol). This confirms the fact that the chemisorption is a rate-controlling step of the hydrogen transfer through membrane.

Insight into the adsorption of chloramphenicol on a vermiculite surface

NASA Astrophysics Data System (ADS)

Tri, Nguyen Ngoc; Carvalho, A. J. P.; Dordio, A. V.; Nguyen, Minh Tho; Trung, Nguyen Tien

2018-05-01

Four stable configurations were found upon adsorption of the chloramphenicol on a period slab model of the vermiculite surface, using the PBE and C09-vdW functionals in a projector-augmented wave (PAW) method approach. The adsorption is a strong chemisorption process, characterized by an adsorption energy of -106.5 kcal mol-1 at the most stable configuration. Stability of configurations contributed mainly by Mg⋯O/Cl attractive electrostatic interactions and C/Osbnd H⋯O hydrogen bonds. It is remarkable that the vermiculite is found to be a solid material with good potential to be used for adsorption and consequent removal of this type of antibiotic drugs.

Sequential desorption energy of hydrogen from nickel clusters

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

Deepika,; Kumar, Rakesh, E-mail: rakesh@iitrpr.ac.in; R, Kamal Raj.

2015-06-24

We report reversible Hydrogen adsorption on Nickel clusters, which act as a catalyst for solid state storage of Hydrogen on a substrate. First-principles technique is employed to investigate the maximum number of chemically adsorbed Hydrogen molecules on Nickel cluster. We observe a maximum of four Hydrogen molecules adsorbed per Nickel atom, but the average Hydrogen molecules adsorbed per Nickel atom decrease with cluster size. The dissociative chemisorption energy per Hydrogen molecule and sequential desorption energy per Hydrogen atom on Nickel cluster is found to decrease with number of adsorbed Hydrogen molecules, which on optimization may help in economical storage andmore » regeneration of Hydrogen as a clean energy carrier.« less

Effects of phosphoric acid on the lead-acid battery reactions

NASA Astrophysics Data System (ADS)

Ikeda, Osamu; Iwakura, Chiaki; Yoneyama, Hiroshi; Tamura, Hideo

1986-10-01

The addition of a small amount of phosphoric acid to 5 M H2SO4 (commercial electrolyte of lead-acid batteries) results in various positive effects on the lead-acid battery reactions: (1) depression of the corrosion rate of the lead substrate through a preferential formation of alpha-PbO2 on the substrate surface; (2) retardation of hard sulfate formation or of deactivation of active materials; and (3) change in the crystal morphology of PbSO2 formed on the discharge of PbO2. Most of these effects results from chemisorption of phosphoric acid on PbSO4 crystals produced in the discharge process of PbO2.

Thermodynamics and vibrational study of hydrogenated carbon nanotubes: A DFT study

NASA Astrophysics Data System (ADS)

Khalil, Rana M. Arif; Hussain, Fayyaz; Rana, Anwar Manzoor; Imran, Muhammad

2018-02-01

Thermodynamic stability of the hydrogenated carbon nanotubes has been explored in the chemisorption limit. Statistical physics and density functional theory calculations have been used to predict hydrogen release temperatures at standard pressure in zigzag and armchair carbon nanotubes. It is found that hydrogen release temperatures decrease with increase in diameters of hydrogenated zigzag carbon nanotubes (CNTs) but opposite trend is noted in armchair CNTs at standard pressure of 1 bar. The smaller diameter hydrogenated zigzag CNTs have large values of hydrogen release temperature due to the stability of Csbnd H bonds. The vibrational density of states for hydrogenated carbon nanotubes have been calculated to confirm the Csbnd H stretching mode caused by sp3 hybridization.

Activated adsorption of methane on clean and oxygen-modified Pt?111? and Pd?110?

NASA Astrophysics Data System (ADS)

Valden, M.; Pere, J.; Hirsimäki, M.; Suhonen, S.; Pessa, M.

1997-04-01

Activated adsorption of CH 4 on clean and oxygen modified Pt{111} and Pd{110} has been studied using molecular beam surface scattering. The absolute dissociation probability of CH 4 was measured as a function of the incident normal energy ( E) and the surface temperature ( Ts). The results from clean Pt{111} and Pd{110} are consistent with a direct dissociation mechanism. The dissociative chemisorption dynamics of CH 4 is addressed by using quantum mechanical and statistical models. The influence of adsorbed oxygen on the dissociative adsorption of CH 4 on both Pt{111} and Pd{110} shows that the dissociation probability decreases linearly with increasing oxygen coverage.

Competition between surface chemisorption and cage formation in Fe12O12 clusters

NASA Astrophysics Data System (ADS)

Gutsev, G. L.; Weatherford, C. A.; Jena, P.; Johnson, E.; Ramachandran, B. R.

2013-01-01

The electronic and geometrical structures of the clusters composed of 12 iron and 12 oxygen atoms are obtained using all-electron density functional theory. It is found that the states with geometrical structures corresponding to oxygen chemisorbed on the ground-state Fe12 cluster surface (Fe12O12) are close in total energy to the states whose geometrical configurations are hollow cages (FeO)12. The lowest total energy state is the ferrimagnetic triplet state of Fe12O12. A ferrimagnetic nonet state of (FeO)12 is only marginally higher in total energy. The clusters are rich in nearly degenerate isomers. Oxygen adsorption dramatically quenches the spin of Fe12 clusters.

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

Gallegos, N.G.; Alvarez, A.M.; Cagnoli, M.V.

SiO{sub 2} covered with MgO has been used as support of iron catalysts in the Fischer-Tropsch reaction. Catalysts of 5% (w/w) iron concentration and 2, 4, and 8% (w/w) of MgO on SiO{sub 2} were prepared. Selective chemisorption of CO, volumetric oxidation, and Moessbauer spectroscopy were used to characterize the type of iron species and the metallic crystal sizes. MgO covers the SiO{sub 2} surface and modifies the metallic crystal size. The activity to total hydrocarbons increases with the amount of MgO added. An optimal concentration of about 4% (w/w) was found to have the highest selectivity to olefins. 45more » refs., 13 figs., 3 tabs.« less

Impact of incomplete metal coverage on the electrical properties of metal-CNT contacts: A large-scale ab initio study

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

Fediai, Artem, E-mail: artem.fediai@nano.tu-dresden.de; Ryndyk, Dmitry A.; Center for Advancing Electronics Dresden, TU Dresden, 01062 Dresden

2016-09-05

Using a dedicated combination of the non-equilibrium Green function formalism and large-scale density functional theory calculations, we investigated how incomplete metal coverage influences two of the most important electrical properties of carbon nanotube (CNT)-based transistors: contact resistance and its scaling with contact length, and maximum current. These quantities have been derived from parameter-free simulations of atomic systems that are as close as possible to experimental geometries. Physical mechanisms that govern these dependences have been identified for various metals, representing different CNT-metal interaction strengths from chemisorption to physisorption. Our results pave the way for an application-oriented design of CNT-metal contacts.

Tuning the conductivity along atomic chains by selective chemisorption

NASA Astrophysics Data System (ADS)

Edler, F.; Miccoli, I.; Stöckmann, J. P.; Pfnür, H.; Braun, C.; Neufeld, S.; Sanna, S.; Schmidt, W. G.; Tegenkamp, C.

2017-03-01

Adsorption of Au on vicinal Si(111) surfaces results in growth of long-range ordered metallic quantum wires. In this paper, we utilized site-specific and selective adsorption of oxygen to modify chemically the transport via different channels in the systems Si(553)-Au and Si(557)-Au. They were analyzed by electron diffraction and four-tip STM-based transport experiments. Modeling of the adsorption process by density functional theory shows that the adatoms and rest atoms on Si(557)-Au provide energetically favored adsorption sites, which predominantly alter the transport along the wire direction. Since this structural motif is missing on Si(553)-Au, the transport channels remain almost unaffected by oxidation.

Nanoscale Metal Oxide Semiconductors for Gas Sensing

NASA Technical Reports Server (NTRS)

Hunter, Gary W.; Evans, Laura; Xu, Jennifer C.; VanderWal, Randy L.; Berger, Gordon M.; Kulis, Michael J.

2011-01-01

A report describes the fabrication and testing of nanoscale metal oxide semiconductors (MOSs) for gas and chemical sensing. This document examines the relationship between processing approaches and resulting sensor behavior. This is a core question related to a range of applications of nanotechnology and a number of different synthesis methods are discussed: thermal evaporation- condensation (TEC), controlled oxidation, and electrospinning. Advantages and limitations of each technique are listed, providing a processing overview to developers of nanotechnology- based systems. The results of a significant amount of testing and comparison are also described. A comparison is made between SnO2, ZnO, and TiO2 single-crystal nanowires and SnO2 polycrystalline nanofibers for gas sensing. The TECsynthesized single-crystal nanowires offer uniform crystal surfaces, resistance to sintering, and their synthesis may be done apart from the substrate. The TECproduced nanowire response is very low, even at the operating temperature of 200 C. In contrast, the electrospun polycrystalline nanofiber response is high, suggesting that junction potentials are superior to a continuous surface depletion layer as a transduction mechanism for chemisorption. Using a catalyst deposited upon the surface in the form of nanoparticles yields dramatic gains in sensitivity for both nanostructured, one-dimensional forms. For the nanowire materials, the response magnitude and response rate uniformly increase with increasing operating temperature. Such changes are interpreted in terms of accelerated surface diffusional processes, yielding greater access to chemisorbed oxygen species and faster dissociative chemisorption, respectively. Regardless of operating temperature, sensitivity of the nanofibers is a factor of 10 to 100 greater than that of nanowires with the same catalyst for the same test condition. In summary, nanostructure appears critical to governing the reactivity, as measured by electrical resistance of these SnO2 nanomaterials towards reducing gases. With regard to the sensitivity of the different nascent nanostructures, the electrospun nanofibers appear preferable

Towards modelling the vibrational signatures of functionalized surfaces: carboxylic acids on H-Si(111) surfaces.

PubMed

Feugmo, Conrard Giresse Tetsassi; Champagne, Benoît; Caudano, Yves; Cecchet, Francesca; Chabal, Yves J; Liégeois, Vincent

2012-03-28

In this work, we investigate the adsorption process of two carboxylic acids (stearic and undecylenic) on a H-Si(111) surface via the calculation of structural and energy changes as well as the simulation of their IR and Raman spectra. The two molecules adsorb differently at the surface since the stearic acid simply physisorbs while the undecylenic acid undergoes a chemical reaction with the hydrogen atoms of the surface. This difference is observed in the change of geometry during the adsorption. Indeed, the chemisorption of the undecylenic acid has a bigger impact on the structure than the physisorption of the stearic acid. Consistently, the former is also characterized by a larger value of adsorption energy and a smaller value of the tilting angle with respect to the normal plane. For both the IR and Raman signatures, the spectra of both molecules adsorbed at the surface are in a first approximation the superposition of the spectra of the Si cluster and of the carboxylic acid considered individually. The main deviation from this simple observation is the peak of the stretching Si-H (ν(Si-H)) mode, which is split into two peaks upon adsorption. As expected, the splitting is bigger for the chemisorption than the physisorption. The modes corresponding to atomic displacements close to the adsorption site display a frequency upshift by a dozen wavenumbers. One can also see the disappearance of the peaks associated with the C=C double bond when the undecylenic acid chemisorbs at the surface. The Raman and IR spectra are complementary and one can observe here that the most active Raman modes are generally IR inactive. Two exceptions to this are the two ν(Si-H) modes which are active in both spectroscopies. Finally, we compare our simulated spectra with some experimental measurements and we find an overall good agreement. © 2012 IOP Publishing Ltd

The role of HH interactions in the formation of ordered structures on Ni and Pd single crystals

NASA Astrophysics Data System (ADS)

Muscat, J. P.

1981-09-01

The interaction between H adatoms on a surface is calculated within the embedded cluster model of chemisorption. The model is first applied to the case of two H atoms on a free electron surface. The interaction energy is found to be an oscillatory function of the H-H separation Rab. Application of the free electron model to the problem of chemisorption on transition metal surfaces leads to unphysical results with the prediction of formation of ordered H overlayers which are not observed in LEED experiments. We next include the l = 2 TM muffin tins. Results for H adsorption on the low index faces of Ni and Pd substrates are presented. Graphitic structures are predicted for the (111) faces of both Ni and Pd with the H atoms occupying both types of three-fold hollow sites on the surface. This agrees with the results of LEED experiments for H/Ni(111). Comparison with experiment is not possible in the case of H/Pd(111) owing to the lack of low temperature studies for that system. Zig-zag chains with the H atoms adsorbed in sites of three-fold coordination on alternate sides of the TM(110) rows are predicted for both Ni and Pd. This is in agreement with the results of He diffraction experiments for H/Ni(110). No structure determination has been done for H/Pd(110). Adsorption in the four-fold centre sites for H on the (100) faces of Ni and Pd is found to be unfavourable. The H atoms are expected to adsorb in sites of three-fold symmetry below the (100) surface for H on Pd with formation of a c(2 × 2) structure in agreement with the LEED observations. For H/Ni(100) the H atoms are believed to adsorb above the surface, away from the centre site and to bond to two surface Ni atoms. No short-range ordered structures are predicted in this case.

The dissociative chemisorption of water on Ni(111): Mode- and bond-selective chemistry on metal surfaces

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

Farjamnia, Azar; Jackson, Bret, E-mail: jackson@chem.umass.edu

A fully quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of H{sub 2}O, HOD, and D{sub 2}O on Ni(111). For this late barrier system, excitation of both the bending and stretching modes significantly enhances dissociative sticking. The vibrational efficacies vary somewhat from mode-to-mode but are all relatively close to one, in contrast to methane dissociation, where the behavior is less statistical. Similar to methane dissociation, the motion of lattice atoms near the dissociating molecule can significantly modify the height of the barrier to dissociation, leading to a strong variation in dissociativemore » sticking with substrate temperature. Given a rescaling of the barrier height, our results are in reasonable agreement with measurements of the dissociative sticking of D{sub 2}O on Ni(111), for both laser-excited molecules with one or two quanta of excitation in the antisymmetric stretch and in the absence of laser excitation. Even without laser excitation, the beam contains vibrationally excited molecules populated at the experimental source temperature, and these make significant contributions to the sticking probability. At high collision energies, above the adiabatic barrier heights, our results correlate with these barrier heights and mode softening effects. At lower energies, dissociative sticking occurs primarily via vibrationally nonadiabatic pathways. We find a preference for O–H over O–D bond cleavage for ground state HOD molecules at all but the highest collision energies, and excitation of the O–H stretch gives close to 100% O–H selectivity at lower energies. Excitation of the O–D stretch gives a lower O–D cleavage selectivity, as the interaction with the surface leads to energy transfer from the O–D stretch into the O–H bond, when mode softening makes these vibrations nearly degenerate.« less

Adsorption of Cd(II) and Pb(II) by in situ oxidized Fe3O4 membrane grafted on 316L porous stainless steel filter tube and its potential application for drinking water treatment.

PubMed

Zhu, Mengfei; Zhu, Li; Wang, Jianlong; Yue, Tianli; Li, Ronghua; Li, Zhonghong

2017-07-01

Removing heavy metal ions from aqueous solutions is one of the most challenging separations. In situ oxidized Fe 3 O 4 membranes using 316L porous stainless steel filter tube have shown great potential for removing anion Cr(VI). Here we report the performances of the in situ oxidized Fe 3 O 4 membranes for removing two toxic cations Cd(II) and Pb(II) commonly existing in water and their potential applications for drinking water purification. The membranes exhibited high removal efficiency: 97% at pH 9.0 for Cd(II) of 1.0 mg/L initial concentration and 100% at pH 5.0-6.0 for Pb(II) of 5.0 mg/L initial concentration. The maximum adsorption capabilities were estimated at 0.800 mg/g and 2.251 mg/g respectively for Cd(II) and Pb(II) at 318 K by the Langmuir model. Results of batch tests revealed the existence of electrostatic attraction and chemisorption. XRD and FT-IR analyses indicated that the chemisorption might be the insertion of Cd(II) and Pb(II) into the Fe 3 O 4 crystal faces of 311 and 511 to form mononuclear or binuclear coordination with O atoms of Fe-O 6 groups. Competitive adsorption of Cd(II) and Pb(II) in binary solutions revealed a preferential adsorption for Pb(II). Na 2 EDTA solution was used to regenerate the membranes, and the maximum desorption ratio was 90.29% and 99.75% respectively for Cd(II) and Pb(II). The membranes were able to efficiently lower Cd(II) and Pb(II) concentrations to meet the drinking water standards recommended by the World Health Organization and are promising for engineering applications aimed at drinking water purification. Copyright © 2017 Elsevier Ltd. All rights reserved.

Synthesis, crystal structures, quantum chemical studies and corrosion inhibition potentials of 4-(((4-ethylphenyl)imino)methyl)phenol and (E)-4-((naphthalen-2-ylimino) methyl) phenol Schiff bases

NASA Astrophysics Data System (ADS)

Elemike, Elias E.; Nwankwo, Henry U.; Onwudiwe, Damian C.; Hosten, Eric C.

2017-11-01

Two Schiff base ligands, 4-(((4-ethylphenyl)imino)methyl)phenol (4EMP) and (E)-4-((naphthalen-2-ylimino) methyl) phenol (4NMP) were synthesized by the reaction of 4-hydroxybenzaldehyde with 4-ethylaniline, 4EMP, or naphthalene-2-amine, 4NMP. The compounds were characterized using NMR (1H and 13C), Fourier transform infra-red (FTIR) and mass spectroscopic techniques. The proton NMR identified the OH peaks at 9.73 and 9.77 ppm for 4EMP and 4NMP respectively, while the 13C NMR showed the imine carbons at 172.57 ppm for 4EMP and at 160.89 ppm for 4NMP. The FTIR spectra showed characteristic peaks at 1605 cm-1 (4EMP) and 1600 cm-1 (4NMP) typical of the azomethine group, and the mass spectra results gave molecular ion peaks of 226.12 and 248.10 respectively. The structures of the compounds were further established by single crystal X-ray analysis. The corrosion inhibition potential of the compounds were studied on mild steel surface in a 1 M hydrochloric acid (HCl) solution, and was analysed using potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS). The results of the electrochemical methods showed that the studied molecules imparted high resistance in allowing flow of electrons across the metal-electrolyte platform and behaved as mixed type inhibitors with 4EMP showing better inhibition properties than 4NMP. Scanning electron microscopy (SEM) showed the formation of film on the mild steel surface. Quantum chemical calculations achieved by density functional theory (DFT) was further applied to explain the adsorption as well as inhibition abilities of the molecules on the mild steel surface. Thermodynamics studies showed that the two compounds obeyed the Langmuir isotherm with 4EMP conforming to chemisorption mechanism while 4NMP involved competitive physisorption and chemisorption mechanism.

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

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

PubMed

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

2017-05-16

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

An investigation of the effect of surface impurities on the adsorption kinetics of hydrogen chemisorbed onto iron

NASA Technical Reports Server (NTRS)

Shanabarger, Mickey R.

1993-01-01

The goal of this program was to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. Although hydrogen degradation of metallic materials is believed to result from dissolved protonic hydrogen, the heterogeneous hydrogen interface transport processes often dominate the kinetics of degradation. The initial step in the interface transport process is the dissociative chemisorption of the molecular species at the metal surface followed by hydrogen absorption into and transport through the bulk. The interaction of hydrogen with the surfaces of alpha-2(Ti3Al) titanium aluminide, gamma(TiAl) titanium aluminide, and beryllium were studied.

CO2 capture by ionic liquids - an answer to anthropogenic CO2 emissions?

PubMed

Sanglard, Pauline; Vorlet, Olivier; Marti, Roger; Naef, Olivier; Vanoli, Ennio

2013-01-01

Ionic liquids (ILs) are efficient solvents for the selective removal of CO2 from flue gas. Conventional, offthe-shelf ILs are limited in use to physisorption, which restricts their absorption capacity. After adding a chemical functionality like amines or alcohols, absorption of CO2 occurs mainly by chemisorption. This greatly enhances CO2 absorption and makes ILs suitable for potential industrial applications. By carefully choosing the anion and the cation of the IL, equimolar absorption of CO2 is possible. This paper reviews the current state of the art of CO2 capture by ILs and presents the current research in this field performed at the ChemTech Institute of the Ecole d'Ingénieurs et d'Architectes de Fribourg.

The influence of coadsorbed sodium atoms on the chemisorption of benzoic acid on Si(100)-2×1

NASA Astrophysics Data System (ADS)

Bitzer, T.; Richardson, N. V.

1999-06-01

The adsorption of benzoic acid on Na-Si(100)-2×1 ( ΘNa=0.5) at room temperature leads to benzoate in a bidentate coordination. High-resolution electron energy loss spectroscopy spectra show an intense ν s(OCO) stretching vibration, which is characteristic for benzoate aligned perpendicular to the substrate surface. In contrast, we observe monodentate benzoate species following the exposure of Si(100)-2×1 to benzoic acid at room temperature. On both surfaces, the dissociated hydrogen atom bonds to one of the silicon surface atoms. Removal of benzoate from Na-Si(100)-2×1 is observed after heating the silicon substrate to 300°C for 1 min.

Cooperative growth phenomena in silicon/germanium low-temperature epitaxy

NASA Astrophysics Data System (ADS)

Meyerson, Bernard S.; Uram, Kevin J.; LeGoues, Francoise K.

1988-12-01

A series of Si:Ge alloys and structures has been prepared by ultrahigh-vacuum chemical vapor deposition. Alloys of composition 0≤Ge/Si≤0.20 are readily deposited at T=550 °C. Commensurate, defect-free strained layers are deposited up to a critical thickness, whereupon the accumulated stress in the films is accommodated by the formation of dislocation networks in the substrate wafers. A cooperative growth phenomenon is observed where the addition of 10% germane to the gaseous deposition source accelerates silane's heterogeneous reaction rate by a factor of 25. A model is proposed where Ge acts as a desorption center for mobile hydrogen adatoms on the Si[100] surface, accelerating heterogeneous silane pyrolysis by the enhanced availability of chemisorption sites.

Adsorption and Dissociation of CO2 on Ru(0001)

PubMed Central

2017-01-01

The adsorption and dissociation of carbon dioxide on a Ru(0001) single crystal surface was investigated by reflection–absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) spectroscopy for CO2 adsorbed at 85 K. RAIRS spectroscopy shows that the adsorption of CO2 on a Ru(0001) single crystal is partially dissociative, resulting in CO2 and CO. The CO vibrational mode was also observed to split into two distinct modes, indicating two general populations of CO present at the surface. Furthermore, a time-dependent blue-shift is observed, which is characteristic of increasing CO surface coverage. TPD showed that coverages of up to 0.3 ML were obtained, and no evidence for chemisorption of oxygen on ruthenium was found. PMID:28413569

A study of Pd/SO4/ZrO2/Al2O3 catalysts in n-hexane isomerization

NASA Astrophysics Data System (ADS)

Dzhikiya, O. V.; Smolikov, M. D.; Kazantsev, K. V.; Yablokova, S. S.; Kireeva, T. V.; Paukshtis, E. A.; Gulyaeva, T. I.; Belyi, A. S.

2017-08-01

The effect of palladium concentration in a range from 0.02 to 1.6 wt.% on characteristics of n-hexane isomerization was studied. The (O2-Hchem) titration and O2 chemisorption study revealed that palladium in Pd/SO4/ZrO2/Al2O3 systems adsorbs hydrogen in a ratio H/Pds = 1.13-1.65 at./at. Investigation of the charge state of the metal by IR spectroscopy of adsorbed CO showed the presence of both the metallic (Pd0) and charged palladium species. Pd/SO4/ZrO2/Al2O3 catalysts with charged palladium atoms exhibit high activity and selectivity in n-hexane isomerization.

Effect of Cobalt Particle Size on Acetone Steam Reforming

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

Sun, Junming; Zhang, He; Yu, Ning

2015-06-11

Carbon-supported cobalt nanoparticles with different particle sizes were synthesized and characterized by complementary characterization techniques such as X-ray diffraction, N-2 sorption, acetone temperature-programmed desorption, transmission electron microscopy, and CO chemisorption. Using acetone steam reforming reaction as a probe reaction, we revealed a volcano-shape curve of the intrinsic activity (turnover frequency of acetone) and the CO2 selectivity as a function of the cobalt particle size with the highest activity and selectivity observed at a particle size of approximately 12.8nm. Our results indicate that the overall performance of acetone steam reforming is related to a combination of particle-size-dependent acetone decomposition, water dissociation,more » and the oxidation state of the cobalt nanoparticles.« less

Theory of carbon nanocones: mechanical chiral inversion of a micron-scale three-dimensional object.

PubMed

Jordan, Stephen P; Crespi, Vincent H

2004-12-17

Graphene cones have two degenerate configurations: their original shape and its inverse. When the apex is depressed by an external probe, the simulated mechanical response is highly nonlinear, with a broad constant-force mode appearing after a short initial Hooke's law regime. For chiral cones, the final state is an atomically exact chiral invert of the original system. If the local reflection symmetry of the graphene sheet is broken by the chemisorption of just five hydrogen atoms to the apex, then the maximal yield strength of the cone increases by approximately 40%. The high symmetry of the conical geometry can concentrate micron-scale mechanical work with atomic precision, providing a way to activate specific chemical bonds.

Correlation study of sodium-atom chemisorption on the GaAs(110) surface

NASA Astrophysics Data System (ADS)

Song, K. M.; Khan, D. C.; Ray, A. K.

1994-01-01

Different possible adsorption sites of sodium atoms on a gallium arsenide surface have been investigated using ab initio self-consistent unrestricted Hartree-Fock total-energy cluster calculations with Hay-Wadt effective core potentials. The effects of electron correlation have been included by invoking the concepts of many-body perturbation theory and are found to be highly significant. We find that the Na-atom adsorption at a site modeled with an NaGa5As4H12 cluster is most favored energetically followed by Na adsorption at the site modeled with the NaGa4As5H12 cluster. The effects of charge transfer from Na to the GaAs surface as also possibilities of metallization are also analyzed and discussed.

Molecular-level Design of Heterogeneous Chiral Catalysts

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

Wilfred T. Tysoe

2007-04-25

It has been shown previously that the adsorption of a chiral 2-butanol template on Pd(111) leads to enantioselective adsorption of chiral propylene oxide probe molecules. Enantioselectivity is expressed over a narrow coverage range where the maximum value of enantioselectivity ratio (ER defined as Θ(R-propylene oxide)/Θ(S-propylene oxide), where Θ is the coverage) reaches ~2. Probe coverages in this case were measured using either reflection-absorption infrared spectroscopy (RAIRS) or temperature-programmed desorption (TPD) [1,2]. The enantioselectivity disappears when the 2-butanol-covered surface was heated to ~200 K since the adsorbed butoxy species decomposes by a β-hydride elimination reaction to yield a non-chiral ketone. Montemore » Carlo calculations of the effect of chiral modifiers have yielded results that are consistent with these experimental observations [3,4]. Similar experiments using 2-methyl butanoic acid as a template, where the chiral center is identical to that in 2-butanol but is now anchored by a carboxylate group rather than by an alkoxide, shows no enantioselectivity. In this case, propylene oxide coverages were measured using the King and Wells method. RAIRS experiments and density functional calculations suggest that the 2-butyl group of the 2-butoxy species is oriented parallel to the surface. A possible origin for the lack of enantioselectivity of a 2-methyl butanoic acid-covered surface may be that the 2-butyl group is farther from the surface, allowing it to rotate more freely, averaging out any asymmetry, resulting in a loss of chirality. In order to test this idea, the alkyl group on the carboxylic acid was functionalized with an amine to anchor the chiral center to the surface. Using the amino-acids alanine and 2-amino butanoic acid as templates restored the enantioselectivity and yielded ER values of 2.0 ± 0.2 and 1.75 ± 0.15 respectively. These results suggest that a two-point attachment of the chiral template is required, one for surface adsorption and the other to allow the enantioselectivity to be expressed. Low-energy electron diffraction (LEED) intensity versus energy (I/E) measurements are used to measure the structure of templates and probes on the Pd(111) surface, where these results will be compared with calculations carried out by the Sholl group. Since the aminoacids are relatively large, initial experiments were carried out to determine the structure of carboxylates on the surface to determine the carboxylate group anchoring site. Since carboxylates do not form ordered structures on Pd(111), we have exploited a method recently developed in collaboration with Professor Saldin to measure structures of disordered overlayers [5]. Results show that the formate OCO plane is oriented perpendicular to the surface with the oxygen atoms located across a short bridge on the (111) surface. The effect of the size of the functional group on the amino acid template (RCH(NH2)COOH) was also investigated where the maximum ER values obtained using propylene oxide were 2.0 ± 0.2 (R=CH3), 1.75 ± 0.15 (R=C2H5), 1.65 ± 0.15 (R=C3H6) and 1.30 ± 0.15 (R=CH2CH(CH3)2) thus showing a decreasing trend with increasing size of the side chain. The enantioselectivity of S-(1-naphthyl) ethylamine-covered surfaces have been explored using propylene oxide as a probe, but these systems showed no enantioselectivity. However, using 2-butanol as a probe lead to enantioselective chemisorption implying that one-to-one modification requires a direct hydrogen-bonding interaction between the probe and modifier. 1. Enantioselective Chemisorption on a Chirally Patterned Surface in Ultrahigh Vacuum: Adsorption of Propylene Oxide on 2-butoxy-Covered Pd(111), D. Stacchiola, L. Burkholder and W.T. Tysoe, J. Am. Chem. Soc., 124, 8984 (2002) 2. Enantioselective Chemisorption on a Chirally Modified Surface in Ultrahigh Vacuum: Adsorption of Propylene Oxide on 2-butoxide-Covered Pd(111), Darío Stacchiola, Luke Burkholder and Wilfred T. Tysoe, J. Mol. Catal A: Chemical, 216, 215 (2004) 3. Theoretical Analysis of the Coverage Dependence of Enantioselective Chemisorption on a Chirally Patterned Surface, F. Roma, D. Stacchiola, G. Zgrablich and W. T. Tysoe, Journal of Chemical Physics, 118, 6030 (2003) 4. Lattice-gas Modeling of Enantioselective Adsorption by Template Chiral Substrates, F. Romá, D. Stacchiola, W.T. Tysoe and G. Zgrablich, Physica A., 338, 493 (2004) 5. Structure Determination of Disordered Organic Molecules on Surfaces from the Bragg Spots of Low Energy Electron Diffraction and Total Energy Calculations, H. C. Poon, M. Weinert, D. K. Saldin, D. Stacchiola, T. Zheng and W. T. Tysoe, Phys. Rev. B., 69, 35401 (2004)« less

Sorption kinetics of Zn (II) ion by thermally treated rice husk

NASA Astrophysics Data System (ADS)

Ong, K. K.; Tarmizi, A. F. A.; Wan Yunus W. M., Z.; Safidin, K. M.; Fitrianto, A.; Hussin, A. G. A.; Azmi, F. M.

2015-05-01

Agricultural wastes such as orange peels, tea leave waste, rice husk and corn cobs have been widely studied as sorbents for heavy metal ion removal from various wastewaters. In order to understand their sorption mechanism, the adsorption kinetics is studied. This report describes the kinetics study of a thermally treated rice husk to adsorb Zn (II) ion from an aqueous solution. The adsorbent was obtained by heating the rice husk in a furnace at 500°C for two hours. Increase the contact period improved percentage of the removal of Zn (II) ion until an equilibrium was reached. The data obtained showed that the adsorption of Zn (II) ion by thermally treated rice husk obeyed pseudo-second order kinetics model, which is in agreement with chemisorption as the rate limiting mechanism.

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

Stair, Peter C.

The research took advantage of our capabilities to perform in-situ and operando Raman spectroscopy on complex systems along with our developing expertise in the synthesis of uniform, supported metal oxide materials to investigate relationships between the catalytically active oxide composition, atomic structure, and support and the corresponding chemical and catalytic properties. The project was organized into two efforts: 1) Synthesis of novel catalyst materials by atomic layer deposition (ALD). 2) Spectroscopic and chemical investigations of coke formation and catalyst deactivation. ALD synthesis was combined with conventional physical characterization, Raman spectroscopy, and probe molecule chemisorption to study the effect of supportedmore » metal oxide composition and atomic structure on acid-base and catalytic properties. Operando Raman spectroscopy studies of olefin polymerization leading to coke formation and catalyst deactivation clarified the mechanism of coke formation by acid catalysts.« less

Studies on the Inhibition of Mild Steel Corrosion by Rauvolfia serpentina in Acid Media

NASA Astrophysics Data System (ADS)

Bothi Raja, P.; Sethuraman, M. G.

2010-07-01

Alkaloid extract of Rauvolfia serpentina was tested as corrosion inhibitor for mild steel in 1 M HCl and H2SO4 using weight loss method at three different temperatures, viz., 303, 313, and 323 K, potentiodynamic polarization, electrochemical impedance spectroscopy and scanning electron microscope (SEM) studies. It is evident from the results of this study that R. serpentina effectively inhibits the corrosion in both the acids through adsorption process following Tempkin adsorption isotherm. The protection efficiency increased with increase in inhibitor concentration and temperature. Free energy of adsorption calculated from the temperature studies also revealed the chemisorption. The mixed mode of action exhibited by the inhibitor was confirmed by the polarization studies while SEM analysis substantiated the formation of protective layer over the mild steel surface.

Interaction between adatoms on surfaces: Application to the system H/Ni(111)

NASA Astrophysics Data System (ADS)

Muscat, J. P.; Newns, D. M.

1981-04-01

The interaction of adatoms on a metal surface is looked at from a novel viewpoint, using the techniques of the embedded cluster model of chemisorption. Application is made to the problem of two hydrogen atoms on a free electron surface with simple derivation of the well known R-5 asymptotic behaviour for the interaction, at large inter-adatom distances R, compared to the corresponding R-3 behaviour for two impurities in a bulk free electron gas. Application of the free electron model to the case of H/Ni(111) does not reproduce the experimental observation of formation of a graphitic structure on the surface. Inclusion of the l = 2 nickel muffin tins corrects for this anomaly, and is seen to favour the formation of the above mentioned structure.

Coherent Electron Transfer at the Ag / Graphite Heterojunction Interface

NASA Astrophysics Data System (ADS)

Tan, Shijing; Dai, Yanan; Zhang, Shengmin; Liu, Liming; Zhao, Jin; Petek, Hrvoje

2018-03-01

Charge transfer in transduction of light to electrical or chemical energy at heterojunctions of metals with semiconductors or semimetals is believed to occur by photogenerated hot electrons in metal undergoing incoherent internal photoemission through the heterojunction interface. Charge transfer, however, can also occur coherently by dipole coupling of electronic bands at the heterojunction interface. Microscopic physical insights into how transfer occurs can be elucidated by following the coherent polarization of the donor and acceptor states on the time scale of electronic dephasing. By time-resolved multiphoton photoemission spectroscopy (MPP), we investigate the coherent electron transfer from an interface state that forms upon chemisorption of Ag nanoclusters onto graphite to a σ symmetry interlayer band of graphite. Multidimensional MPP spectroscopy reveals a resonant two-photon transition, which dephases within 10 fs completing the coherent transfer.

Chemistry of acetylene on platinum (111) and (100) surfaces

PubMed Central

Muetterties, E. L.; Tasi, M.-C.; Kelemen, S. R.

1981-01-01

An ultra-high vacuum experimental study of acetylene chemisorption on Pt(111) and Pt(100) and of the reaction of hydrogen with the acetylene adsorbate has established distinguishing features of carbon-hydrogen bond breaking and making processes as a function of pressure, temperature, and surface crystallography. The rates for both processes are substantially higher on the Pt(100) surface. Net acetylene-hydrogen processes, in the temperature range of 20°C to ≈130°C, are distinctly different on the two surfaces: on Pt(100) the net reaction is hydrogen exchange (1H-2H exchange) and on Pt(111) the only detectable reaction is hydrogenation. Stereochemical differences in the acetylene adsorbate structure are considered to be a contributing factor to the differences in acetylene chemistry on these two surfaces. Images PMID:16593110

Simulated structure and imaging of NTCDI on Si(1 1 1)-7 × 7 : a combined STM, NC-AFM and DFT study

NASA Astrophysics Data System (ADS)

Jarvis, S. P.; Sweetman, A. M.; Lekkas, I.; Champness, N. R.; Kantorovich, L.; Moriarty, P.

2015-02-01

The adsorption of naphthalene tetracarboxylic diimide (NTCDI) on Si(1 1 1)-7 × 7 is investigated through a combination of scanning tunnelling microscopy (STM), noncontact atomic force microscopy (NC-AFM) and density functional theory (DFT) calculations. We show that NTCDI adopts multiple planar adsorption geometries on the Si(1 1 1)-7 × 7 surface which can be imaged with intramolecular bond resolution using NC-AFM. DFT calculations reveal adsorption is dominated by covalent bond formation between the molecular oxygen atoms and the surface silicon adatoms. The chemisorption of the molecule is found to induce subtle distortions to the molecular structure, which are observed in NC-AFM images.

Structure, bonding nature, and binding energy of alkanethiolate on As-rich GaAs (001) surface: a density functional theory study.

PubMed

Voznyy, Oleksandr; Dubowski, Jan J

2006-11-30

Chemisorption of alkanethiols on As-rich GaAs (001) surface under a low coverage condition was studied using first principles density functional calculations in a periodic supercell approach. The thiolate adsorption site, tilt angle and its direction are dictated by the high directionality of As dangling bond and sulfur 3p orbital participating in bonding and steric repulsion of the first three CH2 units from the surface. Small charge transfer between thiolate and surface, strong dependence of total energy on tilt angle, and a relatively short length of 2.28 A of the S-As bond indicate the highly covalent nature of the bonding. Calculated binding energy of 2.1 eV is consistent with the available experimental data.

Hydrotalcite-based CeNiAl mixed oxides for SO2 adsorption and oxidation.

PubMed

Zhao, Ling; Kang, Qi; Guan, Xiongfei; Martyniuk, Christopher J

2018-06-05

The impact of Ce on SO 2 adsoption and oxidation was studied over a series of flower-like hydrotalcite-based CeNiAl mixed oxides. Combined with XRD, BET, pyridine chemisorption, CO 2 -TPD, XPS and H 2 -TPR results, it revealed that introduction of Ce into NiAlO generates new centers for oxygen storage and release, promotes the enhancement of Lewis acid strength, increases weakly and strongly alkaline sites, and increases ability for SO 2 adsorption and oxidation. Furthermore, in situ Fourier transform infrared spectroscopy revealed that adsorbed SO 2 molecules formed surface bidentate binuclear sulfate. Taken together, we propose that the addition of Ce 4+ to NiAlO acts to improve this compound as major adsorbent for SO 2 .

Removal of SO2 from O2-containing flue gas by activated carbon fiber (ACF) impregnated with NH3.

PubMed

Xu, Lüsi; Guo, Jia; Jin, Feng; Zeng, Hancai

2006-02-01

Adsorption of SO(2) from the O(2)-containing flue gas by granular activated carbons (GACs) and activated carbon fibers (ACFs) impregnated with NH(3) was studied in this technical note. Experimental results showed that the ACFs were high-quality adsorbents due to their unique textural properties. In the presence of moisture, the desulphurization efficiency for the ACFs was improved significantly due to the formation of sulfuric acid. After NH(3) impregnation of ACF samples, nitrogen-containing functional groups (pyridyl C(5)H(4)N- and pyrrolyl C(4)H(4)N-) were detected on the sample surface by using an X-ray photoelectron spectrometer. These functional groups accounted for the enhanced SO(2) adsorption via chemisorption and/or catalytic oxidization.

Spontaneous Polarization of Hydrogen-Saturated Composite Materials

NASA Astrophysics Data System (ADS)

Sokolov, A. A.; Sergeev, V. O.; Kharlamov, V. F.

2017-01-01

The paper focuses on the effect of spontaneous electric field emergence in mixtures of cesium nitrate and/or potassium permanganate microparticles with nickel, aluminum and aluminum oxide nanoparticles in the hydrogen atmosphere. It was established that increase in the share of Ni, Al or Al2O3 nanoparticles in the mix with KMnO4 powder from 0 to 0.25 (in terms of weight) leads to gradual decrease in electric field density in the powder to zero (T = 22-250°C). The authors identified the stimulating effect of nickel nanoparticles on hydrogen-initiated electric field emergence in the CsNO3 powder. It was established that spontaneous polarization of powders is caused by dissociative chemisorption of hydrogen molecules on the surface of KMnO4 and CsNO3 particles.

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

Dai, X.; Antal, M.J. Jr.

Macadamia nut shell charcoal was heated in an inert environment to temperatures above 1000 K (carbonized), reacted with oxygen (Po{sub 2} = 2.68--11.3 kPa) at temperatures between 525 and 586 K (oxygenated), and heated again in an inert environment to temperatures above 1000 K (activated) to produce an activated carbon. Carbons produced by this process possess surface areas and iodine numbers in the range of 400--550. Overall yields of these carbons (based on the dry, raw macadamia nut shell feed) ranged from 24 to 30 wt %. Under the conditions employed in this work, the rates of chemisorption and gasificationmore » were not mass transfer limited. Initially, the gasification reaction was first-order with respect to oxygen concentration but became independent of oxygen concentration as the surface sites of the carbon became saturated with oxygen.« less

Mean-field theory of active electrolytes: Dynamic adsorption and overscreening

NASA Astrophysics Data System (ADS)

Frydel, Derek; Podgornik, Rudolf

2018-05-01

We investigate active electrolytes within the mean-field level of description. The focus is on how the double-layer structure of passive, thermalized charges is affected by active dynamics of constituting ions. One feature of active dynamics is that particles adhere to hard surfaces, regardless of chemical properties of a surface and specifically in complete absence of any chemisorption or physisorption. To carry out the mean-field analysis of the system that is out of equilibrium, we develop the "mean-field simulation" technique, where the simulated system consists of charged parallel sheets moving on a line and obeying active dynamics, with the interaction strength rescaled by the number of sheets. The mean-field limit becomes exact in the limit of an infinite number of movable sheets.

PEM Anchorage on Titanium Using Catechol Grafting

PubMed Central

Marie, Hélène; Barrere, Amélie; Schoentstein, Frédérique; Chavanne, Marie-Hélène; Grosgogeat, Brigitte; Mora, Laurence

2012-01-01

Background This study deals with the anchorage of polyelectrolyte films onto titanium surfaces via a cathecol-based linker for biomedical applications. Methodology The following study uses a molecule functionalized with a catechol and a carboxylic acid: 3-(3,4-dihydroxyphenyl)propanoic acid. This molecule is anchored to the TiO2 substrate via the catechol while the carboxylic acid reacts with polymers bearing amine groups. By providing a film anchorage of chemisorption type, it makes possible to deposit polyelectrolytes on the surface of titanium. Principal Findings Infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), contact angle and atomic force microscopy (AFM) measurements show that the different steps of grafting have been successfully performed. Conclusions This method based on catechol anchorage of polyelectrolytes open a window towards large possibilities of clinical applications. PMID:23226262

Two-statge sorption type cryogenic refrigerator including heat regeneration system

NASA Technical Reports Server (NTRS)

Jones, Jack A. (Inventor); Wen, Liang-Chi (Inventor); Bard, Steven (Inventor)

1989-01-01

A lower stage chemisorption refrigeration system physically and functionally coupled to an upper stage physical adsorption refrigeration system. Waste heat generated by the lower stage cycle is regenerated to fuel the upper stage cycle thereby greatly improving the energy efficiency of a two-stage sorption refrigerator. The two stages are joined by disposing a first pressurization chamber providing a high pressure flow of a first refrigerant for the lower stage refrigeration cycle within a second pressurization chamber providing a high pressure flow of a second refrigerant for the upper stage refrigeration cycle. The first pressurization chamber is separated from the second pressurization chamber by a gas-gap thermal switch which at times is filled with a thermoconductive fluid to allow conduction of heat from the first pressurization chamber to the second pressurization chamber.

Communication: Methane dissociation on Ni(111) surface: Importance of azimuth and surface impact site

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

Shen, Xiangjian; State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical Computational Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023; Zhang, Zhaojun, E-mail: zhangzhj@dicp.ac.cn, E-mail: zhangdh@dicp.ac.cn

2016-03-14

Understanding the role of reactant ro-vibrational degrees of freedom (DOFs) in reaction dynamics of polyatomic molecular dissociation on metal surfaces is of great importance to explore the complex chemical reaction mechanism. Here, we present an expensive quantum dynamics study of the dissociative chemisorption of CH{sub 4} on a rigid Ni(111) surface by developing an accurate nine-dimensional quantum dynamical model including the DOF of azimuth. Based on a highly accurate fifteen-dimensional potential energy surface built from first principles, our simulations elucidate that the dissociation probability of CH{sub 4} has the strong dependence on azimuth and surface impact site. Some improvements aremore » suggested to obtain the accurate dissociation probability from quantum dynamics simulations.« less

Fluorine atom abstraction by Si(100). I. Experimental

NASA Astrophysics Data System (ADS)

Tate, M. R.; Gosalvez-Blanco, D.; Pullman, D. P.; Tsekouras, A. A.; Li, Y. L.; Yang, J. J.; Laughlin, K. B.; Eckman, S. C.; Bertino, M. F.; Ceyer, S. T.

1999-08-01

In the interaction of low energy F2 with Si(100) at 250 K, a dissociative chemisorption mechanism called atom abstraction is identified in which only one of the F atoms is adsorbed while the other F atom is scattered into the gas phase. The dynamics of atom abstraction are characterized via time-of-flight measurements of the scattered F atoms. The F atoms are translationally hyperthermal but only carry a small fraction (˜3%) of the tremendous exothermicity of the reaction. The angular distribution of F atoms is unusually broad for the product of an exothermic reaction. These results suggest an "attractive" interaction potential between F2 and the Si dangling bond with a transition state that is not constrained geometrically. These results are in disagreement with the results of theoretical investigations implying that the available potential energy surfaces are inadequate to describe the dynamics of this gas-surface interaction. In addition to single atom abstraction, two atom adsorption, a mechanism analogous to classic dissociative chemisorption in which both F atoms are adsorbed onto the surface, is also observed. The absolute probability of the three scattering channels (single atom abstraction, two atom adsorption, and unreactive scattering) for an incident F2 are determined as a function of F2 exposure. The fluorine coverage is determined by integrating the reaction probabilities over F2 exposure, and the reaction probabilities are recast as a function of fluorine coverage. Two atom adsorption is the dominant channel [P2=0.83±0.03(95%, N=9)] in the limit of zero coverage and decays monotonically to zero. Single atom abstraction is the minor channel (P1=0.13±0.03) at low coverage but increases to a maximum (P1=0.35±0.08) at about 0.5 monolayer (ML) coverage before decaying to zero. The reaction ceases at 0.94±0.11(95%, N=9) ML. Thermal desorption and helium diffraction confirm that the dangling bonds are the abstraction and adsorption sites. No Si lattice bonds are broken, in contrast to speculation by other investigators that the reaction exothermicity causes lattice disorder.

Concurrent removal of elemental mercury and SO2 from flue gas using a thiol-impregnated CaCO3-based adsorbent: a full factorial design study.

PubMed

Balasundaram, Karthik; Sharma, Mukesh

2018-06-01

Mercury (Hg) emitted from coal-based thermal power plants (CTPPs) can accumulate and bio-magnify in the food chain, thereby posing a risk to humans and wildlife. The central idea of this study was to develop an adsorbent which can concurrently remove elemental mercury (Hg 0 ) and SO 2 emitted from coal-based thermal power plants (CTPPs) in a single unit operation. Specifically, a composite adsorbent of CaCO 3 impregnated with 2-mercaptobenimidazole (2-MBI) (referred to as modified calcium carbonate (MCC)) was developed. While 2-MBI having sulfur functional group could selectively adsorb Hg 0 , CaCO 3 could remove SO 2 . Performance of the adsorbent was evaluated in terms of (i) removal (%) of Hg 0 and SO 2 , (ii) adsorption mechanism, (iii) adsorption kinetics, and (iv) leaching potential of mercury from spent adsorbent. The adsorption studies were performed using a 2 2 full factorial design of experiments with 15 ppbV of Hg 0 and 600 ppmV of SO 2 . Two factors, (i) reaction temperature (80 and 120 °C; temperature range in flue gas) and (ii) mass of 2-MBI (10 and 15 wt%), were investigated for the removal of Hg 0 and SO 2 (as %). The maximum Hg 0 and SO 2 removal was 86 and 93%, respectively. The results of XPS characterization showed that chemisorption is the predominant mechanism of Hg 0 and SO 2 adsorption on MCC. The Hg 0 adsorption on MCC followed Elovich kinetic model which is also indicative of chemisorption on heterogeneous surface. The toxicity characteristic leaching procedure (TCLP) and synthetic precipitation leaching procedure (SPLP) leached mercury from the spent adsorbent were within the acceptable levels defined in these tests. The engineering significance of this study is that the 2-MBI-modified CaCO 3 -based adsorbent has potential for concurrent removal of Hg 0 and SO 2 in a single unit operation. With only minor process modifications, the newly developed adsorbent can replace CaCO 3 in the flue-gas desulfurization (FGD) system.

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

Six-dimensional quantum dynamics study for the dissociative adsorption of HCl on Au(111) surface

NASA Astrophysics Data System (ADS)

Liu, Tianhui; Fu, Bina; Zhang, Dong H.

2013-11-01

The six-dimensional quantum dynamics calculations for the dissociative chemisorption of HCl on Au(111) are carried out using the time-dependent wave-packet approach, based on an accurate PES which was recently developed by neural network fitting to density functional theory energy points. The influence of vibrational excitation and rotational orientation of HCl on the reactivity is investigated by calculating the exact six-dimensional dissociation probabilities, as well as the four-dimensional fixed-site dissociation probabilities. The vibrational excitation of HCl enhances the reactivity and the helicopter orientation yields higher dissociation probability than the cartwheel orientation. A new interesting site-averaged effect is found for the title molecule-surface system that one can essentially reproduce the six-dimensional dissociation probability by averaging the four-dimensional dissociation probabilities over 25 fixed sites.

High voltage AC/AC electrochemical capacitor operating at low temperature in salt aqueous electrolyte

NASA Astrophysics Data System (ADS)

Abbas, Qamar; Béguin, François

2016-06-01

We demonstrate that an activated carbon (AC)-based electrochemical capacitor implementing aqueous lithium sulfate electrolyte in 7:3 vol:vol water/methanol mixture can operate down to -40 °C with good electrochemical performance. Three-electrode cell investigations show that the faradaic contributions related with hydrogen chemisorption in the negative AC electrode are thermodynamically unfavored at -40 °C, enabling the system to work as a typical electrical double-layer (EDL) capacitor. After prolonged floating of the AC/AC capacitor at 1.6 V and -40°C, the capacitance, equivalent series resistance and efficiency remain constant, demonstrating the absence of ageing related with side redox reactions at this temperature. Interestingly, when temperature is increased back to 24 °C, the redox behavior due to hydrogen storage reappears and the system behaves as a freshly prepared one.

A study of the initial oxidation of evaporated thin films of aluminum by AES, ELS, and ESD

NASA Technical Reports Server (NTRS)

Bujor, M.; Larson, L. A.; Poppa, H.

1982-01-01

The room temperature, low pressure, oxidation of evaporated aluminum thin films has been studied by AES, ELS, and ESD. ESD was the most sensitive of the three methods to characterize a clean aluminum surface. Two oxidation stages were distinguished in the 0-3000 L oxygen exposure range. Between 0 and 50 L, the chemisorption of oxygen atoms was characterized by a fast decrease of the 67 eV AES Al peak and the 10 eV surface plasmon peak, and by a simultaneous increase of the oxygen AES and ESD signals. After 50 L, a change in slope in all AES and ESD signal variations was attributed to the slow growth of a thin layer of aluminum oxide, which after 3000 L was still only a few angstroms thick.

Biosorption of Azo dyes by spent Rhizopus arrhizus biomass

NASA Astrophysics Data System (ADS)

Salvi, Neeta A.; Chattopadhyay, S.

2017-10-01

In the present study, spent Rhizopus arrhizus biomass was used for the removal of six azo dyes from aqueous solutions. The dye removal capacity of the biomass was evaluated by conducting batch tests as a function of contact time, biomass dosage, pH and initial dye concentrations. The pseudo-second-order kinetic model fitted well with the experimental data with correlation coefficients greater than 0.999, suggesting that chemisorptions might be the rate limiting step. The equilibrium sorption data showed good fit to the Langmuir isotherm model. Among the six dyes tested, the maximum monolayer adsorption capacity for fast red A and metanil yellow was found to be 108.8 and 128.5 mg/g, respectively. These encouraging results suggest that dead Rhizopus arrhizus biomass could be a potential biomaterial for the removal of azo dyes from aqueous dye solution.

The interaction of small particles and thin films of metals with gases. I - A brief review of the early stages of oxide formation

NASA Technical Reports Server (NTRS)

Poppa, H.

1976-01-01

Existing work on gas-solid reactions making use of thin film technologies is reviewed. The discussion concentrates on two major areas of gas-metal interactions: chemisorption and the early stages of oxidation of metals (characterized by a non-volatile reaction product) and catalytic surface reactions (featuring volatile reaction products). A brief survey of oxide formation on metals is presented. Here it is of importance to distinguish between reactions on continuous thin film substrates and reactions on particulate deposits. Small particle-gas interactions also affect the nucleation, growth and sintering processes of thin films. It is shown that various combinations of UHV and high resolution electron microscopy techniques, which include in situ experimentation, can provide the appropriate tools for studying angstrom particle chemistry.

Electron-spectroscopy studies of clean thorium and uranium surfaces. Chemisorption and initial stages of reaction with O2, CO, and CO2

NASA Astrophysics Data System (ADS)

McLean, W.; Colmenares, C. A.; Smith, R. L.; Somorjai, G. A.

1982-01-01

The adsorption of O2, CO, and CO2 on the thorium (111) crystal face and on polycrystalline α-uranium has been investigated by x-ray photoelectron spectroscopy, Auger electron spectroscopy (AES), and secondary-ion mass spectroscopy (SIMS) at 300 K. Oxygen adsorption on both metals resulted in the formation of the metal dioxide. CO and CO2 adsorption on Th(111) produced species derived from atomic carbon and oxygen; the presence of molecular CO was also detected. Only atomic carbon and oxygen were observed on uranium. Elemental depth profiles by AES and SIMS indicated that the carbon produced by the dissociation of CO or CO2 diffused into the bulk of the metals to form a carbide, while the oxygen remained on their surfaces as an oxide.

Two stage sorption type cryogenic refrigerator including heat regeneration system

NASA Technical Reports Server (NTRS)

Jones, Jack A. (Inventor); Wen, Liang-Chi (Inventor); Bard, Steven (Inventor)

1989-01-01

A lower stage chemisorption refrigeration system physically and functionally coupled to an upper stage physical adsorption refrigeration system is disclosed. Waste heat generated by the lower stage cycle is regenerated to fuel the upper stage cycle thereby greatly improving the energy efficiency of a two-stage sorption refrigerator. The two stages are joined by disposing a first pressurization chamber providing a high pressure flow of a first refrigerant for the lower stage refrigeration cycle within a second pressurization chamber providing a high pressure flow of a second refrigerant for the upper stage refrigeration cycle. The first pressurization chamber is separated from the second pressurization chamber by a gas-gap thermal switch which at times is filled with a thermoconductive fluid to allow conduction of heat from the first pressurization chamber to the second pressurization chamber.

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.

Nitrogen-Doped Carbon Nanotube/Graphite Felts as Advanced Electrode Materials for Vanadium Redox Flow Batteries.

PubMed

Wang, Shuangyin; Zhao, Xinsheng; Cochell, Thomas; Manthiram, Arumugam

2012-08-16

Nitrogen-doped carbon nanotubes have been grown, for the first time, on graphite felt (N-CNT/GF) by a chemical vapor deposition approach and examined as an advanced electrode for vanadium redox flow batteries (VRFBs). The unique porous structure and nitrogen doping of N-CNT/GF with increased surface area enhances the battery performance significantly. The enriched porous structure of N-CNTs on graphite felt could potentially facilitate the diffusion of electrolyte, while the N-doping could significantly contribute to the enhanced electrode performance. Specifically, the N-doping (i) modifies the electronic properties of CNT and thereby alters the chemisorption characteristics of the vanadium ions, (ii) generates defect sites that are electrochemically more active, (iii) increases the oxygen species on CNT surface, which is a key factor influencing the VRFB performance, and (iv) makes the N-CNT electrochemically more accessible than the CNT.

Hydrogen storage in N- and B-doped graphene decorated by small platinum clusters: A computational study

NASA Astrophysics Data System (ADS)

Chen, I.-Nan; Wu, Shiuan-Yau; Chen, Hsin-Tsung

2018-05-01

In this work, we perform density functional theory (DFT) calculations to investigate the hydrogen adsorption on Pt4 cluster supported on pristine, B-, and N-doped graphene sheets. It is found that the doping B or N atom in the graphene could enhance the interaction between the Pt4 cluster and the supporting substrate. The first H2 molecule is found to be dissociative chemisorption on the three substrates. Further, dissociative and molecular adsorption of multiple H2 molecules are co-adsorbed on the three substrates. In addition, the interaction between Pt4(H2)x and the substrate is illustrated for the stability of Pt4(H2)x on the substrate. AIMD simulation is also performed to verify the stability and hydrogen storage. Accordingly, the B-graphene is predicted to be the most potential materials for hydrogen storage among these three materials.

SEPARATION OF PLUTONIUM VALUES FROM URANIUM AND FISSION PRODUCT VALUES

DOEpatents

Maddock, A.G.; Booth, A.H.

1960-09-13

Separation of plutonium present in small amounts from neutron irradiated uranium by making use of the phenomenon of chemisorption is described. Plutonium in the tetravalent state is chemically absorbed on a fluoride in solid form. The steps for the separation comprise dissolving the irradiated uranium in nitric acid, oxidizing the plutonium in the resulting solution to the hexavalent state, adding to the solution a soluble calcium salt which by the common ion effect inhibits dissolution of the fluoride by the solution, passing the solution through a bed or column of subdivided calcium fluoride which has been sintered to about 8OO deg C to remove the chemisorbable fission products, reducing the plutonium in the solution thus obtained to the tetravalent state, and again passing the solution through a similar bed or column of calcium fluoride to selectively absorb the plutonium, which may then be recovered by treating the calcium fluoride with a solution of ammonium oxalate.

Research of Co(II) Adsorption on Silica Gel Grafted with Dithiocarbamate (DTC-SiO2) in Aqueous Solution

NASA Astrophysics Data System (ADS)

Yao, Qingxu; Xu, Peng; Huo, Yonggang; Shang, Aiguo; Yu, Fengmei

2018-01-01

Dithiocarbamate grafted silica gel (DTC-SiO2) was prepared following two simple reaction steps. The properties of the composite were characterized by FTIR, SEM and element analysis. Its ability to remove Co2+ ions in aqueous solution with low concentration was also studied by static adsorption experiments. The effects of pH value in solution, contact time and temperature were investigated. The results show that the DTC-SiO2 exhibits excellent adsorption property for Co2+. The adsorption kinetics could be well described by pseudo-second-order model and the adsorption isotherms could be depicted by both Freundlich and Dubinin-Radushkevich models. The adsorption process belongs to chemisorption. The slightly influence of common interfering metal ions (Na+, K+, Ca2+ and Mg2+) on the adsorption capacity revealing the synthesized DTC-SiO2 performs excellent selective adsorption to Co2+.

Electronic structures at the interface between CuPc and black phosphorus

NASA Astrophysics Data System (ADS)

Wang, Can; Niu, Dongmei; Xie, Haipeng; Liu, Baoxing; Wang, Shitan; Zhu, Menglong; Gao, Yongli

2017-08-01

The electronic structure at the organic-inorganic semiconductor interface of π -conjugated copper phthalocyanine (CuPc) on a black phosphorus (BP) crystal surface is studied with photoemission spectroscopy and density functional theory calculations. From the photoemission spectra, we observe a shift of about 0.7 eV for the highest occupied molecular orbital, which originates from the transition of phase in the organic molecular thin film (from the interface phase to the bulk phase). On the other hand, we find 0.2 eV band bending at the CuPc/BP interface while the formation of an interface dipole is very small. According to our photoemission spectrum and theoretical simulation, we also define that the interaction between CuPc and BP is physisorption via van der Waals forces, rather than chemisorption. Our results provide a fundamental understanding of CuPc/BP interfacial interactions that could be important for future two-dimensional organic/inorganic heterostructure devices.

Rapidly reversible redox transformation in nanophase manganese oxides at room temperature triggered by changes in hydration

PubMed Central

Birkner, Nancy; Navrotsky, Alexandra

2014-01-01

Chemisorption of water onto anhydrous nanophase manganese oxide surfaces promotes rapidly reversible redox phase changes as confirmed by calorimetry, X-ray diffraction, and titration for manganese average oxidation state. Surface reduction of bixbyite (Mn2O3) to hausmannite (Mn3O4) occurs in nanoparticles under conditions where no such reactions are seen or expected on grounds of bulk thermodynamics in coarse-grained materials. Additionally, transformation does not occur on nanosurfaces passivated by at least 2% coverage of what is likely an amorphous manganese oxide layer. The transformation is due to thermodynamic control arising from differences in surface energies of the two phases (Mn2O3 and Mn3O4) under wet and dry conditions. Such reversible and rapid transformation near room temperature may affect the behavior of manganese oxides in technological applications and in geologic and environmental settings. PMID:24733903

Investigation of electronic band structure and charge transfer mechanism of oxidized three-dimensional graphene as metal-free anodes material for dye sensitized solar cell application

NASA Astrophysics Data System (ADS)

Loeblein, Manuela; Bruno, Annalisa; Loh, G. C.; Bolker, Asaf; Saguy, Cecile; Antila, Liisa; Tsang, Siu Hon; Teo, Edwin Hang Tong

2017-10-01

Dye-sensitized solar cells (DSSCs) offer an optimal trade-off between conversion-efficiency and low-cost fabrication. However, since all its electrodes need to fulfill stringent work-function requirements, its materials have remained unchanged since DSSC's first report early-90s. Here we describe a new material, oxidized-three-dimensional-graphene (o-3D-C), with a band gap of 0.2 eV and suitable electronic band-structure as alternative metal-free material for DSSCs-anodes. o-3D-C/dye-complex has a strong chemical bonding via carboxylic-group chemisorption with full saturation after 12 sec at capacity of ∼450 mg/g (600x faster and 7x higher than optimized metal surfaces). Furthermore, fluorescence quenching of life-time by 28-35% was measured demonstrating charge-transfer from dye to o-3D-C.

Volatile metal deposits on lunar soils: Relation to volcanism

NASA Technical Reports Server (NTRS)

Reed, G. W., Jr.; Allen, R. O., Jr.; Jovanovic, S.

1977-01-01

Parallel leaching and volatilization experiments conducted on lunar samples and similar experiments on sphalerite do not supply the information needed to resolve the question of the chemical nature of pb 204, Zn, Bi and Tl deposits on lunar soil surfaces. It is proposed that in Apollo 17 mare and terra soils and fractions of pb 204, Zn and Tl that are insoluble under mild, hot pH 5HNO3, leaching conditions and involatile at 600 C were originally surface deposits which became immobilized by migration into the silicate substrate or by chemisorption. Only Bi is predominantly indigenous. The implication is also that the soils over their respective times of evolution were exposed to heavy metal vapors or that an episodic exposure occurred after they had evolved. A sequence of events is proposed to account for orange 74220 and black 74001 glasses by lava fountaining and for soil 74241 as tephra from an explosive volcanic eruption.

A nitride-based epitaxial surface layer formed by ammonia treatment of silicene-terminated ZrB{sub 2}

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

Wiggers, F. B., E-mail: F.B.Wiggers@utwente.nl; Van Bui, H.; Schmitz, J.

We present a method for the formation of an epitaxial  surface layer involving B, N, and Si atoms on a ZrB{sub 2}(0001) thin film on Si(111). It has the potential to be an insulating growth template for 2D semiconductors. The chemical reaction of NH{sub 3} molecules with the silicene-terminated ZrB{sub 2}  surface was characterized by synchrotron-based, high-resolution core-level photoelectron spectroscopy and low-energy electron diffraction. In particular, the dissociative chemisorption of NH{sub 3} at 400 °C leads to surface  nitridation, and subsequent annealing up to 830 °C results in a solid phase reaction with the ZrB{sub 2} subsurface layers. In this way, amore » new nitride-based epitaxial  surface layer is formed with hexagonal symmetry and a single in-plane crystal orientation.« less

Adsorption of dissolved Reactive red dye from aqueous phase onto activated carbon prepared from agricultural waste.

PubMed

Senthilkumaar, S; Kalaamani, P; Porkodi, K; Varadarajan, P R; Subburaam, C V

2006-09-01

The adsorption of Reactive red dye (RR) onto Coconut tree flower carbon (CFC) and Jute fibre carbon (JFC) from aqueous solution was investigated. Adsorption studies were carried out at different initial dye concentrations, initial solution pH and adsorbent doses. The kinetic studies were also conducted; the adsorption of Reactive red onto CFC and JFC followed pseudosecond-order rate equation. The effective diffusion coefficient was evaluated to establish the film diffusion mechanism. Quantitative removal of Reactive red dye was achieved at strongly acidic conditions for both the carbons studied. The adsorption isotherm data were fitted well to Langmuir isotherm and the adsorption capacity were found to be 181.9 and 200 mg/g for CFC and JFC, respectively. The overall rate of dye adsorption appeared to be controlled by chemisorption, in this case in accordance with poor desorption studies.

Rapidly reversible redox transformation in nanophase manganese oxides at room temperature triggered by changes in hydration.

PubMed

Birkner, Nancy; Navrotsky, Alexandra

2014-04-29

Chemisorption of water onto anhydrous nanophase manganese oxide surfaces promotes rapidly reversible redox phase changes as confirmed by calorimetry, X-ray diffraction, and titration for manganese average oxidation state. Surface reduction of bixbyite (Mn2O3) to hausmannite (Mn3O4) occurs in nanoparticles under conditions where no such reactions are seen or expected on grounds of bulk thermodynamics in coarse-grained materials. Additionally, transformation does not occur on nanosurfaces passivated by at least 2% coverage of what is likely an amorphous manganese oxide layer. The transformation is due to thermodynamic control arising from differences in surface energies of the two phases (Mn2O3 and Mn3O4) under wet and dry conditions. Such reversible and rapid transformation near room temperature may affect the behavior of manganese oxides in technological applications and in geologic and environmental settings.

Solid sorbents for removal of carbon dioxide from gas streams at low temperatures

DOEpatents

Sirwardane, Ranjani V.

2005-06-21

New low-cost CO.sub.2 sorbents are provided that can be used in large-scale gas-solid processes. A new method is provided for making these sorbents that involves treating substrates with an amine and/or an ether so that the amine and/or ether comprise at least 50 wt. percent of the sorbent. The sorbent acts by capturing compounds contained in gaseous fluids via chemisorption and/or physisorption between the unit layers of the substrate's lattice where the polar amine liquids and solids and/or polar ether liquids and solids are located. The method eliminates the need for high surface area supports and polymeric materials for the preparation of CO.sub.2 capture systems, and provides sorbents with absorption capabilities that are independent of the sorbents' surface areas. The sorbents can be regenerated by heating at temperatures in excess of 35.degree. C.

van der Waals forces and confinement in carbon nanopores: Interaction between CH 4, COOH, NH 3, OH, SH and single-walled carbon nanotubes

DOE PAGES

Weck, Philippe F.; Kim, Eunja; Wang, Yifeng

2016-04-13

Interactions between CH 4, COOH, NH 3, OH, SH and armchair (n,n)(n=4,7,14) and zigzag (n,0)(n=7,12,25) single-walled carbon nanotubes (SWCNTs) have been systematically investigated within the framework of dispersion-corrected density functional theory (DFT-D2). Endohedral and exohedral molecular adsorption on SWCNT walls is energetically unfavorable or weak, despite the use of C 6/r 6 pairwise London-dispersion corrections. The effects of pore size and chirality on the molecule/SWCNTs interaction were also assessed. Furthermore, chemisorption of COOH, NH 3, OH and SH at SWCNT edge sites was examined using a H-capped (7,0) SWCNT fragment and its impact on electrophilic, nucleophilic and radical attacks wasmore » predicted by means of Fukui functions.« less

Work function tunability of borophene via doping: A first principle study

NASA Astrophysics Data System (ADS)

Katoch, Neha; Sharma, Munish; Thakur, Rajesh; Ahluwalia, P. K.

2018-04-01

A first principle study of structural properties, work function and electronic properties of pristine and substitutional doped borophene atomic layer with X atoms (X = F, Cl, H, Li, Na) have been carried out within the framework of density functional theory (DFT). Studied adsorption energies are high for all dopants indicating adsorption to be chemisorption type. The reduction in work function of pristine borophene has been found with n-type (Li, Na) dopants is of the order of 0.42 eV which is higher than that of the reduction in work function of borophene with p-type (F, Cl) dopants. For H dopants there is no reduction in work function of borophene. Quantum ballistic conductance has been found to modulate with doping. The quantum ballistic conductance is decreasing for doped borophene in the order Li > Cl ˜ H ˜ Na > F as compared to pristine borophene.

A Quantitative PCR-Electrochemical Genosensor Test for the Screening of Biotech Crops

PubMed Central

Moura-Melo, Suely; Miranda-Castro, Rebeca; de-los-Santos-Álvarez, Noemí; Miranda-Ordieres, Arturo J.; dos Santos Junior, José Ribeiro; da Silva Fonseca, Rosana A.; Lobo-Castañón, María Jesús

2017-01-01

The design of screening methods for the detection of genetically modified organisms (GMOs) in food would improve the efficiency in their control. We report here a PCR amplification method combined with a sequence-specific electrochemical genosensor for the quantification of a DNA sequence characteristic of the 35S promoter derived from the cauliflower mosaic virus (CaMV). Specifically, we employ a genosensor constructed by chemisorption of a thiolated capture probe and p-aminothiophenol gold surfaces to entrap on the sensing layer the unpurified PCR amplicons, together with a signaling probe labeled with fluorescein. The proposed test allows for the determination of a transgene copy number in both hemizygous (maize MON810 trait) and homozygous (soybean GTS40-3-2) transformed plants, and exhibits a limit of quantification of at least 0.25% for both kinds of GMO lines. PMID:28420193

Removal of Cd (II) from water using the waste of jatropha fruit ( Jatropha curcas L.)

NASA Astrophysics Data System (ADS)

Nacke, Herbert; Gonçalves, Affonso Celso; Coelho, Gustavo Ferreira; Schwantes, Daniel; Campagnolo, Marcelo Angelo; Leismann, Eduardo Ariel Völz; Junior, Élio Conradi; Miola, Alisson Junior

2017-10-01

The aim of this work was to evaluate the removal of Cd (II) from water using three biosorbents originated from the biomass of jatropha (bark, endosperm, and endosperm + tegument). For that, batch tests were performed to verify the effect of solution pH, adsorbent mass, contact time, initial concentration of Cd (II), and the temperature of the process. The adsorption process was evaluated by the studies of kinetics, isotherms, and thermodynamics. The ideal conditions of solution pH were 5.5 and 8 g L-1 of adsorbent mass of biosorbents by solution volume, with an equilibrium time of 60 min. According to the Langmuir model, the maximum adsorption capacity for bark, endosperm, and bark + endosperm of jatropha was, respectively, 29.665, 19.562, and 34.674 mg g-1, predominating chemisorption in monolayers. The biosorbents presented potential for the remediation of waters contaminated with Cd (II).

Gas sensing at the nanoscale: engineering SWCNT-ITO nano-heterojunctions for the selective detection of NH3 and NO2 target molecules

NASA Astrophysics Data System (ADS)

Rigoni, F.; Drera, G.; Pagliara, S.; Perghem, E.; Pintossi, C.; Goldoni, A.; Sangaletti, L.

2017-01-01

The gas response of single-wall carbon nanotubes (SWCNT) functionalized with indium tin oxide (ITO) nanoparticles (NP) has been studied at room temperature and an enhanced sensitivity to ammonia and nitrogen dioxide is demonstrated. The higher sensitivity in the functionalized sample is related to the creation of nano-heterojunctions at the interface between SWCNT bundles and ITO NP. Furthermore, the different response of the two devices upon NO2 exposure provides a way to enhance also the selectivity. This behavior is rationalized by considering a gas sensing mechanism based on the build-up of space-charge layers at the junctions. Finally, full recovery of the signal after exposure to NO2 is achieved by UV irradiation for the functionalized sample, where the ITO NP can play a role to hinder the poisoning effects on SWCNT due to NO2 chemisorption.

Gas sensing at the nanoscale: engineering SWCNT-ITO nano-heterojunctions for the selective detection of NH3 and NO2 target molecules.

PubMed

Rigoni, F; Drera, G; Pagliara, S; Perghem, E; Pintossi, C; Goldoni, A; Sangaletti, L

2017-01-20

The gas response of single-wall carbon nanotubes (SWCNT) functionalized with indium tin oxide (ITO) nanoparticles (NP) has been studied at room temperature and an enhanced sensitivity to ammonia and nitrogen dioxide is demonstrated. The higher sensitivity in the functionalized sample is related to the creation of nano-heterojunctions at the interface between SWCNT bundles and ITO NP. Furthermore, the different response of the two devices upon NO 2 exposure provides a way to enhance also the selectivity. This behavior is rationalized by considering a gas sensing mechanism based on the build-up of space-charge layers at the junctions. Finally, full recovery of the signal after exposure to NO 2 is achieved by UV irradiation for the functionalized sample, where the ITO NP can play a role to hinder the poisoning effects on SWCNT due to NO 2 chemisorption.

Spatial, Hysteretic, and Adaptive Host-Guest Chemistry in a Metal-Organic Framework with Open Watson-Crick Sites.

PubMed

Cai, Hong; Li, Mian; Lin, Xiao-Rong; Chen, Wei; Chen, Guang-Hui; Huang, Xiao-Chun; Li, Dan

2015-09-01

Biological and artificial molecules and assemblies capable of supramolecular recognition, especially those with nucleobase pairing, usually rely on autonomous or collective binding to function. Advanced site-specific recognition takes advantage of cooperative spatial effects, as in local folding in protein-DNA binding. Herein, we report a new nucleobase-tagged metal-organic framework (MOF), namely ZnBTCA (BTC=benzene-1,3,5-tricarboxyl, A=adenine), in which the exposed Watson-Crick faces of adenine residues are immobilized periodically on the interior crystalline surface. Systematic control experiments demonstrated the cooperation of the open Watson-Crick sites and spatial effects within the nanopores, and thermodynamic and kinetic studies revealed a hysteretic host-guest interaction attributed to mild chemisorption. We further exploited this behavior for adenine-thymine binding within the constrained pores, and a globally adaptive response of the MOF host was observed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Six-dimensional quantum dynamics study for the dissociative adsorption of HCl on Au(111) surface

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

Liu, Tianhui; Fu, Bina; Zhang, Dong H., E-mail: zhangdh@dicp.ac.cn

The six-dimensional quantum dynamics calculations for the dissociative chemisorption of HCl on Au(111) are carried out using the time-dependent wave-packet approach, based on an accurate PES which was recently developed by neural network fitting to density functional theory energy points. The influence of vibrational excitation and rotational orientation of HCl on the reactivity is investigated by calculating the exact six-dimensional dissociation probabilities, as well as the four-dimensional fixed-site dissociation probabilities. The vibrational excitation of HCl enhances the reactivity and the helicopter orientation yields higher dissociation probability than the cartwheel orientation. A new interesting site-averaged effect is found for the titlemore » molecule-surface system that one can essentially reproduce the six-dimensional dissociation probability by averaging the four-dimensional dissociation probabilities over 25 fixed sites.« less

Interaction of tetraethoxysilane with OH-terminated SiO2 (0 0 1) surface: A first principles study

NASA Astrophysics Data System (ADS)

Deng, Xiaodi; Song, Yixu; Li, Jinchun; Pu, Yikang

2014-06-01

First principles calculates have been performed to investigate the surface reaction mechanism of tetraethoxysilane (TEOS) with fully hydroxylated SiO2(0 0 1) substrate. In semiconductor industry, this is the key step to understand and control the SiO2 film growth in chemical vapor deposition (CVD) and atomic layer deposition (ALD) processes. During the calculation, we proposed a model which breaks the surface dissociative chemisorption into two steps and we calculated the activation barriers and thermochemical energies for each step. Our calculation result for step one shows that the first half reaction is thermodynamically favorable. For the second half reaction, we systematically studied the two potential reaction pathways. The comparing result indicates that the pathway which is more energetically favorable will lead to formation of crystalline SiO2 films while the other will lead to formation of disordered SiO2 films.

Thermodynamic and kinetic studies of As2O3 toxicological effects on human insulin in generation diabetes mellitus

NASA Astrophysics Data System (ADS)

Mohsennia, Mohsen; Motaharinejad, Atieh; Rafiee-Pour, Hossain-Ali; Torabbeigi, Marzieh

2017-12-01

The interaction of arsenic trioxide with human insulin was investigated by circular dichroism (CD), cyclic voltammetry and electrophoresis techniques. The interfacial behavior of insulin in presence of As2O3 onto the Ag electrode surface was studied at 310 K in phosphate buffer solution (PBS). According to Far-UV CD spectroscopy results, As2O3 caused to decrease in structural compactness and variety of alpha helix into beta structures. Near-UV CD indicated that As2O3 dissociates disulfide linkage in insulin structure. The kinetic parameters, including charge-transfer coefficient and apparent heterogeneous electron transfer rate constant were also determined. The thermodynamic parameters of insulin denaturation in presence of arsenic trioxide were calculated and reported. The obtained results indicated strong adsorption of insulin in presence of arsenic trioxide onto the Ag surface via chemisorptions.

Theoretical Study of the Structure, Stability and Oxygen Reduction Activity of Ultrathin Platinum Nanowires

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

Matanovic, Ivana; Kent, Paul; Garzon, Fernando

2012-10-10

We use density functional theory to study the difference in the structure, stability and catalytic reactivity between ultrathin, 0.5- 1.0 nm diameter, platinum nanotubes and nanowires. Model nanowires were formed by inserting an inner chain of platinum atoms in small diameter nanotubes. In this way more stable, nonhollow structures were formed. The difference in the electronic structure of platinum nanotubes and nanowires was examined by inspecting the density of surface states and band structure. Furthermore, reactivity towards the oxygen reduction reaction of platinum nanowires was addressed by studying the change in the chemisorption energies of oxygen and hydroxyl groups, inducedmore » by inserting the inner chain of platinum atoms into the hollow nanotubes. Both ultrathin platinum nanotubes and nanowires show distinct properties compared to bulk platinum. Nanotubes with diameters larger than 1 nm show promise for use as oxygen reduction catalysts.« less

Density Functional Study of the Structure, Stability and Oxygen Reduction Activity of Ultrathin Platinum Nanowires

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

Matanovic, Ivana; Kent, Paul; Garzon, Fernando

2013-03-14

We used density functional theory to study the difference in the structure, stability and catalytic reactivity between ultrathin, 0.5–1.0 nm diameter, platinum nanotubes and nanowires. Model nanowires were formed by inserting an inner chain of platinum atoms in small diameter nanotubes. In this way more stable, non-hollow structures were formed. The difference in the electronic structure of platinum nanotubes and nanowires was examined by inspecting the density of surface states and band structure. Furthermore, reactivity toward the oxygen reduction reaction of platinum nanowires was assessed by studying the change in the chemisorption energies of oxygen, hydroxyl, and hydroperoxyl groups, inducedmore » by converting the nanotube models to nanowires. Both ultrathin platinum nanotubes and nanowires show distinct properties compared to bulk platinum. Single-wall nanotubes and platinum nanowires with diameters larger than 1 nm show promise for use as oxygen reduction catalysts.« less

The study of 'microsurfaces' using thermal desorption spectroscopy

NASA Technical Reports Server (NTRS)

Thomas, M. E.; Poppa, H.; Pound, G. M.

1979-01-01

The use of a newly combined ultrahigh vacuum technique for studying continuous and particulate evaporated thin films using thermal desorption spectroscopy (TDS), transmission electron microscopy (TEM), and transmission electron diffraction (TED) is discussed. It is shown that (1) CO thermal desorption energies of epitaxially deposited (111) Ni and (111) Pd surfaces agree perfectly with previously published data on bulk (111) single crystal, (2) contamination and surface structural differences can be detected using TDS as a surface probe and TEM as a complementary technique, and (3) CO desorption signals from deposited metal coverages of one-thousandth of a monolayer should be detectable. These results indicate that the chemisorption properties of supported 'microsurfaces' of metals can now be investigated with very high sensitivity. The combined use of TDS and TEM-TED experimental methods is a very powerful technique for fundamental studies in basic thin film physics and in catalysis.

Effect of the platinum content on the microstructure and micropore size distribution of Pt/alumina-pillared clays.

PubMed

Barrera-Vargas, M; Valencia-Rios, J; Vicente, M A; Korili, S A; Gil, A

2005-12-15

The aim of this work is to study the effect of the platinum content (0-1.8 wt % Pt) on the microstructure of an alumina-pillared clay. For this purpose, the nitrogen physisorption data at -196 degrees C, the micropore size distributions of the supported platinum catalysts, and the hydrogen chemisorption results at 30 degrees C have been analyzed and compared. The preparation of the catalysts has modified the textural properties of the Al-pillared clay support, giving rise to a loss of surface area and micropore volume. After reduction at 420 degrees C, the presence of dispersed metallic platinum with mean crystallite size in the 22-55 A range has been found by hydrogen adsorption. Comparison of all results reveals that the platinum species block the micropore entrances by steric hindrance to nitrogen access as the platinum content increases.

Optimization and adsorption kinetic studies of aqueous manganese ion removal using chitin extracted from shells of edible Philippine crabs

NASA Astrophysics Data System (ADS)

Quimque, Mark Tristan J.; Jimenez, Marvin C.; Acas, Meg Ina S.; Indoc, Danrelle Keth L.; Gomez, Enjelyn C.; Tabuñag, Jenny Syl D.

2017-01-01

Manganese is a common contaminant in drinking water along with other metal pollutants. This paper investigates the use of chitin, extracted from crab shells obtained as restaurant throwaway, as an adsorbent in removing manganese ions from aqueous medium. In particular, this aims to optimize the adsorption parameters and look into the kinetics of the process. The adsorption experiments done in this study employed the batch equilibration method. In the optimization, the following parameters were considered: pH and concentration of Mn (II) sorbate solution, particle size and dosage of adsorbent chitin, and adsorbent-adsorbate contact time. At the optimal condition, the order of the adsorption reaction was estimated using kinetic models which describes the process best. It was found out that the adsorption of aqueous Mn (II) ions onto chitin obeys the pseudo-second order model. This model assumes that the adsorption occurred via chemisorption

Advanced air revitalization system modeling and testing

NASA Technical Reports Server (NTRS)

Dall-Baumann, Liese; Jeng, Frank; Christian, Steve; Edeer, Marybeth; Lin, Chin

1990-01-01

To support manned lunar and Martian exploration, an extensive evaluation of air revitalization subsystems (ARS) is being conducted. The major operations under study include carbon dioxide removal and reduction; oxygen and nitrogen production, storage, and distribution; humidity and temperature control; and trace contaminant control. A comprehensive analysis program based on a generalized block flow model was developed to facilitate the evaluation of various processes and their interaction. ASPEN PLUS was used in modelling carbon dioxide removal and reduction. Several life support test stands were developed to test new and existing technologies for their potential applicability in space. The goal was to identify processes which use compact, lightweight equipment and maximize the recovery of oxygen and water. The carbon dioxide removal test stands include solid amine/vacuum desorption (SAVD), regenerative silver oxide chemisorption, and electrochemical carbon dioxide concentration (EDC). Membrane-based carbon dioxide removal and humidity control, catalytic reduction of carbon dioxide, and catalytic oxidation of trace contaminants were also investigated.

Removal of Lead Hydroxides Complexes from Solutions Formed in Silver/Gold: Cyanidation Process

NASA Astrophysics Data System (ADS)

Parga, José R.; Martinez, Raul Flores; Moreno, Hector; Gomes, Andrew Jewel; Cocke, David L.

2014-04-01

The presence of lead hydroxides in "pregnant cyanide solution" decreases the quality of the Dore obtained in the recovery processes of gold and silver, so it is convenient to remove them. The adsorbent capacity of the low cost cow bone powder was investigated for the removal of lead ions from a solution of lead hydroxide complexes at different initial metal ion concentrations (10 to 50 mg/L), and reaction time. Experiments were carried out in batches. The maximum sorption capacity of lead determined by the Langmuir model was found to be 126.58 mg/g, and the separation factor R L was between 0 and 1, indicating a significant affinity of bone for lead. Experimental data follow pseudo-second order kinetics suggesting chemisorption. It is concluded that cow bone powder can be successfully used for the removal of lead ions, and improves the quality of the silver-gold cyanides precipitate.

Laser Tailoring the Surface Chemistry and Morphology for Wear, Scale and Corrosion Resistant Superhydrophobic Coatings.

PubMed

Boinovich, Ludmila B; Emelyanenko, Kirill A; Domantovsky, Alexander G; Emelyanenko, Alexandre M

2018-06-04

A strategy, combining laser chemical modification with laser texturing, followed by chemisorption of the fluorinated hydrophobic agent was used to fabricate the series of superhydrophobic coatings on an aluminum alloy with varied chemical compositions and parameters of texture. It was shown that high content of aluminum oxynitride and aluminum oxide formed in the surface layer upon laser treatment allows solving the problem of enhancement of superhydrophobic coating resistance to abrasive loads. Besides, the multimodal structure of highly porous surface layer leads to self-healing ability of fabricated coatings. Long-term behavior of designed coatings in "hard" hot water with an essential content of calcium carbonate demonstrated high antiscaling resistance with self-cleaning potential against solid deposits onto the superhydrophobic surfaces. Study of corrosion protection properties and the behavior of coatings at long-term contact with 0.5 M NaCl solution indicated extremely high chemical stability and remarkable anticorrosion properties.

Quantifying the density and utilization of active sites in non-precious metal oxygen electroreduction catalysts

PubMed Central

Sahraie, Nastaran Ranjbar; Kramm, Ulrike I.; Steinberg, Julian; Zhang, Yuanjian; Thomas, Arne; Reier, Tobias; Paraknowitsch, Jens-Peter; Strasser, Peter

2015-01-01

Carbon materials doped with transition metal and nitrogen are highly active, non-precious metal catalysts for the electrochemical conversion of molecular oxygen in fuel cells, metal air batteries, and electrolytic processes. However, accurate measurement of their intrinsic turn-over frequency and active-site density based on metal centres in bulk and surface has remained difficult to date, which has hampered a more rational catalyst design. Here we report a successful quantification of bulk and surface-based active-site density and associated turn-over frequency values of mono- and bimetallic Fe/N-doped carbons using a combination of chemisorption, desorption and 57Fe Mössbauer spectroscopy techniques. Our general approach yields an experimental descriptor for the intrinsic activity and the active-site utilization, aiding in the catalyst development process and enabling a previously unachieved level of understanding of reactivity trends owing to a deconvolution of site density and intrinsic activity. PMID:26486465

Synthesis And Single Molecule Force Spectroscopy Of Poly(hydroxyethyl methacrylate-g-ethylene glycol)

NASA Astrophysics Data System (ADS)

Zhang, Dong; Ortiz, Christine

2003-03-01

With the advent of nanotechnology, miniaturized devices will soon need nanoscale springs with well-controlled nanomechanical properties such as shock absorbers, or to control the adhesive interactions between two components. In order to understand, manipulate, and control single macromolecule nanomechanical properties, mono(thiol)-terminated poly(hydroxyethyl methacrylate-g-ethylene glycol) has been synthesized via atom transfer radical polymerization. End-functionalization, chemical structure, molecular weight, side-chain graft density, radius of gyration, and polydispersity were characterized by 1H nuclear magnetic resonance, static light scattering, and gel permeation chromatography. The polymer chains were attached to Au-coated Si wafers via chemisorption to prepare well-separated "mushrooms", as verified by atomic force microscopy. Single molecule force spectroscopy was then used to measure the extensional elastic properties, i.e. force (nN) versus end-to-end separation distance (nm), of the individual chains by tethering to a Si3N4 probe tip via nonspecific, physisorption interactions.

Consolidation of tin sulfide chalcogels and xerogels with and without adsorbed iodine

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

Riley, Brian J.; Pierce, David A.; Lepry, William C.

Tin sulfide (Sn2S3) chalcogels are one of the most effective non-oxide aerogels evaluated to date for iodine gas capture. This is attributed to the fact that the Sn within the gel network has a strong affinity for chemisorption of iodine to form SnI4. This study demonstrates an approach for consolidating the raw and iodine-sorbed Sn2S3 chalcogels into a chalcogenide glass using GeS2 as a glass forming additive. The system with both iodine-sorbed and iodine-free Sn2S3 chalcogels provides better glass-forming characteristics than Sn-S or Sn-S-I alone, and the quantity of iodine measured in the bulk glass of the consolidated iodine-sorbed Sn2S3more » chalcogel was at ~45 mass%. Additional experiments were also conducted using microwave sintering and hot isostatic pressing with Sn2S3 xerogels.« less

Desorption kinetics of {H}/{Mo(211) }

NASA Astrophysics Data System (ADS)

Lopinski, G. P.; Prybyla, J. A.; Estrup, P. J.

1994-08-01

The desorption kinetics of the {H}/{Mo(211) } chemisorption system were studied by thermal desorption and measurement of adsorption isobars. Analysis of the steady-state measurements permits the independent determination of the desorption energy ( Ed) and prefactor ( v). These quantities are found to depend strongly on coverage, with ( Ed) varying continuously from 145 {kJ}/{mol} at low coverage to 65 {kJ}/{mol} near saturation. Three regions of hydrogen adsorption are clearly indicated by the isobars as well as the thermal desorption traces. These regions can be correlated with structural changes observed previously with HREELS and LEED. The coverage dependence of the kinetic parameters is attributed to hydrogen-induced local distortions of the substrate structure. By relating the desorption energy to the isosteric heat the partial molar entropy is also extracted from the data and indicates localized adsorption as well as significant adsorbate-induced changes in the substrate degrees of freedom.

An AgI@g-C3N4 hybrid core@shell structure: Stable and enhanced photocatalytic degradation

NASA Astrophysics Data System (ADS)

Liu, Li; Qi, Yuehong; Yang, Jinyi; Cui, Wenquan; Li, Xingang; Zhang, Zisheng

2015-12-01

A novel visible-light-active material AgI@g-C3N4 was prepared by ultrasonication/chemisorption method. The core@shell structure AgI@g-C3N4 catalyst showed high efficiency for the degradation of MB under visible light irradiation (λ > 420 nm). Nearly 96.5% of MB was degraded after 120 min of irradiation in the presence of the AgI@g-C3N4 photocatalyst. Superior stability was also observed in the cyclic runs indicating that the as prepared hybrid composite is highly desirable for the remediation of organic contaminated wastewaters. The improved photocatalytic performance is due to synergistic effects at the interface of AgI and g-C3N4 which can effectively accelerate the charge separation and reinforce the photostability of hybrid composite. The possible mechanism for the photocatalytic activity of AgI@g-C3N4 was tentatively proposed.

Interaction of cytidine 5'-monophosphate with Au(111): an in situ infrared spectroscopic study.

PubMed

Doneux, Thomas; Fojt, Lukás

2009-07-13

The interaction of cytidine 5'-monophosphate (CMP) with gold surfaces is studied by means of in situ infrared spectroscopy and cyclic voltammetry at the Au(111)|aqueous solution interface. Similar to other nucleic acid components, cytidine 5'-monophosphate is chemisorbed on the surface at positive potentials, and the amount of adsorbed CMP increases with the potential. Subtractively normalized interfacial Fourier-transform infrared spectroscopy (SNIFTIRS) is used to identify the adsorbed and desorbed species. Upon electrochemical desorption, the molecules released in solution are unprotonated on the N3 atom. Striking similarities are found between the spectrum of adsorbed CMP and the solution spectrum of protonated CMP. The origin of such similarities is discussed. The results strongly suggest that chemisorption occurs through the N3 atom of the pyrimidine ring. A comparison is drawn with cytidine, whose electrochemical and spectroscopic behaviors are also investigated.

Adsorption and reaction of propene on Ni(100)

NASA Astrophysics Data System (ADS)

Kleyna, R.; Borgmann, D.; Wedler, G.

1998-05-01

Photoelectron spectroscopy (UPS, XPS) and thermal desorption techniques were used to study the chemisorption and decomposition reactions of propene on Ni(100). Propene is molecularly adsorbed at temperatures below 150 K. At saturation coverage the TD spectrum shows two propene desorption peaks at 155 and 225 K and three hydrogen desorption peaks at 300, 330 and 380 K with a shoulder at 420 K. No other desorbing species could be detected. The amount of desorption of propene was determined by XPS to be 20% of the saturation coverage. The electronic structure of adsorbed propene and the chemical nature of its decomposition products were deduced from UP and XP spectra taken at saturation coverage. Adsorption at low temperatures results in a π-bonded species which is stable up to 150 K. At temperatures above 150 K the UP spectra point to a σ-bonded species which decomposes further at temperatures above 260 K.

Insight into biosorption equilibrium, kinetics and thermodynamics of crystal violet onto Ananas comosus (pineapple) leaf powder

NASA Astrophysics Data System (ADS)

Chakraborty, Sagnik; Chowdhury, Shamik; Saha, Papita Das

2012-06-01

Biosorption performance of pineapple leaf powder (PLP) for removal of crystal violet (CV) from its aqueous solutions was investigated. To this end, the influence of operational parameters such as pH, biosorbent dose, initial dye concentration and temperature were studied employing a batch experimental setup. The biosorption process followed the Langmuir isotherm model with high correlation coefficients ( R 2 > 0.99) at different temperatures. The maximum monolayer biosorption capacity was found to be 78.22 mg g-1 at 293 K. The kinetic data conformed to the pseudo-second-order kinetic model. The activation energy of the system was calculated as 58.96 kJ mol- 1 , indicating chemisorption nature of the ongoing biosorption process. A thermodynamic study showed spontaneous and exothermic nature of the biosorption process. Owing to its low cost and high dye uptake capacity, PLP has potential for application as biosorbent for removal of CV from aqueous solutions.

Communication: Enhanced chemical reactivity of graphene on a Ni(111) substrate

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

Ambrosetti, Alberto; Silvestrelli, Pier Luigi

2016-03-21

Due to the unique combination of structural, mechanical, and transport properties, graphene has emerged as an exceptional candidate for catalysis applications. The low chemical reactivity caused by sp{sup 2} hybridization and strongly delocalized π electrons, however, represents a main challenge for straightforward use of graphene in its pristine, free-standing form. Following recent experimental indications, we show that due to charge hybridization, a Ni(111) substrate can enhance the chemical reactivity of graphene, as exemplified by the interaction with the CO molecule. While CO only physisorbs on free-standing graphene, chemisorption of CO involving formation of ethylene dione complexes is predicted in Ni(111)-graphene.more » Higher chemical reactivity is also suggested in the case of oxidized graphene, opening the way to a simple and efficient control of graphene chemical properties, devoid of complex defect patterning or active metallic structures deposition.« less

Selective depression of titanaugite in the ilmenite flotation with carboxymethyl starch

NASA Astrophysics Data System (ADS)

Meng, Qingyou; Yuan, Zhitao; Yu, Li; Xu, Yuankai; Du, Yusheng; Zhang, Chen

2018-05-01

In order to intensify the flotation separation of ilmenite from titanaugite, surface modification of mineral particles was carried out using carboxymethyl starch (CMS) by microflotation experiments, zeta potential measurements, Fourier transform infrared (FTIR) and atomic force microscopy (AFM) analysis. Microflotation results showed that CMS was a selective depressant, and it effectively enhanced the floatability difference between ilmenite and titanaugite in the pH range from 6.0 to 10.0. As it was revealed by the zeta potential, FTIR and AFM analysis, the CMS adsorption occurred onto mineral surfaces through chemisorption and hydrogen bonding, while CMS exhibited a stronger interaction with titanaugite than ilmenite. After that, the CMS adsorption impeded the adsorption of sodium oleate collector on titanaugite surfaces, giving rise to a concomitant decrease in the floatability of titanaugite. These findings exhibit great potential for CMS application in the selective flotation of ilmenite.

Ab initio surface properties of Ag-Sn alloys: implications for lead-free soldering.

PubMed

Saleh, Gabriele; Xu, Chen; Sanvito, Stefano

2018-02-07

Ag and Sn are the major components of solder alloys adopted to assemble printed circuit boards. The qualities that make them the alloys of choice for the modern electronic industry are related to their physical and chemical properties. For corrosion resistance and solderability, surface properties are particularly important. Yet, atomic-level information about the surfaces of these alloys is not known. Here we fill this gap by presenting an extensive ab initio investigation of composition, energetics, structure and reactivity of Ag-Sn alloy surfaces. The structure and stability of various surfaces is evaluated, and the main factors determining the energetics of surface formation are uncovered. Oxygen and sulphur chemisorptions are studied and discussed in the framework of corrosion tendency, an important issue for printed circuit boards. Adsorption energy trends are rationalized based on the analysis of structural and electronic features.

Quantum-chemical study of model chemisorption structures on copper-containing catalysts. Communicat ion 1. ab-initio calculations of CuCo and CuCo/sup +/

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

Kuzminskii, M.B.; Bagator'yants, A.A.; Kazanskii, V.B.

1986-08-01

The authors perform ab-initio calculations, by the SCF MO LCAO method, of the electronic and geometric structure of the systems CuCO /SUP n+/ (n=0, 1) and potential curves of CO, depending on the charge state of the copper, with variation of all geometric parameters. The calculations of open-shell electronic states were performed by the unrestricted SCF method in a minimal basis set (I, STO-3G for the C and O, and MINI-1' for the Cu) and in a valence two-exponential basis set (II, MIDI-1 for the C and O, and MIDI'2' for the Cu). The principal results from the calculation inmore » the more flexible basis II are presented and the agreement between the results obtained in the minimal basis I and these data is then analyzed qualitatively.« less

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

Cagnoli, M.V.; Marchetti, S.G.; Gallegos, N.G.

In order to study the influence of the support on high dispersion catalysts used for the CO hydrogenation reaction, two catalysts, Fe/SiO{sub 2} and Fe/Al{sub 2}O{sub 3}, were prepared by the dry impregnation method. Selective chemisorption of CO, volumetric oxidation, and Moessbauer spectroscopy were used to determine the Fe species present as well as the metallic crystal size, the degree of dispersion, and the reduction percentage. The presence of small Fe{sup 0} crystallites with high dispersion was determined in both catalysts. Reaction rates were measured in a differential reactor and significant differences, about one order of magnitude less for themore » Al{sub 2}O{sub 3} than for the SiO{sub 2} supported catalysts, were found in the methane turnover frequencies. They are attributed to the interaction between the metal and the supports. The selectivity differences is also discussed in connection with distinct surface properties.« less

Reversible and non-reversible changes in nanostructured Si in humid atmosphere

NASA Astrophysics Data System (ADS)

Zhigalov, V.; Pyatilova, O.; Timoshenkov, S.; Gavrilov, S.

2014-12-01

Atmosphere water influence in the nanostructured silicon (NSS) was investigated by IR-spectroscopy and electron work function measurement. Long-term non-reversible dynamics of IR-spectra was found as a result of 100% humidity influence on the nanostructured silicon. It was indicated that air humidity affects on the work function. Dynamics of the electron work function consists of reversible and non-reversible components. Reversible component appears as strong anti-correlation between work function and humidity. Work function change of NSS is about 0.4 eV while the humidity changes between 0% and 100%. Reversible component can be explained by physical sorption of water molecules on the surface. Non-reversible component manifests as long-term decreasing trend of work function in humid atmosphere. Transition curve during abruptly humidity changes alters its shape. Non-reversible component can be explained by chemisorption of water.

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

Anti-Corrosion Performance of 1,3-BENZOTHIAZOLE on 410 Martensitic Stainless Steel in H2SO4

NASA Astrophysics Data System (ADS)

Loto, Roland Tolulope

The corrosion inhibition effect of synthesized 1,3-benzothiazole at very low concentrations on 410 martensitic stainless steel in 3MH2SO4 solution was studied through potentiodynamic polarization and weight loss measurements. The observation showed that the organic compound performed effectively with average inhibition efficiencies of 94% and 98% at the concentrations studied from both electrochemical methods due to the inhibition action of protonated inhibitor molecules in the acid solution. The amine and aromatics functional groups of the molecules active in the corrosion inhibition reaction were exposed from Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) spectroscopic analysis. Thermodynamic calculations showed cationic adsorption to be chemisorption adsorption, obeying the Langmuir adsorption isotherm. Images from optical microscopy showed an improved morphology in comparison to images from corroded stainless steel. Severe surface deterioration and macro-pits were observed in the uninhibited samples.

Friction imprint effect in mechanically cleaved BaTiO{sub 3} (001)

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

Long, Christian J.; Maryland Nanocenter, University of Maryland, College Park, Maryland 20742; Ebeling, Daniel

2014-09-28

Adsorption, chemisorption, and reconstruction at the surfaces of ferroelectric materials can all contribute toward the pinning of ferroelectric polarization, which is called the electrical imprint effect. Here, we show that the opposite is also true: freshly cleaved, atomically flat surfaces of (001) oriented BaTiO{sub 3} exhibit a persistent change in surface chemistry that is driven by ferroelectric polarization. This surface modification is explored using lateral force microscopy (LFM), while the ferroelectric polarization is probed using piezoresponse force microscopy. We find that immediately after cleaving BaTiO{sub 3}, LFM reveals friction contrast between ferroelectric domains. We also find that this surface modificationmore » remains after the ferroelectric domain distribution is modified, resulting in an imprint of the original ferroelectric domain distribution on the sample surface. This friction imprint effect has implications for surface patterning as well as ferroelectric device operation and failure.« less

FI-STM study of hydrogen adsorption on Si(100) surface

NASA Astrophysics Data System (ADS)

Hua, Lu; Xiang-dong, Wang; Motai, K.; Hashizume, T.; Sakurai, T.

1992-11-01

Chemisorption of atomic hydrogen on the Si(100)2 × 1 surface has been investigated in detail by using a field ion-scanning tunneling microscope (FI-STM). The results showed that the adsorption geometry changed from the 2 × 1 monohydride phase to the 1 × 1 dihydride phase with increasing exposure of hydrogen. The data of desorption of the hydrogen-saturated Si surface showed that on annealing at 670 K the surface becomes highly disordered: the 1 × 1 dihydride structure is eliminated and the 2 × 1 reconstructed monohydride is also hardly to identify. When the temperature rises to as high as 730 K, the surface is dominated by the 2 × 1 structure with missing dimer rows, and some adatom chains occur on the Si substrate terraces. We attribute the formation of these atomic chains to an epitaxial growth of Si atoms which are formed by the dissociation of SiHx (x = 1, 2, 3 or 4) compounds on the Si surface.

The estimation of quantitative parameters of oligonucleotides immobilization on mica surface

NASA Astrophysics Data System (ADS)

Sharipov, T. I.; Bakhtizin, R. Z.

2017-05-01

Immobilization of nucleic acids on the surface of various materials is increasingly being used in research and some practical applications. Currently, the DNA chip technology is rapidly developing. The basis of the immobilization process can be both physical adsorption and chemisorption. A useful way to control the immobilization of nucleic acids on a surface is to use atomic force microscopy. It allows you to investigate the topography of the surface by its direct imaging with high resolution. Usually, to fix the DNA on the surface of mica are used cations which mediate the interaction between the mica surface and the DNA molecules. In our work we have developed a method for estimation of quantitative parameter of immobilization of oligonucleotides is their degree of aggregation depending on the fixation conditions on the surface of mica. The results on study of aggregation of oligonucleotides immobilized on mica surface will be presented. The single oligonucleotides molecules have been imaged clearly, whereas their surface areas have been calculated and calibration curve has been plotted.

Adsorption studies of methylene blue and gentian violet on sugarcane bagasse modified with EDTA dianhydride (EDTAD) in aqueous solutions: kinetic and equilibrium aspects.

PubMed

Gusmão, Karla Aparecida Guimarães; Gurgel, Leandro Vinícius Alves; Melo, Tânia Márcia Sacramento; Gil, Laurent Frédéric

2013-03-30

In this study the adsorption of cationic dyes by modified sugarcane bagasse with EDTA dianhydride (EB) was examined using methylene blue (MB) and gentian violet (GV) as model compounds in aqueous single solutions. The synthesized adsorbent (EB) was characterized by FTIR, elemental analysis, and BET. The capacity of EB to adsorb dyes was evaluated at different contact times, pH values, and initial dye concentrations. According to the obtained results, the adsorption processes could be described by a pseudo-second-order kinetic model. The adsorption isotherms were well fitted by the Langmuir model. Maximum adsorption capacities for MB and GV on EB were found to be 202.43 and 327.83 mg/g, respectively. The free energy change during adsorption of MB and GV was found to be -22.50 and -24.21 kJ/mol, respectively, suggesting that chemisorption is the main mechanism controlling the adsorption process. Copyright © 2013 Elsevier Ltd. All rights reserved.

NO-sensing performance of vacancy defective monolayer MoS2 predicted by density function theory

NASA Astrophysics Data System (ADS)

Li, Feifei; Shi, Changmin

2018-03-01

Using density functional theory (DFT), we predict the NO-sensing performance of monolayer MoS2 (MoS2-MLs) with and without MoS3-vacancy/S-vacancy defects. Our theoretical results demonstrate that MoS3- and S-vacancy defective MoS2-MLs show stronger chemisorption and greater electron transfer effects than pure MoS2-MLs. The charge transfer analysis showed pure and defective MoS2-MLs all act as donors. Both MoS3-vacancy and S-vacancy defects induce dramatic changes of electronic properties of MoS2-MLs, which have direct relationship with gas sensing performance. In addition, S-vacancy defect leads to more electrons transfer to NO molecule than MoS3-vacancy defect. The H2O molecule urges more electrons transfer from MoS3- or S-vacancy defective MoS2-MLs to NO molecule. We believe that this calculation results will provide some information for future experiment.

DFT simulation on H2 adsorption over Ni-decorated defective h-BN nanosheets

NASA Astrophysics Data System (ADS)

Zhou, Xuan; Chu, Wei; Zhou, Yanan; Sun, Wenjing; Xue, Ying

2018-05-01

Nickel doped defective h-BN nanosheets and their potential application on hydrogen storage were explored by density functional theory (DFT) calculation. Three types of defective h-BN (SW defect, VB and VN substrates) were modeled. In comparison with the SW defect, the B or N vacancy can improve the interaction between Ni atom and h-BN nanosheet strikingly. Furthermore, the Ni-doped SW defect sheet shows chemisorption on H2 molecules, and the Hsbnd H bond is partially dissociated. While on the VB sheet, Ni adatom interacts with H2 in the range of physisorption. However, the Ni-functionalized VN sheet exhibits a desirable adsorption on H2, and the corresponding energy varies from -0.40 to -0.51 eV, which is favorable for H2 adsorption and release at ambient conditions. As a result, the VN substrate is expected to a desirable support for H2 storage. Our work provides an insight into H2 storage on Ni-functionalized defective h-BN monolayer.

Analyte chemisorption and sensing on n- and p-channel copper phthalocyanine thin-film transistors.

PubMed

Yang, Richard D; Park, Jeongwon; Colesniuc, Corneliu N; Schuller, Ivan K; Royer, James E; Trogler, William C; Kummel, Andrew C

2009-04-28

Chemical sensing properties of phthalocyanine thin-film transistors have been investigated using nearly identical n- and p-channel devices. P-type copper phthalocyanine (CuPc) has been modified with fluorine groups to convert the charge carriers from holes to electrons. The sensor responses to the tight binding analyte dimethyl methylphosphonate (DMMP) and weak binding analyte methanol (MeOH) were compared in air and N(2). The results suggest that the sensor response involves counterdoping of pre-adsorbed oxygen (O(2)). A linear dependence of chemical response to DMMP concentration was observed in both n- and p- type devices. For DMMP, there is a factor of 2.5 difference in the chemical sensitivity between n- and p-channel CuPc thin-film transistors, even though it has similar binding strength to n- and p-type CuPc molecules as indicated by the desorption times. The effect is attributed to the difference in the analyte perturbation of electron and hole trap energies in n- and p-type materials.

Development of nanostars as a biocompatible tumor contrast agent: toward in vivo SERS imaging.

PubMed

D'Hollander, Antoine; Mathieu, Evelien; Jans, Hilde; Vande Velde, Greetje; Stakenborg, Tim; Van Dorpe, Pol; Himmelreich, Uwe; Lagae, Liesbet

2016-01-01

The need for sensitive imaging techniques to detect tumor cells is an important issue in cancer diagnosis and therapy. Surface-enhanced Raman scattering (SERS), realized by chemisorption of compounds suitable for Raman spectroscopy onto gold nanoparticles, is a new method for detecting a tumor. As a proof of concept, we studied the use of biocompatible gold nanostars as sensitive SERS contrast agents targeting an ovarian cancer cell line (SKOV3). Due to a high intracellular uptake of gold nanostars after 6 hours of exposure, they could be detected and located with SERS. Using these nanostars for passive targeting after systemic injection in a xenograft mouse model, a detectable signal was measured in the tumor and liver in vivo. These signals were confirmed by ex vivo SERS measurements and darkfield microscopy. In this study, we established SERS nanostars as a highly sensitive contrast agent for tumor detection, which opens the potential for their use as a theranostic agent against cancer.

Defect-Mediated Molecular Interaction and Charge Transfer in Graphene Mesh-Glucose Sensors.

PubMed

Kwon, Sun Sang; Shin, Jae Hyeok; Choi, Jonghyun; Nam, SungWoo; Park, Won Il

2017-04-26

We report the role of defects in enzymatic graphene field-effect transistor sensors by introducing engineered defects in graphene channels. Compared with conventional graphene sensors (Gr sensors), graphene mesh sensors (GM sensors), with an array of circular holes, initially exhibited a higher irreversible response to glucose, involving strong chemisorption to edge defects. However, after immobilization of glucose oxidase, the irreversibility of the responses was substantially diminished, without any reduction in the sensitivity of the GM sensors (i.e., -0.53 mV/mM for the GM sensor vs -0.37 mV/mM for Gr sensor). Furthermore, multiple cycle operation led to rapid sensing and improved the reversibility of GM sensors. In addition, control tests with sensors containing a linker showed that sensitivity was increased in Gr sensors but decreased in GM sensors. Our findings indicate that edge defects can be used to replace linkers for immobilization of glucose oxidase and improve charge transfer across glucose oxidase-graphene interfaces.

Volatile metal deposits on lunar soils - Relation to volcanism

NASA Technical Reports Server (NTRS)

Reed, G. W., Jr.; Jovanovic, S.; Allen, R. O., Jr.

1977-01-01

Parallel leaching and volatilization experiments conducted on lunar samples and similar experiments on sphalerite do not supply the information needed to resolve the question of the chemical nature of Pb-204, Zn, Bi, and Tl deposits on lunar soil surfaces. It is proposed that in Apollo 17 mare and terra soils the fractions of Pb-204, Zn, and Tl that are insoluble under mild, hot pH 5 HNO3, leaching conditions and involatile at 600 C were originally surface deposits which became immobilized by migration into the silicate substrate or by chemisorption. Most of the Bi does not seem to be the result of such a deposit. The implication is also that the soils, over their respective times of evolution, were exposed to heavy metal vapors or that an episodic exposure occurred after they had evolved. A sequence of events is proposed to account for orange 74220 and black 74001 glasses by lava fountaining and for soil 74241 as tephra from an explosive volcanic eruption.

Chemisorption of polysulfides through redox reactions with organic molecules for lithium-sulfur batteries.

PubMed

Li, Ge; Wang, Xiaolei; Seo, Min Ho; Li, Matthew; Ma, Lu; Yuan, Yifei; Wu, Tianpin; Yu, Aiping; Wang, Shun; Lu, Jun; Chen, Zhongwei

2018-02-16

Lithium-sulfur battery possesses high energy density but suffers from severe capacity fading due to the dissolution of lithium polysulfides. Novel design and mechanisms to encapsulate lithium polysulfides are greatly desired by high-performance lithium-sulfur batteries towards practical applications. Herein, we report a strategy of utilizing anthraquinone, a natural abundant organic molecule, to suppress dissolution and diffusion of polysulfides species through redox reactions during cycling. The keto groups of anthraquinone play a critical role in forming strong Lewis acid-based chemical bonding. This mechanism leads to a long cycling stability of sulfur-based electrodes. With a high sulfur content of ~73%, a low capacity decay of 0.019% per cycle for 300 cycles and retention of 81.7% over 500 cycles at 0.5 C rate can be achieved. This finding and understanding paves an alternative avenue for the future design of sulfur-based cathodes toward the practical application of lithium-sulfur batteries.

Modification of 13X Molecular Sieve by Chitosan for Adsorptive Removal of Cadmium from Simulated Wastewater.

PubMed

Shi, Yan; Sun, Ken; Huo, Lixin; Li, Xiuxiu; Qi, Xuebin; Li, Zhaohui

2017-09-19

Chitosan was used to modify a 13X molecular sieve to improve its cadmium removal capability. After being modified with 2% chitosan-acetate for 2 h at 30 °C, significant uptake of Cd 2+ could be achieved. The uptake of Cd 2+ on the modified 13X molecular sieve followed the Langmuir isotherms with a capacity of 1 mg/g. The kinetics of Cd 2+ removal by modified 13X molecular sieve followed a pseudo second-order reaction, suggesting chemisorption or surface complexation. The Cd 2+ removal with a sorbent dose of 2 g/L from an initial concentration of 100 μg/L reached more than 95% in 90 min. The equilibrium Cd 2+ concentration was <5 μg/L, which meets the requirements of "Standards for Irrigation Water Quality" (GB5084-2005) (10 μg/L) and MCL and MCLG for groundwater and drinking water (5 μg/L) set by United States Environmental Protection Agency.

Study the Formation of H2, HD and D2 under Various Interstellar Conditions

NASA Astrophysics Data System (ADS)

Sahu, Dipen; Chakrabarti, Sandip Kumar; Das, Ankan

2016-07-01

Hydrogen is the most abundant molecule in the Interstellar medium (ISM). Formation of gas phase hydrogen molecule is inefficient; perhaps grain surface acts as a necessary ingredients for the formation of H_2 molecule. H atoms accrete on the grain surface, recombine there and desorb in the gas phase. Similarly, deuterium accretion on grain surfaces can produce simple dueterated molecules (HD and D_2) on the ISM. Unlike gas phase reactions, rate equations can not yield accurate result for grain surface reactions due to inherent randomness of surface species. We use Monte-Carlo method to follow this surface chemistry which effectively take care of this randomness. We use square grids and impose periodic boundary condition on them to mimic the spherical nature of grains. Various types of rough surfaces are considered to study the impact on effective production rates. We found that these simple but most important molecules are produced in low temperature (physisorption sites) as well as in high temperature (chemisorption sites) regions.

Preparation and antibacterial properties of Ag@polydopamine/graphene oxide sheet nanocomposite

NASA Astrophysics Data System (ADS)

Zhou, Hao; Liu, Yunfang; Chi, Weidong; Yu, Changyuan; Yu, Yingjie

2013-10-01

Immobilization of silver nanoparticles (Ag NPs) on poly-dopamine (PDA) functionalized graphene oxide sheets (GOSs) were carried out by an easy in situ reduction method. The PDA layer was coated on the surface of the GOSs via the self-polymerization of dopamine under atmosphere condition. The PDA layer not only works as the chemisorption and reduction sites for silver ions to form Ag NPs but also stabilizes them. High-resolution transmission electron microscopy observation shows that the average size of the Ag NPs anchored on the PDA/GOS composite is about 2.8 nm. The inhibition zone diameter of the Ag@PDA/GOS nanocomposite is about 23.7 mm, whereas said diameter of the Ag NPs is only 18.5 mm. The minimum bactericidal concentration of the Ag@PDA/GOS nanocomposite is about 25 μg/ml that is only half of said concentration of the Ag NPs. The Ag@PDA/GOS nanocomposite exhibits an excellent antibacterial property.

Gas Interactions with Carbon Nanotubes - Chapter 11 in the book "Chemistry of Carbon Nanotubes," ed. by V.A. Basiuk and E.V. Basiuk, May 2008, American Scientific Publishers, Valencia, CA, ISBN: 978-1-58883-128-6, v. 1, pp. 217-236

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

Matranga, C.S.

2008-05-01

This book chapter will review the growing body of literature reporting on how gases interact with carbon nanotubes. The chapter will include both experimental and computational results. Issues related to the energetics, mechanism, geometry, and nature of adsorption sites in CNTs will be highlighted. An excellent review by Migone and Talaptra has detailed a large body of experimental results for the physisorption of gases on CNTs [1]. The current review chapter will not duplicate their efforts, but instead will focus on topics not included in their work: trapped molecules, molecular transport, chemisorption, and new physisorption results of significance. Research papersmore » related to hydrogen adsorption and storage have been omitted from this chapter since there are several reviews already published on this topic.« less

Adsorption of Ni(II) onto Chemically Modified Spent Grated Coconut (Cocos Nucifera)

NASA Astrophysics Data System (ADS)

Hamzah, F. I.; Khalid, K.; Hanafiah, M. A. K. M.

2017-06-01

A new adsorbent of plant waste origin from coconut processing food factory was explored for removing Ni(II) from aqueous solutions. Several parameters such as pH, dosage, concentration and contact time were studied to obtain optimum conditions for treatment of Ni(II) contaminated wastewater. Spent grated coconut (Cocos nucifera) treated with sulfuric acid (SSGC) showed good adsorption capacity for Ni(II) ion. The amount adsorbed was affected by solution pH with the highest value achieved at pH 5. Other optimum conditions found were; dosage of 0.02 g, and 60 min of equilibrium time. Ni(II) adsorption obeyed the pseudo-second order kinetic model which suggested that chemisorption mechanism occurred in the adsorption process. The equilibrium data presented a better fitting to the Langmuir isotherm model, an indication that monolayer adsorption occurred onto a homogeneous surface. The maximum adsorption capacity, qmax was 97.09 mg g-1, thus SSGC can be classified as good and comparable with other plant waste adsorbents.

Biosorption of food dyes onto Spirulina platensis nanoparticles: equilibrium isotherm and thermodynamic analysis.

PubMed

Dotto, G L; Lima, E C; Pinto, L A A

2012-01-01

The biosorption of food dyes FD&C red no. 40 and acid blue 9 onto Spirulina platensis nanoparticles was studied at different conditions of pH and temperature. Four isotherm models were used to evaluate the biosorption equilibrium and the thermodynamic parameters were estimated. Infra red analysis (FT-IR) and energy dispersive X-ray spectroscopy (EDS) were used to verify the biosorption behavior. The maximum biosorption capacities of FD&C red no. 40 and acid blue 9 were found at pH 4 and 298 K, and the values were 468.7 mg g(-1) and 1619.4 mg g(-1), respectively. The Sips model was more adequate to fit the equilibrium experimental data (R2>0.99 and ARE<5%). Thermodynamic study showed that the biosorption was exothermic, spontaneous and favorable. FT-IR and EDS analysis suggested that at pH 4 and 298 K, the biosorption of both dyes onto nanoparticles occurred by chemisorption. Copyright © 2011 Elsevier Ltd. All rights reserved.

Highly efficient adsorption of cationic dye by biochar produced with Korean cabbage waste.

PubMed

Sewu, Divine D; Boakye, Patrick; Woo, Seung H

2017-01-01

Biochar was produced from Korean cabbage (KC), rice straw (RS) and wood chip (WC) and the use as alternative adsorbents to activated carbon (AC) in wastewater treatment was investigated. Congo red (CR) and crystal violet (CV) were used as a model anionic and cationic dye, respectively. Initial solution pH had little effect on CR and CV adsorption onto all biochars except for AC on CR. The isotherm models and kinetic data showed that adsorption of CR and CV onto all biochars were dominantly by chemisorption. All biochars had lower adsorption capacity for CR than AC. KC showed higher Langmuir maximum adsorption capacity (1304mg/g) than AC (271.0mg/g), RS (620.3mg/g) and WC (195.6mg/g) for CV. KC may be a good alternative to conventional AC as cheap, superb and industrially viable adsorbent for removal of cationic dyes in wastewater. Copyright © 2016 Elsevier Ltd. All rights reserved.

Time scale of random sequential adsorption.

PubMed

Erban, Radek; Chapman, S Jonathan

2007-04-01

A simple multiscale approach to the diffusion-driven adsorption from a solution to a solid surface is presented. The model combines two important features of the adsorption process: (i) The kinetics of the chemical reaction between adsorbing molecules and the surface and (ii) geometrical constraints on the surface made by molecules which are already adsorbed. The process (i) is modeled in a diffusion-driven context, i.e., the conditional probability of adsorbing a molecule provided that the molecule hits the surface is related to the macroscopic surface reaction rate. The geometrical constraint (ii) is modeled using random sequential adsorption (RSA), which is the sequential addition of molecules at random positions on a surface; one attempt to attach a molecule is made per one RSA simulation time step. By coupling RSA with the diffusion of molecules in the solution above the surface the RSA simulation time step is related to the real physical time. The method is illustrated on a model of chemisorption of reactive polymers to a virus surface.

Self-assembled monolayers of alendronate on Ti6Al4V alloy surfaces enhance osteogenesis in mesenchymal stem cells

NASA Astrophysics Data System (ADS)

Rojo, Luis; Gharibi, Borzo; McLister, Robert; Meenan, Brian J.; Deb, Sanjukta

2016-07-01

Phosphonates have emerged as an alternative for functionalization of titanium surfaces by the formation of homogeneous self-assembled monolayers (SAMs) via Ti-O-P linkages. This study presents results from an investigation of the modification of Ti6Al4V alloy by chemisorption of osseoinductive alendronate using a simple, effective and clean methodology. The modified surfaces showed a tailored topography and surface chemistry as determined by SEM microscopy and RAMAN spectroscopy. X-ray photoelectron spectroscopy revealed that an effective mode of bonding is created between the metal oxide surface and the phosphate residue of alendronate, leading to formation of homogenous drug distribution along the surface. In-vitro studies showed that alendronate SAMs induce differentiation of hMSC to a bone cell phenotype and promote bone formation on modified surfaces. Here we show that this novel method for the preparation of functional coatings on titanium-based medical devices provides osseoinductive bioactive molecules to promote enhanced integration at the site of implantation.

Importance and Definition of Materials in Tribology. Status of Understanding

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1984-01-01

In general, tribological systems consist of three basic components: the material surfaces in contact, the lubricant, and the environment. The materials in contact and the influence of both bulk and surface properties, indicating the importance of material characterization, on tribological behavior are addressed. Since metals and metallic alloys are the most widely used class of materials in practical devices, attention is focused principally on them. With respect to surface behavior, the effect of contaminants both from within the material and from the environment on adhesive behavior is addressed. The various surface events that alter adhesion, friction, and wear are discussed. These include surface reconstruction, segregation, chemisorption, and compound formation. Examples of these events are presented. Minor nuances in the structure of the outermost layers of solids have a pronounced effect on tribological properties. The importance of characterizing the materials of solids in contact in order to achieve a fundamental understanding of adhesion, friction, and wear and accordingly of methods for their control are addressed.

A Novel Schiff Base of 3-acetyl-4-hydroxy-6-methyl-(2H)pyran-2-one and 2,2'-(ethylenedioxy)diethylamine as Potential Corrosion Inhibitor for Mild Steel in Acidic Medium

PubMed Central

Asegbeloyin, Jonnie N.; Ejikeme, Paul M.; Olasunkanmi, Lukman O.; Adekunle, Abolanle S.; Ebenso, Eno E.

2015-01-01

The corrosion inhibition activity of a newly synthesized Schiff base (SB) from 3-acetyl-4-hydroxy-6-methyl-(2H)-pyran-2-one and 2,2'-(ethylenedioxy)diethylamine was investigated on the corrosion of mild steel in 1 M HCl solution using potentiodynamic polarization and electrochemical impedance spectroscopic techniques. Ultraviolet-visible (UV-vis) and Raman spectroscopic techniques were used to study the chemical interactions between SB and mild steel surface. SB was found to be a relatively good inhibitor of mild steel corrosion in 1 M HCl. The inhibition efficiency increases with increase in concentration of SB. The inhibition activity of SB was ascribed to its adsorption onto mild steel surface, through physisorption and chemisorption, and described by the Langmuir adsorption model. Quantum chemical calculations indicated the presence of atomic sites with potential nucleophilic and electrophilic characteristics with which SB can establish electronic interactions with the charged mild steel surface.

Quantum and classical dynamics of water dissociation on Ni(111): A test of the site-averaging model in dissociative chemisorption of polyatomic molecules

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

Jiang, Bin; Department of Chemical Physics, University of Science and Technology of China, Hefei 230026; Guo, Hua, E-mail: hguo@unm.edu

Recently, we reported the first highly accurate nine-dimensional global potential energy surface (PES) for water interacting with a rigid Ni(111) surface, built on a large number of density functional theory points [B. Jiang and H. Guo, Phys. Rev. Lett. 114, 166101 (2015)]. Here, we investigate site-specific reaction probabilities on this PES using a quasi-seven-dimensional quantum dynamical model. It is shown that the site-specific reactivity is largely controlled by the topography of the PES instead of the barrier height alone, underscoring the importance of multidimensional dynamics. In addition, the full-dimensional dissociation probability is estimated by averaging fixed-site reaction probabilities with appropriatemore » weights. To validate this model and gain insights into the dynamics, additional quasi-classical trajectory calculations in both full and reduced dimensions have also been performed and important dynamical factors such as the steering effect are discussed.« less

Self-assembled monolayers of alendronate on Ti6Al4V alloy surfaces enhance osteogenesis in mesenchymal stem cells

PubMed Central

Rojo, Luis; Gharibi, Borzo; McLister, Robert; Meenan, Brian J.; Deb, Sanjukta

2016-01-01

Phosphonates have emerged as an alternative for functionalization of titanium surfaces by the formation of homogeneous self-assembled monolayers (SAMs) via Ti-O-P linkages. This study presents results from an investigation of the modification of Ti6Al4V alloy by chemisorption of osseoinductive alendronate using a simple, effective and clean methodology. The modified surfaces showed a tailored topography and surface chemistry as determined by SEM microscopy and RAMAN spectroscopy. X-ray photoelectron spectroscopy revealed that an effective mode of bonding is created between the metal oxide surface and the phosphate residue of alendronate, leading to formation of homogenous drug distribution along the surface. In-vitro studies showed that alendronate SAMs induce differentiation of hMSC to a bone cell phenotype and promote bone formation on modified surfaces. Here we show that this novel method for the preparation of functional coatings on titanium-based medical devices provides osseoinductive bioactive molecules to promote enhanced integration at the site of implantation. PMID:27468811

Isothermal-desorption-rate measurements in the vicinity of the Curie temperature for H2 chemisorbed on nickel films

NASA Technical Reports Server (NTRS)

Shanabarger, M. R.

1979-01-01

Measurements of the isothermal desorption rate of H2 chemisorbed onto polycrystalline nickel films made for temperatures spanning the Curie temperature of the nickel film are presented. Desorption kinetics were followed by measuring the decay of the change in resistance of the nickel film brought about by hydrogen chemisorption after gas-phase H2 had been rapidly evacuated. The desorption rate is found to undergo an anomalous decrease in the vicinity of the Curie temperature, accompanied by an increase in the desorption activation energy and the equilibrium constant for the chemisorbed hydrogen. The results are interpreted in terms of anomalous variations in rate constants for the formation of the precursor molecular adsorbed state and the chemisorbed atomic state due to the phase transition in the nickel. The changes in rate constants are also considered to be in qualitative agreement with theoretical predictions based on a spin coupling between the adatom and the magnetic substrate.

Adsorptive removal of direct azo dye from aqueous phase onto coal based sorbents: a kinetic and mechanistic study.

PubMed

Venkata Mohan, S; Chandrasekhar Rao, N; Karthikeyan, J

2002-03-01

This communication presents the results pertaining to the investigation conducted on color removal of trisazo direct dye, C.I. Direct Brown 1:1 by adsorption onto coal based sorbents viz. charfines, lignite coal, bituminous coal and comparing results with activated carbon (Filtrasorb-400). The kinetic sorption data indicated the sorption capacity of the different coal based sorbents. The sorption interaction of direct dye on to coal based sorbents obeys first-order irreversible rate equation and activated carbon fits with the first-order reversible rate equation. Intraparticle diffusion studies revealed the dye sorption interaction was complex and intraparticle diffusion was not only the rate limiting step. Isothermal data fit well with the rearranged Langmuir adsorption model. R(L) factor revealed the favorable nature of the isotherm of the dye-coal system. Neutral solution pH yielded maximum dye color removal. Desorption and interruption studies further indicated that the coal based sorbents facilitated chemisorption in the process of dye sorption while, activated carbon resulted in physisorption interaction.

Understanding and Controlling the Aggregative Growth of Platinum Nanoparticles in Atomic Layer Deposition: An Avenue to Size Selection

PubMed Central

2017-01-01

We present an atomistic understanding of the evolution of the size distribution with temperature and number of cycles in atomic layer deposition (ALD) of Pt nanoparticles (NPs). Atomistic modeling of our experiments teaches us that the NPs grow mostly via NP diffusion and coalescence rather than through single-atom processes such as precursor chemisorption, atom attachment, and Ostwald ripening. In particular, our analysis shows that the NP aggregation takes place during the oxygen half-reaction and that the NP mobility exhibits a size- and temperature-dependent scaling. Finally, we show that contrary to what has been widely reported, in general, one cannot simply control the NP size by the number of cycles alone. Instead, while the amount of Pt deposited can be precisely controlled over a wide range of temperatures, ALD-like precision over the NP size requires low deposition temperatures (e.g., T < 100 °C) when growth is dominated by atom attachment. PMID:28178779

SeO2 adsorption on CaO surface: DFT and experimental study on the adsorption of multiple SeO2 molecules

NASA Astrophysics Data System (ADS)

Fan, Yaming; Zhuo, Yuqun; Li, Liangliang

2017-10-01

SeO2 adsorption mechanisms on CaO surface were firstly investigated by both density functional theory (DFT) calculations and adsorption experiments. Adsorption of multiple SeO2 on the CaO (001) surface was investigated using slab model. Based on the results of adsorption energy and surface property, a double-layer adsorption mechanisms were proposed. In experiments, the SeO2 adsorption products were prepared in a U-shaped quartz reactor at 200 °C. The surface morphology was investigated by field emission scanning electron microscopy (FE-SEM). The superficial and total SeO2 mass fractions were measured by X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES), respectively. The surface valence state and bulk structure are determined by XPS and X-Ray Diffraction (XRD). The experimental results are in good agreement with the DFT results. In conclusion, the fundamental SeO2 chemisorption mechanisms on CaO surface were suggested.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design

DOE PAGES

Tao, Xinyong; Wang, Jianguo; Liu, Chong; ...

2016-04-05

Lithium–sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance.more » Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Lastly, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.« less

Enhancement of Cr(VI) Ion Removal Using Nanochitosan Coated on Bituminous Activated Carbon.

PubMed

Chooaksorn, Wanida; Nitisoravut, Rachnarin; Polprasert, Chongrak; Babel, Sandhya; Laohhasurayotin, Kritapas; Kangwansupamonkon, Wiyong

2016-11-01

  Bituminous activated carbon (AC) has been widely used as a sorbent for adsorption of non-polar species, but its performance for removal of ionic species such as heavy metals has not been as efficient. In this study, AC was modified with chitosan nanoparticles (CN) using facile methods of dip coating and wet impregnation. The CN-coated AC demonstrated an increase in Cr(VI) removal efficiency in both kinetics and adsorption capacity. The adsorption capacity of the CN-coated AC (mg/g) was more than twice that of the uncoated AC (36.36 mg/g), or pure chitosan (32.57 mg/g). The sizes of the synthesized CN (160-2,000 nm) can be controlled by varying the concentration of the chitosan/reagents used. The adsorption isotherms are better described using the Freundlich rather than the Langmuir model and are in agreement with the heterogeneity of the surfaces. Adsorption kinetics followed that of the pseudo-second-order kinetics, suggesting chemisorption as a rate limiting step.

Properties at the interface of graphene and Ti2C MXene

NASA Astrophysics Data System (ADS)

Paul, Pallavi; Chakraborty, Poulami; Das, Tilak; Nafday, Dhani; Saha-Dasgupta, Tanusri

2017-07-01

Employing ab initio calculations, we characterize the interfaces formed between graphene, a much discussed two-dimensional material, and MXene, another two-dimensional material of recent interest. Our study considering the specific case of Ti2C , a member of the MXene family, shows the formation of chemical bonds between Ti atoms and C atoms of graphene. This results in reconstruction of the electronic structure at the interface, making the interface metallic, though graphene is a zero-gap semiconductor and Ti2C is an antiferromagnetic insulator in their respective native form. The optical and phonon properties of the interfaces are found to be strongly dependent on the stacking arrangement, driven by the nature of chemical-bond formation. Consideration of O-passivated Ti2C is found to weaken the interaction between graphene and Ti2C substantially, making it a physisorption process rather than chemisorption in the unpassivated situation. Our first-principles study is expected to motivate future experimental investigation.

A Multistage Fluidized Bed for the Deep Removal of Sour Gases: Proof of Concept and Tray Efficiencies

PubMed Central

2018-01-01

Currently there are significant amounts of natural gas that cannot be produced and treated to meet pipeline specifications, because that would not be economically viable. This work investigates a bench scale multistage fluidized bed (MSFB) with shallow beds for sour gas removal from natural gas using a commercially available supported amine sorbent. A MSFB is regarded as a promising adsorber type for deep sour gas removal to parts per million concentrations. A series of experiments was conducted using carbon dioxide as sour gas and nitrogen to mimic natural gas. Removal below 3 mol ppm was successfully demonstrated. This indicates that gas bypassing is minor (that is, good gas–solid contacting) and that apparent adsorption kinetics are fast for the amine sorbent applied. Tray efficiencies for a chemisorption/adsorption system were reported for one of the first times. Current experiments performed at atmospheric pressure strongly indicate that deep removal is possible at higher pressures in a multistage fluidized bed. PMID:29606794

Tunable 3D Nanoresonators for Gas-Sensing Applications

DOE PAGES

Arnold, Georg; Winkler, Robert; Stermitz, Martin; ...

2018-03-15

Here, the detection of gas species with high sensitivity is a significant task for fundamental sciences as well as for industrial applications. Similarly, the ongoing trend for device miniaturization brings new challenges for advanced fabrication including on–demand functionality tuning. Following this motivation, here the additive, direct–write fabrication of freestanding 3D nanoarchitectures is introduced, which can be brought into mechanical resonance via electric AC fields. Specifically, this study focuses on the 3D nanostructure synthesis, the subsequent determination of Young's modulus, and demonstrates a postgrowth procedure, which can precisely tune the material modulus. As–fabricated resonators reveal a Young's modulus of 9–13 GPa,more » which can be increased by a factor greater than 5. Next, the electric readout of the resonance behavior is demonstrated via electric current measurement as an essential element for the resonance sensor applications. Finally, the implications of gas–physisorption and gas–chemisorption on the resonance frequencies are studied, representing a proof–of–principle for sensing applications by the here presented approach.« less

Tunable 3D Nanoresonators for Gas-Sensing Applications

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

Arnold, Georg; Winkler, Robert; Stermitz, Martin

Here, the detection of gas species with high sensitivity is a significant task for fundamental sciences as well as for industrial applications. Similarly, the ongoing trend for device miniaturization brings new challenges for advanced fabrication including on–demand functionality tuning. Following this motivation, here the additive, direct–write fabrication of freestanding 3D nanoarchitectures is introduced, which can be brought into mechanical resonance via electric AC fields. Specifically, this study focuses on the 3D nanostructure synthesis, the subsequent determination of Young's modulus, and demonstrates a postgrowth procedure, which can precisely tune the material modulus. As–fabricated resonators reveal a Young's modulus of 9–13 GPa,more » which can be increased by a factor greater than 5. Next, the electric readout of the resonance behavior is demonstrated via electric current measurement as an essential element for the resonance sensor applications. Finally, the implications of gas–physisorption and gas–chemisorption on the resonance frequencies are studied, representing a proof–of–principle for sensing applications by the here presented approach.« less

X-ray photoemission analysis of clean and carbon monoxide-chemisorbed platinum(111) stepped surfaces using a curved crystal

DOE PAGES

Walter, Andrew L.; Schiller, Frederik; Corso, Martina; ...

2015-11-12

Surface chemistry and catalysis studies could significantly gain from the systematic variation of surface active sites, tested under the very same conditions. Curved crystals are excellent platforms to perform such systematics, which may in turn allow to better resolve fundamental properties and reveal new phenomena. This is demonstrated here for the carbon monoxide/platinum system. We curve a platinum crystal around the high-symmetry (111) direction and carry out photoemission scans on top. This renders the spatial core-level imaging of carbon monoxide adsorbed on a 'tunable' vicinal surface, allowing a straightforward visualization of the rich chemisorption phenomenology at steps and terraces. Throughmore » such photoemission images we probe a characteristic elastic strain variation at stepped surfaces, and unveil subtle stress-release effects on clean and covered vicinal surfaces. Lastly, these results offer the prospect of applying the curved surface approach to rationally investigate the chemical activity of surfaces under real pressure conditions.« less

Surface interaction of H2S, SO2, and SO3 on fullerene-like gallium nitride (GaN) nanostructure semiconductor

NASA Astrophysics Data System (ADS)

Salimifard, M.; Rad, A. Shokuhi; Mahanpoor, K.

2017-10-01

Density functional theory (DFT) using MPW1PW91 and B3LYP hybrid functionals was utilized for quantum-based investigations of three major sulfur compounds (H2S, SO2, and SO3) adsorption onto fullerene-like Ga12N12 nanocluster. All chemicals showed high chemisorption with the order of SO3>SO2>>H2S. Results of charge analysis showed that during adsorption, transfer of charge is from H2S to nanocluster while reverse direction of charge transfer is found for SO2 and SO3 molecules. Partial dissociation is found for adsorbates especially for SO2 and SO3 molecules. Results of thermochemistry analysis show negative values for enthalpy and Gibbs free energy of adsorption, confirming exothermic spontaneous process. Analysis of frontier molecular orbital (FMO) showed important role of orbital hybridizing towards formation of new bonds upon adsorption. As a result, we introduce Ga12N12 nanocluster as a strong adsorbent for sulfur compounds.

Sulfur mustard gas adsorption on ZnO fullerene-like nanocage: Quantum chemical calculations

NASA Astrophysics Data System (ADS)

Kazemi, Mohammad; Rad, Ali Shokuhi

2017-06-01

In the present study, we used density functional theory calculations (at B3LYP and ωB97XD Levels) to search on the adsorption of Sulfur mustard gas (defined as mustard gas) on the surface of fullerene-like ZnO nanocage as a semiconductor. We found three different configurations of adsorbed gas on the surface of this nanostructure semiconductor. The values of adsorption energy of mustard gas are calculated in the range of -144∼ -200 kJ/mol with enthalpies in the range of -132∼-195 kJ/mol and Gibbs free energies in the range of -88∼-144 kJ/mol (T = 298 K, based on ωB97XD level), which indicate exothermic and spontaneous chemisorption. For all geometries, we calculated geometry parameters by taking into account the charge analysis and frontier molecular orbital study. The result of this study can be a support for next studies to develop new nanomaterials as adsorbent/sensor for mustard gas.

Chemisorption of Hydroxide on 2D Materials from DFT Calculations: Graphene versus Hexagonal Boron Nitride.

PubMed

Grosjean, Benoit; Pean, Clarisse; Siria, Alessandro; Bocquet, Lydéric; Vuilleumier, Rodolphe; Bocquet, Marie-Laure

2016-11-17

Recent nanofluidic experiments revealed strongly different surface charge measurements for boron-nitride (BN) and graphitic nanotubes when in contact with saline and alkaline water (Nature 2013, 494, 455-458; Phys. Rev. Lett. 2016, 116, 154501). These observations contrast with the similar reactivity of a graphene layer and its BN counterpart, using density functional theory (DFT) framework, for intact and dissociative adsorption of gaseous water molecules. Here we investigate, by DFT in implicit water, single and multiple adsorption of anionic hydroxide on single layers. A differential adsorption strength is found in vacuum for the first ionic adsorption on the two materials-chemisorbed on BN while physisorbed on graphene. The effect of implicit solvation reduces all adsorption values, resulting in a favorable (nonfavorable) adsorption on BN (graphene). We also calculate a pK a ≃ 6 for BN in water, in good agreement with experiments. Comparatively, the unfavorable results for graphene in water echo the weaker surface charge measurements but point to an alternative scenario.

Chemisorption of Hydroxide on 2D Materials From DFT Calculations: Graphene Versus Hexagonal Boron Nitride

PubMed Central

Grosjean, Benoit; Pean, Clarisse; Siria, Alessandro; Bocquet, Lyderic; Vuilleumier, Rodolphe; Bocquet, Marie-Laure

2017-01-01

Recent nanofluidic measurements revealed strongly different surface charge measurements for boron-nitride and graphitic nanotubes when in contact with saline and alkaline water. 1,2 These observations contrast with the similar reactivity of a graphene layer and its boron nitride counterpart, using Density Functional Theory (DFT) framework, for intact and dissociative adsorption of gaseous water molecules. Here, we investigate, by DFT in implicit water, single and multiple adsorption of anionic hydroxide on single layers. A differential adsorption strength is found in vacuum for the first ionic adsorption on the two materials – chemisorbed on BN while physisorbed on graphene. The effect of implicit solvation reduces all adsorption values resulting in a favorable (non-favorable) adsorption on BN (graphene). We also calculate a pKa ≃ 6 for BN in water, in good agreement with experiments. Comparatively, the unfavorable results for graphene in water echoes the weaker surface charge measurements, but points to an alternative scenario. PMID:27809540

X-ray photoemission analysis of clean and carbon monoxide-chemisorbed platinum(111) stepped surfaces using a curved crystal

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

Walter, Andrew L.; Schiller, Frederik; Corso, Martina

Surface chemistry and catalysis studies could significantly gain from the systematic variation of surface active sites, tested under the very same conditions. Curved crystals are excellent platforms to perform such systematics, which may in turn allow to better resolve fundamental properties and reveal new phenomena. This is demonstrated here for the carbon monoxide/platinum system. We curve a platinum crystal around the high-symmetry (111) direction and carry out photoemission scans on top. This renders the spatial core-level imaging of carbon monoxide adsorbed on a 'tunable' vicinal surface, allowing a straightforward visualization of the rich chemisorption phenomenology at steps and terraces. Throughmore » such photoemission images we probe a characteristic elastic strain variation at stepped surfaces, and unveil subtle stress-release effects on clean and covered vicinal surfaces. Lastly, these results offer the prospect of applying the curved surface approach to rationally investigate the chemical activity of surfaces under real pressure conditions.« less

Electronic Structure Calculations of Ammonia Adsorption on Graphene and Graphene Oxide with Epoxide and Hydroxyl Groups

NASA Astrophysics Data System (ADS)

Nancy Anna Anasthasiya, A.; Khaneja, Mamta; Jeyaprakash, B. G.

2017-10-01

Ammonia adsorption on graphene (G) and graphene oxide (GO) was investigated through density functional theory calculations. In the GO system, the obtained binding energy, band gap, charge transfer and electronic structure revealed that the epoxide (GO-O) and hydroxyl groups (GO-OH) in GO enhance the NH3 adsorption, which leads to the chemisorption of NH3 on GO. The dissociation of NH3 to NH2 and formation of OH was also observed when the O and H atoms were separated at 0.985 Å, 1.019 Å, 1.035 Å, and 1.044 Å for various GO systems. The maximum charge transfer value was found to be 0.054 |e| with the binding energy of 1.143 eV for GO with a single epoxide (GO-1O) group. The charge transfer from NH3 to G or GO and the bond formation in this study agree with the reported experimental results.

Role of humidity in reducing the friction of graphene layers on textured surfaces

NASA Astrophysics Data System (ADS)

Li, Zheng-yang; Yang, Wen-jing; Wu, Yan-ping; Wu, Song-bo; Cai, Zhen-bing

2017-05-01

A multiple-layer graphene was prepared on steel surface to reduce friction and wear. A graphene-containing ethanol solution was dripped on the steel surface, and several layers of graphene flakes were deposited on the surface after ethanol evaporated. Tribological performance of graphene-contained surface (GCS) was induced by reciprocating ball against plate contact in different RH (0% (dry nitrogen), 30%, 60%, and 90%). Morphology and wear scar were analyzed by OM, 2D profile, SEM, Raman spectroscopy, and XPS. Results show that GCS can substantially reduce the wear and coefficient of friction (COF) in 60% relative humidity (RH). Low COF occurs due to graphene layer providing a small shear stress on the friction interface. Meanwhile, conditions of high RH and textured surface could make the low COF persist for a longer time. High moisture content can stabilize and protect the graphene C-network from damage due to water dissociative chemisorption with carbon dangling bonds, and the textured surface was attributed to release graphene layer stored in the dimple.

Diatomite Modified Immobilized Delftia sp. for the Bio-Abiotic Removal of Antibiotics Amoxicillin in the Aqueous System

NASA Astrophysics Data System (ADS)

Gao, Lijuan; Sun, Jing; Guan, Kai; Shen, Tingting; Wang, Xikui

2017-05-01

Diatomite modified sodium alginate (Si/SA) immobilized Delftia sp. A2(2011) (STT01) was applied to degrade amoxicillin. The immobilized pellets provided a direct and visual probe for the degradation process due to their intrinsic bright colour. The results demonstrated that 100% of amoxicillin and 68.5% of CODcr removal were achieved after 72 h, comparing with the cases of sodium alginate (SA) system (81.2%, 46.9%) and the free cells system (60.5%, 35.5%). The degradation kinetics was in good agreement with Michaelis-Menten equation. The maximum rate (Vm ) and Michaelis constant (Km ) were calculated as 9.09 mg L-1 h-1 and 228 mg L-1, respectively. The results further revealed that diatomite not only acted as immobilization support to improve the mechanical strength and lifetime of the pellets but also as absorbent to promote the treatment efficiency. Therefore, both enzymatic catalysis and chemisorption were responsible for the removal of amoxicillin.

Enhancement of elemental mercury adsorption by silver supported material.

PubMed

Khunphonoi, Rattabal; Khamdahsag, Pummarin; Chiarakorn, Siriluk; Grisdanurak, Nurak; Paerungruang, Adjana; Predapitakkun, Somrudee

2015-06-01

Mercury, generally found in natural gas, is extremely hazardous. Although average mercury levels are relatively low, they are further reduced to comply with future mercury regulations, which are stringent in order to avoid releasing to the environment. Herein, vapor mercury adsorption was therefore investigated using two kinds of supports, granular activated carbon (GAC) and titanium dioxide (TiO2). Both supports were impregnated by silver (5 and 15 wt.%), before testing against a commercial adsorbent (sulfur-impregnated activated carbon, SAC). The adsorption isotherm, kinetics, and its thermodynamics of mercury adsorption were reported. The results revealed that Langmuir isotherm provided a better fit to the experimental data. Pseudo second-order was applicable to describe adsorption kinetics. The higher uniform Ag dispersion was a key factor for the higher mercury uptake. TiO2 supported silver adsorbent showed higher mercury adsorption than the commercial one by approximately 2 times. Chemisorption of mercury onto silver active sites was confirmed by an amalgam formation found in the spent adsorbents. Copyright © 2015. Published by Elsevier B.V.

Covalent functionalization of octagraphene with magnetic octahedral B6- and non-planar C6- clusters

NASA Astrophysics Data System (ADS)

Chigo-Anota, E.; Cárdenas-Jirón, G.; Salazar Villanueva, M.; Bautista Hernández, A.; Castro, M.

2017-10-01

The interaction between the magnetic boron octahedral (B6-) and non-planar (C6-) carbon clusters with semimetal nano-sheet of octa-graphene (C64H24) in the gas phase is studied by means of DFT calculations. These results reveal that non-planar-1 (anion) carbon cluster exhibits structural stability, low chemical reactivity, magnetic (1.0 magneton bohr) and semiconductor behavior. On the other hand, there is chemisorption phenomena when the stable B6- and C6- clusters are absorbed on octa-graphene nanosheets. Such absorption generates high polarity and the low-reactivity remains as on the individual pristine cases. Electronic charge transference occurs from the clusters toward the nanosheets, producing a reduction of the work function for the complexes and also induces a magnetic behavior on the functionalized sheets. The quantum descriptors obtained for these systems reveal that they are feasible candidates for the design of molecular circuits, magnetic devices, and nano-vehicles for drug delivery.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design

NASA Astrophysics Data System (ADS)

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-04-01

Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design.

PubMed

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-04-05

Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.

Simultaneous capture of metal, sulfur and chlorine by sorbents during fluidized bed incineration.

PubMed

Ho, T C; Chuang, T C; Chelluri, S; Lee, Y; Hopper, J R

2001-01-01

Metal capture experiments were carried out in an atmospheric fluidized bed incinerator to investigate the effect of sulfur and chlorine on metal capture efficiency and the potential for simultaneous capture of metal, sulfur and chlorine by sorbents. In addition to experimental investigation, the effect of sulfur and chlorine on the metal capture process was also theoretically investigated through performing equilibrium calculations based on the minimization of system free energy. The observed results have indicated that, in general, the existence of sulfur and chlorine enhances the efficiency of metal capture especially at low to medium combustion temperatures. The capture mechanisms appear to include particulate scrubbing and chemisorption depending on the type of sorbents. Among the three sorbents tested, calcined limestone is capable of capturing all the three air pollutants simultaneously. The results also indicate that a mixture of the three sorbents, in general, captures more metals than a single sorbent during the process. In addition, the existence of sulfur and chlorine apparently enhances the metal capture process.

Separation of acid blue 25 from aqueous solution using water lettuce and agro-wastes by batch adsorption studies

NASA Astrophysics Data System (ADS)

Kooh, Muhammad Raziq Rahimi; Dahri, Muhammad Khairud; Lim, Linda B. L.; Lim, Lee Hoon; Chan, Chin Mei

2018-05-01

Three plant-based materials, namely water lettuce (WL), tarap peel (TP) and cempedak peel (CP), were used to investigate their potentials as adsorbents using acid blue 25 (AB25) dye as a model for acidic dye. The adsorbents were characterised using Fourier transform infrared spectroscopy, X-ray fluorescence and scanning electron microscope. Batch experiments involving parameters such as pH, temperature, contact time, and initial dye concentration were done to investigate the optimal conditions for the adsorption of AB25 onto the adsorbents. Thermodynamics study showed that the uptake of AB25 by the three adsorbents was feasible and endothermic in nature. Both the Langmuir and Freundlich isotherm models can be used to describe the adsorption process of AB25 onto WL and CP while pseudo-second-order fitted the kinetics data, suggesting that chemisorptions were majorly involved. The use of 0.1 M of NaOH showed the best results in regenerating of the WL, TP and CP's adsorption ability after AB25 treatment.

Development of Metal-impregnated Single Walled Carbon Nanotubes for Toxic Gas Contaminant Control in Advanced Life Support Systems

NASA Technical Reports Server (NTRS)

Pisharody, Suresh A.; Fisher, John W.; Wignarajah, K.

2002-01-01

The success of physico-chemical waste processing and resource recovery technologies for life support application depends partly on the ability of gas clean-up systems to efficiently remove trace contaminants generated during the process with minimal use of expendables. Carbon nanotubes promise superior performance over conventional approaches to gas clean-up due to their ability to direct the selective uptake of gaseous species based on their controlled pore size, high surface area, ordered chemical structure that allows functionalization and their effectiveness also as catalyst support materials for toxic gas conversion. We present results and findings from a preliminary study on the effectiveness of metal impregnated single walled nanotubes as catalyst/catalyst support materials for toxic gas contaminate control. The study included the purification of single walled nanotubes, the catalyst impregnation of the purified nanotubes, the experimental characterization of the surface properties of purified single walled nanotubes and the characterization of physisorption and chemisorption of uptake molecules.

The effects of cations and anions on hydrogen chemisorption at Pt

NASA Technical Reports Server (NTRS)

Huang, J. C.; Ogrady, W. E.; Yeager, E.

1977-01-01

Experimental evidence based on linear sweep voltammetry is presented to substantiate the view that ionic adsorption substantially shifts electrode potentials in addition to the relative heights of the hydrogen adsorption peaks. HClO4 and HF are chosen as better reference electrolytes for anion studies. The voltammetry curves for 0.1M HF and 0.1M HClO4 as well as the effect of adding successively increasing amounts of H2SO4 to these electrolytes are discussed. The measurements are also extended to alkaline solutions. Mechanisms whereby the addition of various cations and anions to electrolytes such as HF and HClO4 can induce changes in the structure of the hydrogen adsorption region in the voltammetry curves are identified: (1) blocking of sites by anion adsorption and coupling of hydrogen adsorption and anion desorption, (2) modification in the hydrogen adsorption energies for sites adjacent to adsorbed anions, (3) changes in the potential distribution across the interface, and (4) surface restructuring.

Assembly of porous hierarchical copolymers/resin proppants: New approaches to smart proppant immobilization via molecular anchors.

PubMed

Alexander, Shirin; Dunnill, Charles W; Barron, Andrew R

2016-03-15

The assembly of temperature/pH sensitive complex microparticle structures through chemisorption and physisorption provides a responsive system that offers application as routes to immobilization of proppants in-situ. Thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) along with energy dispersive X-ray analysis (EDX) have been used to characterize a series of bi-functionalized monolayers and/or multilayers grown on alumina microparticles and investigate the reactive nature of both temperature sensitive cross-linker (epoxy resin) with the layers and pH-responsive bridging layer (polyetheramine). The bifunctional acids, behaving as molecular anchors, allow for a controlled reaction with a cross-linker (resin or polymer) with the formation of networks, which is either irreversible or reversible based on the nature of the cross-linker. The networks results in formation of porous hierarchical particles that offer a potential route to the creation of immobile proppant pack. Copyright © 2015 Elsevier Inc. All rights reserved.

Construction and direct electrochemistry of orientation controlled laccase electrode.

PubMed

Li, Ying; Zhang, Jiwei; Huang, Xirong; Wang, Tianhong

2014-03-28

A laccase has multiple redox centres. Chemisorption of laccases on a gold electrode through a polypeptide tag introduced at the protein surface provides an isotropic orientation of laccases on the Au surface, which allows the orientation dependent study of the direct electrochemistry of laccase. In this paper, using genetic engineering technology, two forms of recombinant laccase which has Cys-6×His tag at the N or C terminus were generated. Via the Au-S linkage, the recombinant laccase was assembled orientationally on gold electrode. A direct electron transfer and a bioelectrocatalytic activity toward oxygen reduction were observed on the two orientation controlled laccase electrodes, but their electrochemical behaviors were found to be quite different. The orientation of laccase on the gold electrode affects both the electron transfer pathway and the electron transfer efficiency of O2 reduction. The present study is helpful not only to the in-depth understanding of the direct electrochemistry of laccase, but also to the development of laccase-based biofuel cells. Copyright © 2014 Elsevier Inc. All rights reserved.

Adsorption of selected volatile organic vapors on multiwall carbon nanotubes.

PubMed

Shih, Yang-hsin; Li, Mei-syue

2008-06-15

Carbon nanotubes are expected to play an important role in sensing, pollution treatment and separation techniques. This study examines the adsorption behaviors of volatile organic compounds (VOCs), n-hexane, benzene, trichloroethylene and acetone on two multiwall carbon nanotubes (MWCNTs), CNT1 and CNT2. Among these VOCs, acetone exhibits the highest adsorption capacity. The highest adsorption enthalpies and desorption energies of acetone were also observed. The strong chemical interactions between acetone and both MWCNTs may be the result from chemisorption on the topological defects. The adsorption heats of trichloroethylene, benzene, and n-hexane are indicative of physisorption on the surfaces of both MWCNTs. CNT2 presents a higher adsorption capacity than CNT1 due to the existence of an exterior amorphous carbon layer on CNT2. The amorphous carbon enhances the adsorption capacity of organic chemicals on carbon nanotubes. The morphological and structure order of carbon nanotubes are the primary affects on the adsorption process of organic chemicals.

Grain-boundary unzipping by oxidation in polycrystalline graphene

NASA Astrophysics Data System (ADS)

Alexandre, Simone; Lucio, Aline; Nunes, Ricardo

2011-03-01

The need for large-scale production of graphene will inevitably lead to synthesis of the polycrystalline material [1,2]. Understanding the chemical, mechanical, and electronic properties of grain boundaries in graphene polycrystals will be crucial for the development of graphene-based electronics. Oxidation of this material has been suggested to lead to graphene ribbons, by the oxygen-driven unzipping mechanism. A cooperative-strain mechanism, based on the formation of epoxy groups along lines of parallel bonds in the hexagons of graphene's honeycomb lattice, was proposed to explain the unzipping effect in bulk graphene In this work we employ ab initio calculations to study the oxidation of polycrystalline graphene by chemisorption of oxygen at the grain boundaries. Our results indicate that oxygen tends to segregate at the boundaries, and that the unzipping mechanism is also operative along the grain boundaries, despite the lack of the parallel bonds due to the presence of fivefold and sevenfold carbon rings along the boundary core. We acknowledge support from the Brazilian agencies: CNPq, Fapemig, and INCT-Materiais de Carbono.

Sorption of diclofenac and naproxen onto MWCNT in model wastewater treated by H2O2 and/or UV.

PubMed

Czech, Bożena; Oleszczuk, Patryk

2016-04-01

The application of oxidation processes such as UV and/or H2O2 will change the physicochemical properties of carbon nanotubes (CNT). It may affect the sorption affinity of CNT to different contaminants and then affect their fate in the environment. In the present study the adsorption of two very common used pharmaceuticals (diclofenac and naproxen) onto CNT treated by UV, H2O2 or UV/H2O2 was investigated. Four different adsorption models (Freundlich, Langmuir, Temkin, Dubinin-Radushkevich) were tested. The best fitting of experimental data was observed for Freundlich or Langmuir model. The significant relationships between Q calculated from Langmuir model with O% and dispersity were observed. Kinetics of diclofenac and naproxen followed mainly pseudo-second order indicating for chemisorption limiting step of adsorption. The data showed that the mechanism of sorption was physical or chemical depending on the type of CNT modification. Copyright © 2015 Elsevier Ltd. All rights reserved.

Surface passivation of semiconducting oxides by self-assembled nanoparticles

PubMed Central

Park, Dae-Sung; Wang, Haiyuan; Vasheghani Farahani, Sepehr K.; Walker, Marc; Bhatnagar, Akash; Seghier, Djelloul; Choi, Chel-Jong; Kang, Jie-Hun; McConville, Chris F.

2016-01-01

Physiochemical interactions which occur at the surfaces of oxide materials can significantly impair their performance in many device applications. As a result, surface passivation of oxide materials has been attempted via several deposition methods and with a number of different inert materials. Here, we demonstrate a novel approach to passivate the surface of a versatile semiconducting oxide, zinc oxide (ZnO), evoking a self-assembly methodology. This is achieved via thermodynamic phase transformation, to passivate the surface of ZnO thin films with BeO nanoparticles. Our unique approach involves the use of BexZn1-xO (BZO) alloy as a starting material that ultimately yields the required coverage of secondary phase BeO nanoparticles, and prevents thermally-induced lattice dissociation and defect-mediated chemisorption, which are undesirable features observed at the surface of undoped ZnO. This approach to surface passivation will allow the use of semiconducting oxides in a variety of different electronic applications, while maintaining the inherent properties of the materials. PMID:26757827

Interaction of benzene thiol and thiolate with small gold clusters.

PubMed

Letardi, Sara; Cleri, Fabrizio

2004-06-01

We studied the interaction between benzene thiol and thiolate molecules, and gold clusters made of 1 to 3 atoms, by means of ab initio density functional theory in the local density approximation. We find that the thiolate is energetically more stable than the thiol, however the process of detachment of H from the thiol appears to be possibly mediated by the intermediate step of H chemisorption on Au. Cleavage of the S-H bond is accompanied by a 90 degrees rotation of the molecule around the S-Au bond, showing a strong steric specificity. Such a rotation is induced by the relative energy shift of the S atom p orbitals with respect to the benzene pi ring and the Au d orbitals. By analyzing the correlation of the bond energy, bond lengths, and HOMO-LUMO gap with the number of S-Au bonds, we find that the thiolate S atom appears to prefer a low-coordination condition on Au clusters. (c) 2004 American Institute of Physics.

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

NASA Astrophysics Data System (ADS)

Thoa Dao, Thi Kim; Loc Luu, Cam

2015-09-01

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

A Multistage Fluidized Bed for the Deep Removal of Sour Gases: Proof of Concept and Tray Efficiencies.

PubMed

Driessen, Rick T; Bos, Martin J; Brilman, Derk W F

2018-03-21

Currently there are significant amounts of natural gas that cannot be produced and treated to meet pipeline specifications, because that would not be economically viable. This work investigates a bench scale multistage fluidized bed (MSFB) with shallow beds for sour gas removal from natural gas using a commercially available supported amine sorbent. A MSFB is regarded as a promising adsorber type for deep sour gas removal to parts per million concentrations. A series of experiments was conducted using carbon dioxide as sour gas and nitrogen to mimic natural gas. Removal below 3 mol ppm was successfully demonstrated. This indicates that gas bypassing is minor (that is, good gas-solid contacting) and that apparent adsorption kinetics are fast for the amine sorbent applied. Tray efficiencies for a chemisorption/adsorption system were reported for one of the first times. Current experiments performed at atmospheric pressure strongly indicate that deep removal is possible at higher pressures in a multistage fluidized bed.

Surface modification of a low cost bentonite for post-combustion CO2 capture

NASA Astrophysics Data System (ADS)

Chen, Chao; Park, Dong-Wha; Ahn, Wha-Seung

2013-10-01

A low cost bentonite was modified with PEI (polyethylenimine) through a physical impregnation method. Bentonite in its natural state and after amine modification were characterized by scanning electron microscopy-energy dispersive X-ray spectroscopy, X-ray diffraction, N2 adsorption-desorption isotherms, and investigated for CO2 capture using a thermogravimetric analysis unit connected to a flow panel. The effect of adsorption temperature, PEI loading and CO2 partial pressure on the CO2 capture performance of the PEI-modified bentonite was examined. A cyclic CO2 adsorption-desorption test was also carried out to assess the stability of PEI-modified bentonite as a CO2 adsorbent. Bentonite in its natural state showed negligible CO2 uptake. After amine modification, the CO2 uptake increased significantly due to CO2 capture by amine species introduced via chemisorption. The PEI-modified bentonites showed high CO2 capture selectivity over N2, and exhibited excellent stability in cyclic CO2 adsorption-desorption runs.

Adsorption and mobility of metals in build-up on road surfaces.

PubMed

Gunawardana, Chandima; Egodawatta, Prasanna; Goonetilleke, Ashantha

2015-01-01

The study investigated the adsorption and bioavailability characteristics of traffic generated metals common to urban land uses, in road deposited solids particles. To validate the outcomes derived from the analysis of field samples, adsorption and desorption experiments were undertaken. The analysis of field samples revealed that metals are selectively adsorbed to different charge sites on solids. Zinc, copper, lead and nickel are adsorbed preferentially to oxides of manganese, iron and aluminium. Lead is adsorbed to organic matter through chemisorption. Cadmium and chromium form weak bonding through cation exchange with most of the particle sizes. Adsorption and desorption experiments revealed that at high metal concentrations, chromium, copper and lead form relatively strong bonds with solids particles while zinc is adsorbed through cation exchange with high likelihood of being released back into solution. Outcomes from this study provide specific guidance for the removal of metals from stormwater based on solids removal. Copyright © 2014 Elsevier Ltd. All rights reserved.

High translational energy release in H2 (D2) associative desorption from H (D) chemisorbed on C(0001).

PubMed

Baouche, S; Gamborg, G; Petrunin, V V; Luntz, A C; Baurichter, A; Hornekaer, L

2006-08-28

Highly energetic translational energy distributions are reported for hydrogen and deuterium molecules desorbing associatively from the atomic chemisorption states on highly oriented pyrolytic graphite (HOPG). Laser assisted associative desorption is used to measure the time of flight of molecules desorbing from a hydrogen (deuterium) saturated HOPG surface produced by atomic exposure from a thermal atom source at around 2100 K. The translational energy distributions normal to the surface are very broad, from approximately 0.5 to approximately 3 eV, with a peak at approximately 1.3 eV. The highest translational energy measured is close to the theoretically predicted barrier height. The angular distribution of the desorbing molecules is sharply peaked along the surface normal and is consistent with thermal broadening contributing to energy release parallel to the surface. All results are in qualitative agreement with recent density functional theory calculations suggesting a lowest energy para-type dimer recombination path.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design

PubMed Central

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-01-01

Lithium–sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides. PMID:27046216

Effects of an iron-silicon material, a synthetic zeolite and an alkaline clay on vegetable uptake of As and Cd from a polluted agricultural soil and proposed remediation mechanisms.

PubMed

Yao, Aijun; Wang, Yani; Ling, Xiaodan; Chen, Zhe; Tang, Yetao; Qiu, Hao; Ying, Rongrong; Qiu, Rongliang

2017-04-01

Economic and highly effective methods of in situ remediation of Cd and As polluted farmland in mining areas are urgently needed. Pot experiments with Brassica chinensis L. were carried out to determine the effects of three soil amendments [a novel iron-silicon material (ISM), a synthetic zeolite (SZ) and an alkaline clay (AC)] on vegetable uptake of As and Cd. SEM-EDS and XRD analyses were used to investigate the remediation mechanisms involved. Amendment with ISM significantly reduced the concentrations of As and Cd in edible parts of B. chinensis (by 84-94 % and 38-87 %, respectively), to levels that met food safety regulations and was much lower than those achieved by SZ and AC. ISM also significantly increased fresh biomass by 169-1412 % and 436-731 % in two consecutive growing seasons, while SZ and AC did not significantly affect vegetable growth. Correlation analysis suggested that it was the mitigating effects of ISM on soil acidity and on As and Cd toxicity, rather than nutrient amelioration, that contributed to the improvement in plant growth. SEM-EDS analysis showed that ISM contained far more Ca, Fe and Mn than did SZ or AC, and XRD analysis showed that in the ISM these elements were primarily in the form of silicates, oxides and phosphates that had high capacities for chemisorption of metal(loid)s. After incubation with solutions containing 800 mg L -1 AsO 4 2- or Cd 2+ , ISM bound distinctly higher levels of As (6.18 % in relative mass percent by EDS analysis) and Cd (7.21 % in relative mass percent by EDS analysis) compared to SZ and AC. XRD analysis also showed that ISM facilitated the precipitation of Cd 2+ as silicates, phosphates and hydroxides, and that arsenate combined with Fe, Al, Ca and Mg to form insoluble arsenate compounds. These precipitation mechanisms were much more active in ISM than in SZ or AC. Due to the greater pH elevation caused by the abundant calcium silicate, chemisorption and precipitation mechanisms in ISM treatments could be further enhanced. That heavy metal(loid)s fixation mechanisms of ISM ensure the remediation more irreversible and more resilient to environmental changes. With appropriate application rate and proper nutrients supplement, the readily available and economic ISM is a very promising amendment for safe crop production on multi-metal(loids) polluted soils.

Measuring binding kinetics of aromatic thiolated molecules with nanoparticles via surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Devetter, Brent M.; Mukherjee, Prabuddha; Murphy, Catherine J.; Bhargava, Rohit

2015-05-01

Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this study, we report the development of surface-enhanced Raman spectroscopy (SERS) as a method to monitor the kinetics of gold-thiolate bond formation on colloidal gold nanoparticles. A theoretical model combining SERS enhancement with the Beer-Lambert law is proposed to explain ensemble scattering and absorption effects in colloids during chemisorption. In order to maximize biological relevance and signal reproducibility, experiments used to validate the model focused on maintaining nanoparticle stability after the addition of water-soluble aromatic thiolated molecules. Our results indicate that ligand exchange on gold nanoparticles follow a first-order Langmuir adsorption model with rate constants on the order of 0.01 min-1. This study demonstrates an experimental spectroscopic method and theoretical model for monitoring binding kinetics that may prove useful for designing novel probes.Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this study, we report the development of surface-enhanced Raman spectroscopy (SERS) as a method to monitor the kinetics of gold-thiolate bond formation on colloidal gold nanoparticles. A theoretical model combining SERS enhancement with the Beer-Lambert law is proposed to explain ensemble scattering and absorption effects in colloids during chemisorption. In order to maximize biological relevance and signal reproducibility, experiments used to validate the model focused on maintaining nanoparticle stability after the addition of water-soluble aromatic thiolated molecules. Our results indicate that ligand exchange on gold nanoparticles follow a first-order Langmuir adsorption model with rate constants on the order of 0.01 min-1. This study demonstrates an experimental spectroscopic method and theoretical model for monitoring binding kinetics that may prove useful for designing novel probes. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01006c

In silico carbon molecular beam epitaxial growth of graphene on the h-BN substrate: carbon source effect on van der Waals epitaxy

NASA Astrophysics Data System (ADS)

Lee, Jonghoon; Varshney, Vikas; Park, Jeongho; Farmer, Barry L.; Roy, Ajit K.

2016-05-01

Against the presumption that hexagonal boron-nitride (h-BN) should provide an ideal substrate for van der Waals (vdW) epitaxy to grow high quality graphene films, carbon molecular beam epitaxy (CMBE) techniques using solid carbon sublimation have reported relatively poor quality of the graphene. In this article, the CMBE growth of graphene on the h-BN substrate is numerically studied in order to identify the effect of the carbon source on the quality of the graphene film. The carbon molecular beam generated by the sublimation of solid carbon source materials such as graphite and glassy carbon is mostly composed of atomic carbon, carbon dimers and carbon trimers. Therefore, the graphene film growth becomes a complex process involving various deposition characteristics of a multitude of carbon entities. Based on the study of surface adsorption and film growth characteristics of these three major carbon entities comprising graphite vapour, we report that carbon trimers convey strong traits of vdW epitaxy prone to high quality graphene growth, while atomic carbon deposition is a surface-reaction limited process accompanied by strong chemisorption. The vdW epitaxial behaviour of carbon trimers is found to be substantial enough to nucleate and develop into graphene like planar films within a nanosecond of high flux growth simulation, while reactive atomic carbons tend to impair the structural integrity of the crystalline h-BN substrate upon deposition to form an amorphous interface between the substrate and the growing carbon film. The content of reactive atomic carbons in the molecular beam is suspected to be the primary cause of low quality graphene reported in the literature. A possible optimization of the molecular beam composition towards the synthesis of better quality graphene films is suggested.Against the presumption that hexagonal boron-nitride (h-BN) should provide an ideal substrate for van der Waals (vdW) epitaxy to grow high quality graphene films, carbon molecular beam epitaxy (CMBE) techniques using solid carbon sublimation have reported relatively poor quality of the graphene. In this article, the CMBE growth of graphene on the h-BN substrate is numerically studied in order to identify the effect of the carbon source on the quality of the graphene film. The carbon molecular beam generated by the sublimation of solid carbon source materials such as graphite and glassy carbon is mostly composed of atomic carbon, carbon dimers and carbon trimers. Therefore, the graphene film growth becomes a complex process involving various deposition characteristics of a multitude of carbon entities. Based on the study of surface adsorption and film growth characteristics of these three major carbon entities comprising graphite vapour, we report that carbon trimers convey strong traits of vdW epitaxy prone to high quality graphene growth, while atomic carbon deposition is a surface-reaction limited process accompanied by strong chemisorption. The vdW epitaxial behaviour of carbon trimers is found to be substantial enough to nucleate and develop into graphene like planar films within a nanosecond of high flux growth simulation, while reactive atomic carbons tend to impair the structural integrity of the crystalline h-BN substrate upon deposition to form an amorphous interface between the substrate and the growing carbon film. The content of reactive atomic carbons in the molecular beam is suspected to be the primary cause of low quality graphene reported in the literature. A possible optimization of the molecular beam composition towards the synthesis of better quality graphene films is suggested. Electronic supplementary information (ESI) available: Three movie files: 3mer-physorption.mpg and 3mer-chemisorption.mpg feature examples of the adsorption state sampling of a carbon trimer on the heated h-BN substrate as mentioned in the ``Single Molecule Adsorption Study'' section. In 3mer-film-growth.mpg, an instance of honey comb formation during the initial phase of graphene growth simulation using a carbon trimer beam is captured. An initially sp hybridized carbon atom (red colored) becomes sp2 hybridized as a result of additional covalent bonding with the impinging carbon trimer. As the bond angle around the red carbon changes from 180 degree (sp) to 120 degree (sp2), nearby carbon atoms enclose to form a hexagon structure composed of 6 carbon atoms. See DOI: 10.1039/c6nr01396a

Chemical structural analysis of diamondlike carbon films: II. Raman analysis

NASA Astrophysics Data System (ADS)

Takabayashi, Susumu; Ješko, Radek; Shinohara, Masanori; Hayashi, Hiroyuki; Sugimoto, Rintaro; Ogawa, Shuichi; Takakuwa, Yuji

2018-02-01

The chemical structure of diamondlike carbon (DLC) films, synthesized by photoemission-assisted glow discharge, has been analyzed by Raman spectroscopy. Raman analysis in conjunction with the sp2 cluster model clarified the film structure. The sp2 clusters in DLC films synthesized at low temperature preferred various aliphatic structures. Sufficient argon-ion assist allowed for formation of less strained DLC films containing large amounts of hydrogen. As the synthesis temperature was increased, thermal desorption of hydrogen left carbon dangling bonds with active unpaired electrons in the films, and the reactions that followed created strained films containing aromatic sp2 clusters. In parallel, the desorption of methane molecules from the growing surface by chemisorption of hydrogen radicals prevented the action of argon ions, promoting internal strain of the films. However, in synthesis at very high temperature, where sp2 clusters are sufficiently dominant, the strain was dissolved gradually. In contrast, the DLC films synthesized at low temperature were more stable than other films synthesized at the same temperature because of stable hydrogen-carbon bonds in the films.

High-Energy Faceted SnO₂-Coated TiO₂ Nanobelt Heterostructure for Near-Ambient Temperature-Responsive Ethanol Sensor.

PubMed

Chen, Guohui; Ji, Shaozheng; Li, Haidong; Kang, Xueliang; Chang, Sujie; Wang, Yana; Yu, Guangwei; Lu, Jianren; Claverie, Jerome; Sang, Yuanhua; Liu, Hong

2015-11-11

A SnO2 gas sensor was prepared by a two-step oxidation process whereby a Sn(II) precursor was partially oxidized by a hydrothermal process and the resulting Sn3O4 nanoplates were thermally oxidized to yield SnO2 nanoplates. The SnO2 sensor was selective and responsive toward ethanol at a temperature as low as 43 °C. This low sensing temperature stems from the rapid charge transport within SnO2 and from the presence of high-energy (001) facets available for oxygen chemisorption. SnO2/TiO2 nanobelt heterostructures were fabricated by a similar two-step process in which TiO2 nanobelts acted as support for the epitaxial growth of intermediate Sn3O4. At temperatures ranging from 43 to 276 °C, the response of these branched nanobelts is more than double the response of SnO2 for ethanol detection. Our observations demonstrate the potential of low-cost SnO2-based sensors with controlled morphology and reactive facets for detecting gases around room temperature.

The sensing mechanism of N-doped SWCNTs toward SF6 decomposition products: A first-principle study

NASA Astrophysics Data System (ADS)

Gui, Yingang; Tang, Chao; Zhou, Qu; Xu, Lingna; Zhao, Zhongyong; Zhang, Xiaoxing

2018-05-01

In order to monitor the insulation status of SF6-insulated equipment on-line, SOF2 and SO2F2, two typical decomposition products of SF6 under electric discharge condition, are chosen as the target gases to evaluate the type and severity of discharge. In this work, single N atom doping method is adopted to improve the gas sensitivity of single wall carbon nanotubes to SOF2 and SO2F2. Single and double gas molecules adsorptions are considered to completely analyze the adsorption properties of N-doped single wall carbon nanotubes. Calculation results show that N atom doping enhances the surface activity of carbon nanotubes. When gas molecules physically adsorbed on N-doped single wall carbon nanotubes, the weak interaction between gas molecules and N-doped single wall carbon nanotubes nearly not changes the electrical property according to analysis of the density of states and molecular orbitals. While the chemisorption between gas molecules and N-doped single wall carbon nanotubes distinctly decreases the conductivity of adsorption system.

Mercury ion thruster research, 1978

NASA Technical Reports Server (NTRS)

Wilbur, P. J.

1978-01-01

The effects of 8 cm thruster main and neutralizer cathode operating conditions on cathode orifice plate temperatures were studied. The effects of cathode operating conditions on insert temperature profiles and keeper voltages are presented for three different types of inserts. The bulk of the emission current is generally observed to come from the downstream end of the insert rather than from the cathode orifice plate. Results of a test in which the screen grid plasma sheath of a thruster was probed as the beam current was varied are shown. Grid performance obtained with a grid machined from glass ceramic is discussed. The effects of copper and nitrogen impurities on the sputtering rates of thruster materials are measured experimentally and a model describing the rate of nitrogen chemisorption on materials in either the beam or the discharge chamber is presented. The results of optimization of a radial field thruster design are presented. Performance of this device is shown to be comparable to that of a divergent field thruster and efficient operation with the screen grid biased to floating potential, where its susceptibility to sputter erosion damage is reduced, is demonstrated.

A bond-order potential for the Al–Cu–H ternary system

DOE PAGES

Zhou, X. W.; Ward, D. K.; Foster, M. E.

2018-02-27

Al-Based Al–Cu alloys have a very high strength to density ratio, and are therefore important materials for transportation systems including vehicles and aircrafts. These alloys also appear to have a high resistance to hydrogen embrittlement, and as a result, are being explored for hydrogen related applications. To enable fundamental studies of mechanical behavior of Al–Cu alloys under hydrogen environments, we have developed an Al–Cu–H bond-order potential according to the formalism implemented in the molecular dynamics code LAMMPS. Our potential not only fits well to properties of a variety of elemental and compound configurations (with coordination varying from 1 to 12)more » including small clusters, bulk lattices, defects, and surfaces, but also passes stringent molecular dynamics simulation tests that sample chaotic configurations. Careful studies verified that this Al–Cu–H potential predicts structural property trends close to experimental results and quantum-mechanical calculations; in addition, it properly captures Al–Cu, Al–H, and Cu–H phase diagrams and enables simulations of H 2 dissociation, chemisorption, and absorption on Al–Cu surfaces.« less

Starch-g-Poly-(N, N-dimethyl acrylamide-co-acrylic acid): an efficient Cr (VI) ion binder.

PubMed

Kolya, Haradhan; Roy, Anirban; Tripathy, Tridib

2015-01-01

Synthesis of Starch-g-(Poly N, N-dimethylacrylamide-co-acrylic acid) was carried out by solution polymerization technique using potassium perdisulfate (K(2)S(2)O(8)) as the initiator. The graft copolymer was characterized by measuring molecular weight, using size exclusion chromatography (SEC), FTIR spectroscopy and X-ray diffraction (XRD) studies. The synthetic graft copolymer was used for removal of hexavalent chromium ion [Cr (VI)] from its aqueous solution. Various operating variables affecting the metal sorption such as, the amount of adsorbent, solution pH, contact time, temperature and the Cr (VI) solution concentration were extensively investigated. FTIR and UV-VIS spectroscopy, cyclic voltammetry (CV) were employed to study the metal complexation. The adsorption data could be well described by the pseudo-second-order and Langmuir isotherm model which indicate a chemisorption process. Calculation of the various thermodynamic parameters for the adsorption was also done. The negative value of free energy change (ΔG°) indicates the spontaneous nature of the adsorption. Copyright © 2014 Elsevier B.V. All rights reserved.

Surface Response of Brominated Carbon Media on Laser and Thermal Excitation: Optical and Thermal Analysis Study.

PubMed

Multian, Volodymyr V; Kinzerskyi, Fillip E; Vakaliuk, Anna V; Grishchenko, Liudmyla M; Diyuk, Vitaliy E; Boldyrieva, Olga Yu; Kozhanov, Vadim O; Mischanchuk, Oleksandr V; Lisnyak, Vladyslav V; Gayvoronsky, Volodymyr Ya

2017-12-01

The present study is objected to develop an analytical remote optical diagnostics of the functionalized carbons surface. Carbon composites with up to 1 mmol g -1 of irreversibly adsorbed bromine were produced by the room temperature plasma treatment of an activated carbon fabric (ACF) derived from polyacrylonitrile textile. The brominated ACF (BrACF) was studied by elastic optical scattering indicatrix analysis at wavelength 532 nm. The obtained data were interpreted within results of the thermogravimetric analysis, X-ray photoelectron spectroscopy and temperature programmed desorption mass spectrometry. The bromination dramatically reduces the microporosity producing practically non-porous material, while the incorporated into the micropores bromine induces the dielectric and structural impact on surface polarizability and conductivity due to the charging effect. We have found that the elastic optical scattering in proper solid angles in the forward and the backward hemispheres is sensitive to the kind of the bromine bonding, e.g., physical adsorption or chemisorption, and the bromination level, respectively, that can be utilized for the express remote fabrication control of the nanoscale carbons with given interfaces.

Preparation and characterization of corn cob activated carbon coated with nano-sized magnetite particles for the removal of Cr(VI).

PubMed

Nethaji, S; Sivasamy, A; Mandal, A B

2013-04-01

Activated carbon prepared from corn cob biomass, magnetized by magnetite nanoparticles (MCCAC) was used for the adsorption of hexavalent chromium from aqueous solution. The adsorbent was characterized by SEM, TEM, XRD, VSM, surface functionality and zero-point charge. The iron oxide nanoparticles were of 50 nm sizes and the saturation magnetization value for the adsorbent is 48.43 emu/g. Adsorption was maximum at pH 2. Isotherm data were modeled using Langmuir, Freundlich and Temkin isotherm. The prepared MCCAC had a heterogeneous surface. The maximum monolayer adsorption capacity was 57.37 mg/g. Kinetic studies were carried out and the data fitted the pseudo second-order equation. The mechanism of the adsorption process was studied by incorporating the kinetic data with intraparticle diffusion model, Bangham equation and Boyd plot. The adsorption was by chemisorption and the external mass transfer was the rate-determining step. A micro column was designed and the basic column parameters were estimated. Copyright © 2013 Elsevier Ltd. All rights reserved.

A plausible mechanism of biosorption in dual symbioses by vesicular-arbuscular mycorrhizal in plants.

PubMed

Azmat, Rafia; Hamid, Neelofer

2015-03-01

Dual symbioses of vesicular-arbuscular mycorrhizal (VAM) fungi with growth of Momordica charantia were elucidated in terms of plausible mechanism of biosorption in this article. The experiment was conducted in green house and mixed inoculum of the VAM fungi was used in the three replicates. Results demonstrated that the starch contents were the main source of C for the VAM to builds their hyphae. The increased plant height and leaves surface area were explained in relation with an increase in the photosynthetic rates to produce rapid sugar contents for the survival of plants. A decreased in protein, and amino acid contents and increased proline and protease activity in VAM plants suggested that these contents were the main bio-indicators of the plants under biotic stress. The decline in protein may be due to the degradation of these contents, which later on converted into dextrose where it can easily be absorbed by for the period of symbioses. A mechanism of C chemisorption in relation with physiology and morphology of plant was discussed.

A F-doped tree-like nanofiber structural poly-m-phenyleneisophthalamide separator for high-performance lithium-sulfur batteries

NASA Astrophysics Data System (ADS)

Deng, Nanping; Wang, Yan; Yan, Jing; Ju, Jingge; Li, Zongjie; Fan, Lanlan; Zhao, Huijuan; Kang, Weimin; Cheng, Bowen

2017-09-01

In this study, F-doped tree-like nanofiber structural poly-m-phenyleneisophthalamide (PMIA) membranes are prepared via one-step electrospinning approach and their application performance as separators for lithium-sulfur batteries are discussed. The F-doped PMIA membrane can be regarded as matrix to form gel polymer electrolyte. The F doping endows the PMIA membranes with extraordinary high electrolyte uptake, excellent ability of preserving the liquid electrolyte and forceful chemisorption to polysulfides. And the tree-like structure effectively blocks polysulfides by the physical confinement. The lithium-sulfur cell with the F-doped PMIA separator exhibits high first-cycle discharge capacity of 1222.5 mAh g-1 and excellent cycling stability with good capacity retention of 745.7 mAh g-1 and coulombic efficiency of 97.97% after 800 cycles. The remarkable performance can be ascribed to the suppressed shuttle effects through both the physical trapping of polysulfides by the gel polymer electrolyte based on matrix with F-doped PMIA membrane and the tree-like structure in a working cell.

Strong lithium polysulfide chemisorption on electroactive sites of nitrogen-doped carbon composites for high-performance lithium-sulfur battery cathodes.

PubMed

Song, Jiangxuan; Gordin, Mikhail L; Xu, Terrence; Chen, Shuru; Yu, Zhaoxin; Sohn, Hiesang; Lu, Jun; Ren, Yang; Duan, Yuhua; Wang, Donghai

2015-03-27

Despite the high theoretical capacity of lithium-sulfur batteries, their practical applications are severely hindered by a fast capacity decay, stemming from the dissolution and diffusion of lithium polysulfides in the electrolyte. A novel functional carbon composite (carbon-nanotube-interpenetrated mesoporous nitrogen-doped carbon spheres, MNCS/CNT), which can strongly adsorb lithium polysulfides, is now reported to act as a sulfur host. The nitrogen functional groups of this composite enable the effective trapping of lithium polysulfides on electroactive sites within the cathode, leading to a much improved electrochemical performance (1200 mAh g(-1) after 200 cycles). The enhancement in adsorption can be attributed to the chemical bonding of lithium ions by nitrogen functional groups in the MNCS/CNT framework. Furthermore, the micrometer-sized spherical structure of the material yields a high areal capacity (ca. 6 mAh cm(-2)) with a high sulfur loading of approximately 5 mg cm(-2), which is ideal for practical applications of the lithium-sulfur batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A bond-order potential for the Al–Cu–H ternary system

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

Zhou, X. W.; Ward, D. K.; Foster, M. E.

Al-Based Al–Cu alloys have a very high strength to density ratio, and are therefore important materials for transportation systems including vehicles and aircrafts. These alloys also appear to have a high resistance to hydrogen embrittlement, and as a result, are being explored for hydrogen related applications. To enable fundamental studies of mechanical behavior of Al–Cu alloys under hydrogen environments, we have developed an Al–Cu–H bond-order potential according to the formalism implemented in the molecular dynamics code LAMMPS. Our potential not only fits well to properties of a variety of elemental and compound configurations (with coordination varying from 1 to 12)more » including small clusters, bulk lattices, defects, and surfaces, but also passes stringent molecular dynamics simulation tests that sample chaotic configurations. Careful studies verified that this Al–Cu–H potential predicts structural property trends close to experimental results and quantum-mechanical calculations; in addition, it properly captures Al–Cu, Al–H, and Cu–H phase diagrams and enables simulations of H 2 dissociation, chemisorption, and absorption on Al–Cu surfaces.« less

Preparation of Activated Carbon From Polygonum orientale Linn. to Remove the Phenol in Aqueous Solutions

PubMed Central

Feng, Jia; Shi, Shengli; Pei, Liangyu; Lv, Junping; Liu, Qi; Xie, Shulian

2016-01-01

Phenol components are major industry contaminants of aquatic environment. Among all practical methods for removing phenol substances from polluted water, activated carbon absorption is the most effective way. Here, we have produced low-cost activated carbon using Polygonum orientale Linn, a wide spreading species with large biomass. The phenol adsorption ability of this activated carbon was evaluated at different physico-chemical conditions. Average equilibrium time for adsorption was 120 min. The phenol adsorption ability of the P. orientale activated carbon was increased as the pH increases and reached to the max at pH 9.00. By contrast, the ionic strength had little effect on the phenol absorption. The optimum dose for phenol adsorption by the P. orientale activated carbon was 20.00 g/L. The dominant adsorption mechanism of the P. orientale activated carbon was chemisorption as its phenol adsorption kinetics matched with the pseudo-second-order kinetics. In addition, the equilibrium data were fit to the Langmuir model, with the negative standard free energy and the positive enthalpy, suggesting that adsorption was spontaneous and endothermic. PMID:27741305

Synthesis of {111} Facet-Exposed MgO with Surface Oxygen Vacancies for Reactive Oxygen Species Generation in the Dark.

PubMed

Hao, Ying-Juan; Liu, Bing; Tian, Li-Gang; Li, Fa-Tang; Ren, Jie; Liu, Shao-Jia; Liu, Ying; Zhao, Jun; Wang, Xiao-Jing

2017-04-12

Seeking a simple and moderate route to generate reactive oxygen species (ROS) for antibiosis is of great interest and challenge. This work demonstrates that molecule transition and electron rearrangement processes can directly occur only through chemisorption interaction between the adsorbed O 2 and high-energy {111} facet-exposed MgO with abundant surface oxygen vacancies (SOVs), hence producing singlet oxygen and superoxide anion radicals without light irradiation. These ROS were confirmed by electron paramagnetic resonance, in situ Raman, and scavenger experiments. Furthermore, heat plays a crucial role for the electron transfer process to accelerate the formation of ·O 2 - , which is verified by temperature kinetic experiments of nitro blue tetrazolium reduction in the dark. Therefore, the presence of oxygen vacancy can be considered as an intensification of the activation process. The designed MgO is acquired in one step via constructing a reduction atmosphere during the combustion reaction process, which has an ability similar to that of noble metal Pd to activate molecular oxygen and can be used as an effective bacteriocide in the dark.

Synthesis, characterization, and potential application of Mn2+-intercalated bentonite in fluoride removal: adsorption modeling and mechanism evaluation

NASA Astrophysics Data System (ADS)

Mudzielwana, Rabelani; Gitari, Wilson M.; Akinyemi, Segun A.; Msagati, Titus A. M.

2017-12-01

The study synthesizes a low-cost adsorbent made from Mn2+-modified bentonite clay for groundwater defluoridation. The clays were characterized using X-ray diffraction, X-ray fluorescence, scanning electron microscopy, and Fourier transform infrared techniques. The fluoride adsorption capacity of the modified clay was evaluated using batch experiments. The adsorption kinetics results showed that the optimum fluoride (F-) uptake was achieved within the 30 min' contact time. The data fitted well to pseudo-second-order of reaction kinetics indicating that adsorption of F- occurred via chemisorption. In addition, the adsorption isotherm data fitted well to Langmuir isotherm model indicating that adsorption occurred on a mono-layered surface. Maximum F- removal of 57% was achieved from groundwater with an initial F- concentration of 5.4 mg L-1 and natural pH of 8.6 using adsorbent dosage of 1 g/100 mL. Fluoride adsorption occurred through ligands and ion exchange mechanisms. The synthesized adsorbent was successfully regenerated for up to five times. The study shows that Mn2+-intercalated bentonite clay has potential for application in defluoridation of groundwater.

Simulating the reactions of CO2 in aqueous monoethanolamine solution by reaction ensemble Monte Carlo using the continuous fractional component method.

PubMed

Balaji, Sayee Prasaad; Gangarapu, Satesh; Ramdin, Mahinder; Torres-Knoop, Ariana; Zuilhof, Han; Goetheer, Earl L V; Dubbeldam, David; Vlugt, Thijs J H

2015-06-09

Molecular simulations were used to compute the equilibrium concentrations of the different species in CO2/monoethanolamine solutions for different CO2 loadings. Simulations were performed in the Reaction Ensemble using the continuous fractional component Monte Carlo method at temperatures of 293, 333, and 353 K. The resulting computed equilibrium concentrations are in excellent agreement with experimental data. The effect of different reaction pathways was investigated. For a complete understanding of the equilibrium speciation, it is essential to take all elementary reactions into account because considering only the overall reaction of CO2 with MEA is insufficient. The effects of electrostatics and intermolecular van der Waals interactions were also studied, clearly showing that solvation of reactants and products is essential for the reaction. The Reaction Ensemble Monte Carlo using the continuous fractional component method opens the possibility of investigating the effects of the solvent on CO2 chemisorption by eliminating the need to study different reaction pathways and concentrate only on the thermodynamics of the system.

The effect of the surface composition of Ru-Pt bimetallic catalysts for methanol oxidation

DOE PAGES

Garrick, Taylor R.; Diao, Weijian; Tengco, John M.; ...

2016-02-23

Here, a series of Ru-Pt bimetallic catalysts prepared by the electroless deposition of controlled and variable amounts of Ru on the Pt surface of a commercially-available 20 wt% Pt/C catalyst has been characterized and evaluated for the oxidation of methanol. The activity of each Ru-Pt catalyst was determined as a function of surface composition via cyclic voltammetry. For the Ru-Pt bimetallic catalysts, activity passed through a maximum at approximately 50% monodisperse Ru surface coverage. However, due to the monolayer coverage of Ru on Pt, the amount of metal in the catalyst is minimized compared to a bulk 1:1 atomic ratiomore » of Ru:Pt seen in commercial bimetallic catalysts. Chemisorption and temperature programmed reduction experiments confirmed that the surface had characteristics of a true bimetallic catalyst. On a mass of Pt basis, the activity of this composition for methanol oxidation was 7 times higher than pure Pt and 3.5 times higher than a commercial catalyst with a 1:1 Pt:Ru bulk atomic ratio.« less

Isolation and evolution of labile sulfur allotropes via kinetic encapsulation in interactive porous networks

PubMed Central

Kitagawa, Hakuba; Ohtsu, Hiroyoshi; Cruz-Cabeza, Aurora J.; Kawano, Masaki

2016-01-01

The isolation and characterization of small sulfur allotropes have long remained unachievable because of their extreme lability. This study reports the first direct observation of disulfur (S2) with X-ray crystallography. Sulfur gas was kinetically trapped and frozen into the pores of two Cu-based porous coordination networks containing interactive iodide sites. Stabilization of S2 was achieved either through physisorption or chemisorption on iodide anions. One of the networks displayed shape selectivity for linear molecules only, therefore S2 was trapped and remained stable within the material at room temperature and higher. In the second network, however, the S2 molecules reacted further to produce bent-S3 species as the temperature was increased. Following the thermal evolution of the S2 species in this network using X-ray diffraction and Raman spectroscopy unveiled the generation of a new reaction intermediate never observed before, the cyclo-tri­sulfur dication (cyclo-S3 2+). It is envisaged that kinetic guest trapping in interactive crystalline porous networks will be a promising method to investigate transient chemical species. PMID:27437110

The dissociative chemisorption of methane on Ni(100) and Ni(111): Classical and quantum studies based on the reaction path Hamiltonian

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

Mastromatteo, Michael; Jackson, Bret, E-mail: jackson@chem.umass.edu

Electronic structure methods based on density functional theory are used to construct a reaction path Hamiltonian for CH{sub 4} dissociation on the Ni(100) and Ni(111) surfaces. Both quantum and quasi-classical trajectory approaches are used to compute dissociative sticking probabilities, including all molecular degrees of freedom and the effects of lattice motion. Both approaches show a large enhancement in sticking when the incident molecule is vibrationally excited, and both can reproduce the mode specificity observed in experiments. However, the quasi-classical calculations significantly overestimate the ground state dissociative sticking at all energies, and the magnitude of the enhancement in sticking with vibrationalmore » excitation is much smaller than that computed using the quantum approach or observed in the experiments. The origin of this behavior is an unphysical flow of zero point energy from the nine normal vibrational modes into the reaction coordinate, giving large values for reaction at energies below the activation energy. Perturbative assumptions made in the quantum studies are shown to be accurate at all energies studied.« less

An equilibrium ab initio atomistic thermodynamics study of chlorine adsorption on the Cu(001) surface.

PubMed

Suleiman, Ibrahim A; Radny, Marian W; Gladys, Michael J; Smith, Phillip V; Mackie, John C; Kennedy, Eric M; Dlugogorski, Bogdan Z

2011-06-07

The effect of chlorine (Cl) chemisorption on the energetics and atomic structure of the Cu(001) surface over a wide range of chlorine pressures and temperatures has been studied using equilibrium ab initio atomistic thermodynamics to elucidate the formation of cuprous chloride (CuCl) as part of the Deacon reaction on copper metal. The calculated surface free energies show that the 1/2 monolayer (ML) c(2 × 2)-Cl phase with chlorine atoms adsorbed at the hollow sites is the most stable structure for a wide range of Cl chemical potential, in agreement with experimental observations. It is also found that at very low pressure and exposure, but elevated temperature, the 1/9 ML and 1/4 ML phases become the most stable. By contrast, a high coverage of Cl does not lead to thermodynamically stable geometries. The subsurface adsorption of Cl atoms, however, dramatically increases the stability of the 1 ML and 2 ML adsorption configurations providing a possible pathway for the formation of the bulk-chloride surface phases in the kinetic regime.

Quarterly Technical Progress Report - Investigation of Syngas Interaction in Alcohol Synthesis Catalysts

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

Murty A. Akundi

This report presents the work done on " Investigation of Syngas Interaction in Alcohol Synthesis Catalysts" during the last quarter. The major activity during this period is on FTIR absorption studies of Co/Cr catalysts using CO as a probe molecule. Transition metals cobalt and copper play significant roles in the conversion of syngas (CO + H2 ) to liquid fuels. With a view to examine the nature of interaction between CO and metal, the FTIR spectra of CO adsorbed on Co-Cr2 O3 composites were investigated. The results indicate that as cobalt loading increases, the intensity of the CO adsorption bandsmore » increase and several vibrational modes seem to be promoted. Heat treatment of the sample revealed two distinct processes of adsorption. Bands due to physisorption disappeared while bands due to chemisorption not only increased in intensity but persisted even after desorption. It seems that the physisorption process is more active when the catalyst is fresh and is hindered when carbidic/carbonyl formations occur on the metal surfaces.« less

Removal of formaldehyde from air using functionalized silica supports.

PubMed

Ewlad-Ahmed, Abdunaser M; Morris, Michael A; Patwardhan, Siddharth V; Gibson, Lorraine T

2012-12-18

This paper demonstrates the use of functionalized meso-silica materials (MCM-41 or SBA-15) as adsorbents for formaldehyde (H₂CO) vapor from contaminated air. Additionally new green nanosilica (GNs) materials were prepared via a bioinspired synthesis route and were assessed for removal of H₂CO from contaminated indoor air. These exciting new materials were prepared via rapid, 15 min, environmentally friendly synthesis routes avoiding any secondary pollution. They provided an excellent platform for functionalization and extraction of H₂CO demonstrating similar performance to the conventional meso-silica materials. To the authors' knowledge this is the first reported practical application of this material type. Prior to trapping, all materials were functionalized with amino-propyl groups which led to chemisorption of H₂CO; removing it permanently from air. No retention of H₂CO was achieved with nonfunctionalized material and it was observed that best extraction performance required a dynamic adsorption setup when compared to passive application. These results demonstrate the first application of GNs as potential adsorbents and functionalized meso-silica for use in remediation of air pollution in indoor air.

Preparation of Activated Carbon From Polygonum orientale Linn. to Remove the Phenol in Aqueous Solutions.

PubMed

Feng, Jia; Shi, Shengli; Pei, Liangyu; Lv, Junping; Liu, Qi; Xie, Shulian

2016-01-01

Phenol components are major industry contaminants of aquatic environment. Among all practical methods for removing phenol substances from polluted water, activated carbon absorption is the most effective way. Here, we have produced low-cost activated carbon using Polygonum orientale Linn, a wide spreading species with large biomass. The phenol adsorption ability of this activated carbon was evaluated at different physico-chemical conditions. Average equilibrium time for adsorption was 120 min. The phenol adsorption ability of the P. orientale activated carbon was increased as the pH increases and reached to the max at pH 9.00. By contrast, the ionic strength had little effect on the phenol absorption. The optimum dose for phenol adsorption by the P. orientale activated carbon was 20.00 g/L. The dominant adsorption mechanism of the P. orientale activated carbon was chemisorption as its phenol adsorption kinetics matched with the pseudo-second-order kinetics. In addition, the equilibrium data were fit to the Langmuir model, with the negative standard free energy and the positive enthalpy, suggesting that adsorption was spontaneous and endothermic.

Solution-processed field-effect transistors based on dihexylquaterthiophene films with performances exceeding those of vacuum-sublimed films.

PubMed

Leydecker, Tim; Trong Duong, Duc; Salleo, Alberto; Orgiu, Emanuele; Samorì, Paolo

2014-12-10

Solution-processable oligothiophenes are model systems for charge transport and fabrication of organic field-effect transistors (OFET) . Herein we report a structure vs function relationship study focused on the electrical characteristics of solution-processed dihexylquaterthiophene (DH4T)-based OFET. We show that by combining the tailoring of all interfaces in the bottom-contact bottom-gate transistor, via chemisorption of ad hoc molecules on electrodes and dielectric, with suitable choice of the film preparation conditions (including solvent type, concentration, volume, and deposition method), it is possible to fabricate devices exhibiting field-effect mobilities exceeding those of vacuum-processed DH4T transistors. In particular, the evaporation rate of the solvent, the processing temperature, as well as the concentration of the semiconducting material were found to hold a paramount importance in driving the self-assembly toward the formation of highly ordered and low-dimensional supramolecular architectures, confirming the kinetically governed nature of the self-assembly process. Among the various architectures, hundreds-of-micrometers long and thin DH4T crystallites exhibited enhanced charge transport.

Kinetic studies of adsorption of thiocyanate onto ZnCl2 activated carbon from coir pith, an agricultural solid waste.

PubMed

Namasivayam, C; Sangeetha, D

2005-09-01

The adsorption of thiocyanate onto ZnCl2 activated carbon developed from coir pith was investigated to assess the possible use of this adsorbent. The influence of various parameters such as agitation time, thiocyanate concentration, adsorbent dose, pH and temperature has been studied. Adsorption followed second-order rate kinetics. Two theoretical adsorption isotherms, namely, Langmuir and Freundlich were used to describe the experimental results. The Langmuir adsorption capacity (Q0) was found to be 16.2 mg g(-1) of the adsorbent. The per cent adsorption was maximum in the pH range 3.0-7.0. pH effect and desorption studies showed that ion exchange and chemisorption mechanism are involved in the adsorption process. Thermodynamic parameters such as DeltaG0, DeltaH0 and DeltaS0 for the adsorption were evaluated. The negative values of DeltaH0 confirm the exothermic nature of adsorption. Effects of foreign ions on the adsorption of thiocyanate have been investigated. Removal of thiocyanate from ground water was also tested.

Charge-functionalized and mechanically durable composite cryogels from Q-NFC and CS for highly selective removal of anionic dyes.

PubMed

Chen, Yufei; Ru, Jing; Geng, Biyao; Wang, Haiying; Tong, Congcong; Du, Chungui; Wu, Shengchun; Liu, Hongzhi

2017-10-15

A composite cryogel was prepared from quaternized nanofibrillated cellulose (Q-NFC) and chitosan (CS) through a combination of freeze-drying and cross-linking with epichlorohydrin. The specific surface area of the composite cryogel was approximately two times that of Q-NFC cryogel. And the composite cryogel exhibited superior adsorption properties of anionic dyes than either the Q-NFC or CS cryogel controls. The adsorption isotherm well fitted the Langmuir model with the maximum theoretical adsorption capacity up to 473.9mg/g. The adsorption behavior was found to follow pseudo second-order kinetic model, indicating the chemisorption nature. Notably, the composite cryogel could effectively separate the cationic dye from anionic one. Furthermore, the composite cryogel displayed excellent reusability, evidenced by the removal percentage of Acid red 88 still as high as 96% even after five adsorption-desorption cycles. These advantages would make it an environmentally friendly candidate for the use in the separation and efficient removal of anionic dyes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Infrared spectra of the photosorption products of hydrogen and carbon monoxide on Al/sub 2/O/sub 3/ and SiO/sub 2/ containing transition-metal ions

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

Gerasimov, S.F.; Filimonov, V.N.

1981-10-01

It has been demonstrated by IR spectroscopy that the irradiation of samples of V/sup 5 +//SiO/sub 2/, V/sup 5 +//Al/sub 2/O/sub 3/, and Ni/sup 2 +//Al/sub 2/O/sub 3/ in an atmosphere of D/sub 2/ causes the isotope replacement of hydrogen atoms of the hydroxyl groups on the surface of the support and results in the formation of OD groups on photoinduced V/sup 4 +/O/sup -/ sites. Molecules of CO are photosorbed both on reduced ions of transition metals in the form of M-CVertical BarO surface carbonyls and on O/sup -/ ions. In the latter case, CO/sub 2/, which is easilymore » desorbed from V/sup 5 +//SiO/sub 2/, but is tightly bound to V/sup 5 +//Al/sub 2/O/sub 3/ owing to the chemisorption on the surface of the support, is formed on the samples containing vanadium.« less

Computational materials chemistry for carbon capture using porous materials

NASA Astrophysics Data System (ADS)

Sharma, Abhishek; Huang, Runhong; Malani, Ateeque; Babarao, Ravichandar

2017-11-01

Control over carbon dioxide (CO2) release is extremely important to decrease its hazardous effects on the environment such as global warming, ocean acidification, etc. For CO2 capture and storage at industrial point sources, nanoporous materials offer an energetically viable and economically feasible approach compared to chemisorption in amines. There is a growing need to design and synthesize new nanoporous materials with enhanced capability for carbon capture. Computational materials chemistry offers tools to screen and design cost-effective materials for CO2 separation and storage, and it is less time consuming compared to trial and error experimental synthesis. It also provides a guide to synthesize new materials with better properties for real world applications. In this review, we briefly highlight the various carbon capture technologies and the need of computational materials design for carbon capture. This review discusses the commonly used computational chemistry-based simulation methods for structural characterization and prediction of thermodynamic properties of adsorbed gases in porous materials. Finally, simulation studies reported on various potential porous materials, such as zeolites, porous carbon, metal organic frameworks (MOFs) and covalent organic frameworks (COFs), for CO2 capture are discussed.

Polymer Brushes: Synthesis, Characterization, Applications

NASA Astrophysics Data System (ADS)

Advincula, Rigoberto C.; Brittain, William J.; Caster, Kenneth C.; Rühe, Jürgen

2004-09-01

Materials scientists, polymer chemists, surface physicists and materials engineers will find this book a complete and detailed treatise on the field of polymer brushes, their synthesis, characterization and manifold applications. In a first section, the various synthetic pathways and different surface materials are introduced and explained, followed by a second section covering important aspects of characterization and analysis in both flat surfaces and particles. These specific surface initiated polymerization (SIP) systems such as linear polymers, homopolymers, block copolymers, and hyperbranched polymers are unique compared to previously reported systems by chemisorption or physisorption. They have found their way in both large-scale and miniature applications of polymer brushes, which is covered in the last section. Such 'hairy' surfaces offer fascinating opportunities for addressing numerous problems of both academic and, in particular, industrial interest: high-quality, functional or protective coatings, composite materials, surface engineered particles, metal-organic interfaces, biological applications, micro-patterning, colloids, nanoparticles, functional devices, and many more. It is the desire of the authors that this book will be of benefit to readers who want to "brush-up on polymers".

Texture control and seeded nucleation of nanosize structures of ferroelectric thin films

NASA Astrophysics Data System (ADS)

Muralt, Paul

2006-09-01

An overview is given on nucleation phenomena of Pb(Zr ,Ti)O3 (PZT) thin films on Pt(111)-based substrates. Emphasis is given on in situ growth methods, particularly in situ reactive sputtering from three metallic targets. Growth of PZT thin films is discussed from the point of view of the PbOx-TiO2 phase diagram, PbO vapor pressure, and classical nucleation theory. The role of thin TiO2 affinity layers and spots is explained in the frame of this theory. Activation energies for desorption and chemisorption are adapted to comply with the fact that nucleation rates on TiO2 are much larger than the ones on bare Pt(111). The model reproduces well the PbO surface flux from bare Pt(111) to the affinity spots in the case of PbTiO3 nucleation and the reversed tendency in the case of PZT 40/60 nucleation, explaining experimental observations. The critical size of nuclei was calculated to contain 8-10unit cells for PbTiO3/Pt nucleation and 14-17 for PZT/Pt nucleation.

Adsorption of Congo red dye onto antimicrobial terephthaloyl thiourea cross-linked chitosan hydrogels.

PubMed

El-Harby, Nouf F; Ibrahim, Shaimaa M A; Mohamed, Nadia A

2017-11-01

Adsorption capacity of three antimicrobial terephthaloyl thiourea cross-linked chitosan hydrogels for Congo red dye removal from its aqueous solution has been investigated for the first time in this work. These hydrogels were prepared by reacting chitosan with various amounts of terephthaloyl diisothiocyanate cross-linker. The effect of the hydrogel structural variations and several dye adsorption processing parameters to achieve the best adsorption capacity were investigated. The hydrogels' structural variations were obtained by varying their terephthaloyl thiourea moieties content. The processing variables included initial concentration of the dye solution, temperature and time of exposure to the dye. The adsorption kinetics and isotherms showed that the sorption processes were better fitted by the pseudo-second-order equation and the Langmuir equation, respectively. On the basis of the Langmuir analysis Congo red dye gave the maximum sorption capacity of 44.248 mg/g. The results obtained confirmed that the sorption phenomena are most likely to be controlled by chemisorption process. The adsorption reaction was endothermic and spontaneous according to the calculated results of adsorption thermodynamics.

Medical Imaging for the Tracking of Micromotors.

PubMed

Vilela, Diana; Cossío, Unai; Parmar, Jemish; Martínez-Villacorta, Angel M; Gómez-Vallejo, Vanessa; Llop, Jordi; Sánchez, Samuel

2018-02-27

Micro/nanomotors are useful tools for several biomedical applications, including targeted drug delivery and minimally invasive microsurgeries. However, major challenges such as in vivo imaging need to be addressed before they can be safely applied on a living body. Here, we show that positron emission tomography (PET), a molecular imaging technique widely used in medical imaging, can also be used to track a large population of tubular Au/PEDOT/Pt micromotors. Chemisorption of an iodine isotope onto the micromotor's Au surface rendered them detectable by PET, and we could track their movements in a tubular phantom over time frames of up to 15 min. In a second set of experiments, micromotors and the bubbles released during self-propulsion were optically tracked by video imaging and bright-field microscopy. The results from direct optical tracking agreed with those from PET tracking, demonstrating that PET is a suitable technique for the imaging of large populations of active micromotors in opaque environments, thus opening opportunities for the use of this mature imaging technology for the in vivo localization of artificial swimmers.

Charge transfer photodissociation of phenol on Ag(111)

NASA Astrophysics Data System (ADS)

Lee, Junseok; Ryu, Sunmin; Ku, Jong Seok; Kim, Seong Keun

2001-12-01

The photochemistry of phenol on Ag(111) has been investigated by post-irradiation temperature programmed desorption (TPD). Ultraviolet (UV) irradiation at 355 and 266 nm was found to affect only the chemisorption layer in direct contact with the metal surface, while leaving the multilayer virtually intact. The main photoinduced reaction was found to be photodissociation of the O-H bond of phenol. Two new peaks were observed at the mass of phenol in the post-irradiation TPD spectrum at 335 K and 455 K. These peaks were assigned to the recombinative desorption of phenoxy with the hydrogen from O-H bond photodissociation and from thermal C-H bond fission, respectively. The photodissociation cross section was measured at different wavelengths and coverages. A charge transfer type photodissociation mechanism was proposed, where hot electrons generated in the substrate by UV photons attach to the affinity level of the adsorbed phenol. The transition to the transient anionic potential then leads to facile dissociation of O-H bond. The affinity level of phenol has been estimated to lie at 3.2-3.5 eV above the Fermi level for the 1 ML case.

A Recyclable Metal-Organic Framework as a Dual Detector and Adsorbent for Ammonia.

PubMed

Gładysiak, Andrzej; Nguyen, Tu N; Navarro, Jorge A R; Rosseinsky, Matthew J; Stylianou, Kyriakos C

2017-10-04

Recyclable materials for simultaneous detection and uptake of ammonia (NH 3 ) are of great interest due to the hazardous nature of NH 3 . The structural versatility and porous nature of metal-organic frameworks (MOFs) make them ideal candidates for NH 3 capture. Herein, the synthesis of a water-stable and porous 3-dimensional Cu II -based MOF (SION-10) displaying a ship-in-a-bottle structure is reported; the pores of the host SION-10 framework accommodate mononuclear Cu II -complexes. SION-10 spontaneously uptakes NH 3 as a result of two concurrent mechanisms: chemisorption due to the presence of active Cu II sites and physisorption (bulk permanent porosity). The color of the material changes from green to blue upon NH 3 capture, with the shifts of the UV/Vis absorption bands clearly seen at NH 3 concentrations as low as 300 ppm. SION-10 can be recovered upon immersion of SION-10⊃NH 3 in water and can be further reused for NH 3 capture for at least three cycles. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption and chemical reaction of gaseous mixtures of hydrogen chloride and water on aluminum oxide and application to solid-propellant rocket exhaust clouds

NASA Technical Reports Server (NTRS)

Cofer, W. R., III; Pellett, G. L.

1978-01-01

Hydrogen chloride (HCl) and aluminum oxide (Al2O3) are major exhaust products of solid rocket motors (SRM). Samples of calcination-produced alumina were exposed to continuously flowing mixtures of gaseous HCl/H2O in nitrogen. Transient sorption rates, as well as maximum sorptive capacities, were found to be largely controlled by specific surface area for samples of alpha, theta, and gamma alumina. Sorption rates for small samples were characterized linearly with an empirical relationship that accounted for specific area and logarithmic time. Chemisorption occurred on all aluminas studied and appeared to form from the sorption of about a 2/5 HCl-to-H2O mole ratio. The chemisorbed phase was predominantly water soluble, yielding chloride/aluminum III ion mole ratios of about 3.3/1 suggestive of dissolved surface chlorides and/or oxychlorides. Isopiestic experiments in hydrochloric acid indicated that dissolution of alumina led to an increase in water-vapor pressure. Dissolution in aqueous SRM acid aerosol droplets, therefore, might be expected to promote evaporation.

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

Liau, Leo Chau-Kuang, E-mail: lckliau@saturn.yzu.edu.tw; Hsu, Tzu-Hsien; Lo, Pei-Hsuan

We report the characteristics of p-channel thin film transistors (p-TFTs) with ZnO/hydrated polyvinyl alcohol (PVA) (ZnO/PVA) conducting channels. The metal-oxide-semiconductor structure of the p-TFTs was composed of indium tin oxide (ITO)/SiO{sub 2}/ZnO/PVA layers. The TFT was assembled using PVA gel, which was glued to ITO substrates patterned to form source and drain electrodes. The ZnO/PVA composite film acted as an effective conducting film because of the chemisorption reaction at the film interface where free electrons can be generated. The formation of the conducting channel was also affected by V{sub G} applied to the TFT. The ZnO/PVA-based TFTs demonstrated p-channel transistormore » performance, shown by current-voltage (I-V) data analysis. The electrical parameters of the device were evaluated, including the on/off ratio (∼10{sup 3}), threshold voltage (V{sub th}, −1 V), and subthreshold swing (−2.2 V/dec). The PVA/ZnO-based p-TFTs were fabricated using simple and cost-effective approaches instead of doping methods.« less

Influence of ɣ and ultrasonic irradiations on the physicochemical properties of CeO2-Fe2O3-Al2O3 for textile dyes removal applications

NASA Astrophysics Data System (ADS)

Ibrahim, Marwa M.; El-Molla, Sahar A.; Ismail, Sahar A.

2018-04-01

In this study highly effective adsorbent ternary mixed oxide CeO2-Fe2O3-Al2O3 was prepared by precipitation method. Various methods used to treat the mixed hydroxide like calcination, ultrasonic, hydrothermal and ɣ radiation with different doses to obtain the ternary mixed oxide. XRD, TEM, EDX, FTIR and SBET are used to study the physicochemical properties of nanoparticles. The CFAH and CFAɣ0.8 have the different morphologies and high surface area. Batch adsorption experiments were performed to remove anionic Remazol Red RB-133 dye. The experimental data showed that The CFAH and CFAɣ0.8 have high adsorption rate for removing of dye. The removal of dye is enhanced by ultrasonic radiation and high temperature. The adsorption process was fitted well for pseudo second order kinetics and followed the Freundlich isotherm model. In addition to, Thermodynamic results of adsorption process displayed that, the adsorption of dye on adsorbent was spontaneous, endothermic and chemisorptions process.

Structure and reaction properties of thin Al films deposited on Ni(110)

NASA Astrophysics Data System (ADS)

Hahn, Peter; Bertino, Massimo F.; Toennies, J. Peter; Ritter, Michael; Weiss, Werner

1998-09-01

A variety of experimental techniques, including scanning tunneling microscopy (STM) and thermal desorption spectroscopy (TDS) have been used to investigate the structure and reaction properties of thin Al films on Ni(110) as a model for technical Raney nickel catalysts. The measurements show that Al grows by the Volmer-Weber growth mode, with Al islands reaching a height of 30 Å before the first Al layer is completed. On exposure to deuterium the TDS spectra indicate that the addition of Al produces a new deuterium chemisorption state with a desorption energy which decreases from 27 to 14 kJ/mol with increasing deuterium coverage. This new bound state is attributed to deuterium atoms bound to adsorption sites in the vicinity of Al islands. Thermal desorption measurements also reveal that the deuterium initial sticking coefficient S0 decreases with Al coverage. The results can be explained by a simple model which shows that for low Al coverages each Al island inhibits deuterium dissociation in a region which is about three times larger than the island area.

Universal binding energy relations in metallic adhesion

NASA Technical Reports Server (NTRS)

Ferrante, J.; Smith, J. R.; Rose, J. J.

1984-01-01

Rose, Smith, and Ferrante have discovered scaling relations which map the adhesive binding energy calculated by Ferrante and Smith onto a single universal binding energy curve. These binding energies are calculated for all combinations of Al(111), Zn(0001), Mg(0001), and Na(110) in contact. The scaling involves normalizing the energy by the maximum binding energy and normalizing distances by a suitable combination of Thomas-Fermi screening lengths. Rose et al. have also found that the calculated cohesive energies of K, Ba, Cu, Mo, and Sm scale by similar simple relations, suggesting the universal relation may be more general than for the simple free electron metals for which it was derived. In addition, the scaling length was defined more generally in order to relate it to measurable physical properties. Further this universality can be extended to chemisorption. A simple and yet quite accurate prediction of a zero temperature equation of state (volume as a function of pressure for metals and alloys) is presented. Thermal expansion coefficients and melting temperatures are predicted by simple, analytic expressions, and results compare favorably with experiment for a broad range of metals.

Hybrid structure of polyaniline/ZnO nanograss and its application in dye-sensitized solar cell with performance improvement

NASA Astrophysics Data System (ADS)

Zhu, Shibu; Wei, Wei; Chen, Xiangnan; Jiang, Man; Zhou, Zuowan

2012-06-01

Polyaniline (PANI) hybridized ZnO photoanode for dye-sensitized solar cell (DSSC) was primarily prepared via a two-step process which involved hydrothermal growth of ZnO nanograss on the fluorine-doped tin oxide (FTO) substrate and subsequently chemisorption of PANI on the surfaces of the ZnO nanorods. The PANI hybridized ZnO nanograss films were characterized by scanning electron microscope (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectra (FT-IR), and the results indicated that there were chemical interactions between PANI and ZnO. Both pure ZnO nanograss and PANI hybridized ZnO nanograss were applied to DSSC. The results of photoelectrochemical measurement showed that the photocurrent density of PANI (100 mg/L) hybridized ZnO nanograss photoanode was significantly enhanced, and the overall light-conversion efficiency increased by 60%. The electrochemical impedance spectra (EIS) displayed that the electron densities in photoanodes of PANI hybridized ZnO nanograss were larger than that in pure ZnO nanograss. This is ascribed to more effective charge separation and faster interfacial charge transferring occurred in the hybrid photoanode.

Biosorption of landfill leachate by Phanerochaete sp. ISTL01: isotherms, kinetics and toxicological assessment.

PubMed

Ghosh, Pooja; Thakur, Indu Shekhar

2017-07-01

The study investigates the ability of fungus Phanerochaete sp. ISTL01 for biosorption of color from landfill leachate. Batch mode experiments were conducted to study the effects of pH, temperature, adsorbent dose, contact time and initial leachate concentration on biosorption. Maximum biosorption capacity was determined as 17.73 mg g -1 of biomass. Equilibrium isotherms and kinetics were further studied. The biosorption data were found to fit well to the Freundlich isotherm and pseudo-second-order kinetic model. The value of activation energy suggested that chemisorption mechanism was involved. Biosorption efficiency was also evaluated by the Methyltetrazolium (MTT) assay for cytotoxicity and alkaline comet assay in HepG2 human hepato-carcinoma cells. The fungus reduced toxicity as shown by 1.3-fold increase in MTT EC 50 and 1.5- and 1.1-fold reduction in Tail moment and Olive tail moment, respectively, after 12 h biosorption. The fungus showed good biosorption characteristics in terms of contaminant-level reduction per unit mass of adsorbent, process kinetics and toxicity reduction, envisaging its application in leachate treatment.

Improvement of sulfur resistance of Pd/Ce-Zr-Al-O catalysts for CO oxidation

NASA Astrophysics Data System (ADS)

Shin, Haebin; Baek, Minsung; Ro, Youngsoo; Song, Changyeol; Lee, Kwan-Young; Song, In Kyu

2018-01-01

Two kinds of mesoporous ceria-zirconia-alumina supports were prepared by a single-step epoxide-driven sol-gel method (SGCZA) and by a co-precipitation method (PCZA). Palladium catalysts supported on these materials were then prepared by a wet impregnation method (Pd/SGCZA and Pd/PCZA). The prepared catalysts were applied to the CO oxidation reaction before and after sulfur aging. XRD and N2 adsorption-desorption analyses revealed that these two catalysts retained different physicochemical properties. Pd/SGCZA had higher surface area and larger pore volume than Pd/PCZA before and after sulfur aging. TPR (Temperature-programmed reduction), CO chemisorption, FT-IR, and XPS analyses showed that the catalysts were differently influenced by sulfur species. Pd/SGCZA formed less sulfate and retained higher palladium dispersion than Pd/PCZA after sulfur aging. In the CO oxidation, Pd/PCZA showed better activity than Pd/SGCZA before sulfur aging. However, Pd/SGCZA showed higher CO conversion than Pd/PCZA after sulfur aging. We concluded that Pd/SGCZA was less poisoned by sulfur species than Pd/PCZA.

Hydrogen adsorption in metal-decorated silicon carbide nanotubes

NASA Astrophysics Data System (ADS)

Singh, Ram Sevak; Solanki, Ankit

2016-09-01

Hydrogen storage for fuel cell is an active area of research and appropriate materials with excellent hydrogen adsorption properties are highly demanded. Nanotubes, having high surface to volume ratio, are promising storage materials for hydrogen. Recently, silicon carbide nanotubes have been predicted as potential materials for future hydrogen storage application, and studies in this area are ongoing. Here, we report a systematic study on hydrogen adsorption properties in metal (Pt, Ni and Al) decorated silicon carbide nanotubes (SiCNTs) using first principles calculations based on density functional theory. The hydrogen adsorption properties are investigated by calculations of adsorption energy, electronic band structure, density of states (DOS) and Mulliken charge population analysis. Our findings show that hydrogen adsorptions on Pt, Ni and Al-decorated SiCNTs undergo spontaneous exothermic reactions with significant modulation of electronic structure of SiCNTs in all cases. Importantly, according to the Mulliken charge population analysis, dipole-dipole interaction causes chemisorptions of hydrogen in Pt, Ni and Al decorated SiCNTs with formation of chemical bonds. The study is a platform for the development of metal decorated SiCNTs for hydrogen adsorption or hydrogen storage application.

Monolayer group-III monochalcogenides by oxygen functionalization: a promising class of two-dimensional topological insulators

NASA Astrophysics Data System (ADS)

Zhou, Si; Liu, Cheng-Cheng; Zhao, Jijun; Yao, Yugui

2018-03-01

Monolayer group-III monochalcogenides (MX, M = Ga, In; X = S, Se, Te), an emerging category of two-dimensional (2D) semiconductors, hold great promise for electronics, optoelectronics and catalysts. By first-principles calculations, we show that the phonon dispersion and Raman spectra, as well as the electronic and topological properties of monolayer MX can be tuned by oxygen functionalization. Chemisorption of oxygen atoms on one side or both sides of the MX sheet narrows or even closes the band gap, enlarges work function, and significantly reduces the carrier effective mass. More excitingly, InS, InSe, and InTe monolayers with double-side oxygen functionalization are 2D topological insulators with sizeable bulk gap up to 0.21 eV. Their low-energy bands near the Fermi level are dominated by the px and py orbitals of atoms, allowing band engineering via in-plane strains. Our studies provide viable strategy for realizing quantum spin Hall effect in monolayer group-III monochalcogenides at room temperature, and utilizing these novel 2D materials for high-speed and dissipationless transport devices.

Charge injection and transport in a single organic monolayer island

NASA Astrophysics Data System (ADS)

Vuillaume, Dominique

2005-03-01

We report how electrons and holes, that are locally injected in a single organic monolayer island (where organic monolayers are made from sublimated oligomers (pentacene and other oligoacenes), or made from chemisorption in solution (self-assembled monolayers) of pi-conjugated moieties), stay localized or are able to delocalize over the island as a function of the molecular conformation (order vs. disorder) of this island. Charge carriers were locally injected by the apex of an atomic force microscope tip, and the resulting two-dimensional distribution and concentration of injected charges were measured by electrical force microscopy (EFM) experiments. We show that in crystalline monolayer islands, both electrons and holes can be equally injected, at a similar charge concentration for symmetric injection bias conditions, and that both charge carriers are delocalized over the whole island. On the contrary, charges injected into a more disordered monolayer stay localized at their injection point. These different results are discussed in relation with the electrical performances of molecular devices made from these monolayers (OFET, SAMFET). These results provide insight into the electronic properties, at the nanometer scale, of these molecular devices.

Electronic properties and gas adsorption behaviour of pristine, silicon-, and boron-doped (8, 0) single-walled carbon nanotube: A first principles study.

PubMed

Azam, Mohd Asyadi; Alias, Farizul Muiz; Tack, Liew Weng; Seman, Raja Noor Amalina Raja; Taib, Mohamad Fariz Mohamad

2017-08-01

Carbon nanotubes (CNTs) have received enormous attention due to their fascinating properties to be used in various applications including electronics, sensing, energy storage and conversion. The first principles calculations within density functional theory (DFT) have been carried out in order to investigate the structural, electronic and optical properties of un-doped and doped CNT nanostructures. O 2 , CO 2 , and CH 3 OH have been chosen as gas molecules to study the adsorption properties based on zigzag (8,0) SWCNTs. The results demonstrate that the adsorption of O 2 , CO 2, and CH 3 OH gas molecules on pristine, Si-doped and B-doped SWCNTs are either physisorption or chemisorption. Moreover, the electronic properties indicating SWCNT shows significant improvement toward gas adsorption which provides the impact of selecting the best gas sensor materials towards detecting gas molecule. Therefore, these pristine, Si-, and B-doped SWCNTs can be considered to be very good potential candidates for sensing application. Copyright © 2017 Elsevier Inc. All rights reserved.

Bioaccumulation of nickel by intercalation into polycrystalline hydrogen uranyl phosphate deposited via an enzymatic mechanism.

PubMed

Bonthrone, K M; Basnakova, G; Lin, F; Macaskie, L E

1996-05-01

A Citrobacter sp. accumulates uranyl ion (UO2(2+)) as crystalline HUO2PO4.4H2O (HUP), using enzymatically generated inorganic phosphate. Ni was not removed by this mechanism, but cells already loaded with HUP removed Ni2+ by intercalative ion-exchange, forming Ni(UO2PO4)2.7H2O, as concluded by x-ray diffraction (XRD) and proton induced x-ray emission (PIXE) analyses. The loaded biomass became saturated with Ni rapidly, with a molar ratio of Ni:U in the cellbound deposit of approx. 1:6; Ni penetration was probably surface-localized. Cochallenge of the cells with Ni2+ and UO2(2+), and glycerol 2-phosphate (phosphate donor for phosphate release and metal bioprecipitation) gave sustained removal of both metals in a flow through bioreactor, with more extensively accumulated Ni. We propose 'Microbially Enhanced Chemisorption of Heavy Metals' (MECHM) to describe this hybrid mechanism of metal bioaccumulation via intercalation into preformed, biogenic crystals, and note also that MECHM can promote the removal of the transuranic radionuclide neptunium, which is difficult to achieve by conventional methods.

Kinetic and thermodynamic studies on the adsorption of anionic surfactant on quaternary ammonium cationic cellulose.

PubMed

Zhang, Yuanzhang; Shi, Wenjian; Zhou, Hualan; Fu, Xing; Chen, Xuan

2010-06-01

Removal of anionic surfactants from aqueous solutions by adsorption onto quaternary ammonium cationic cellulose (QACC) was investigated. The effects of solution acidity, initial concentration, adsorption time, and temperature on the adsorption of sodium dodecyl-benzene sulfonate (SDBS), sodium lauryl sulfate (SLS), and sodium dodecyl sulfonate (SDS) were studied. The kinetic experimental data fit well with the pseudo-second-order model; the rate constant of the adsorption increased with temperature. The values of apparent activation energy for the adsorption were calculated as ranging from 10.2 to 17.4 kJ/ mol. The adsorption isotherm can be described by the Langmuir isotherm. The values of thermodynamic parameters (deltaH0, deltaS0, and deltaG0) for the adsorption indicated that this process was spontaneous and endothermic. At 318 K, the saturated adsorption capacities of QACC for SDBS, SLS, and SDS were 1.75, 1.53, and 1.39 mmol/g, respectively. The adsorption process was mainly chemisorption and partially physisorption. The results show that QACC is effective for the removal of anionic surfactants.

Electrochemical Functionalization of Graphene at the Nanoscale with Self-Assembling Diazonium Salts.

PubMed

Xia, Zhenyuan; Leonardi, Francesca; Gobbi, Marco; Liu, Yi; Bellani, Vittorio; Liscio, Andrea; Kovtun, Alessandro; Li, Rongjin; Feng, Xinliang; Orgiu, Emanuele; Samorì, Paolo; Treossi, Emanuele; Palermo, Vincenzo

2016-07-26

We describe a fast and versatile method to functionalize high-quality graphene with organic molecules by exploiting the synergistic effect of supramolecular and covalent chemistry. With this goal, we designed and synthesized molecules comprising a long aliphatic chain and an aryl diazonium salt. Thanks to the long chain, these molecules physisorb from solution onto CVD graphene or bulk graphite, self-assembling in an ordered monolayer. The sample is successively transferred into an aqueous electrolyte, to block any reorganization or desorption of the monolayer. An electrochemical impulse is used to transform the diazonium group into a radical capable of grafting covalently to the substrate and transforming the physisorption into a covalent chemisorption. During covalent grafting in water, the molecules retain the ordered packing formed upon self-assembly. Our two-step approach is characterized by the independent control over the processes of immobilization of molecules on the substrate and their covalent tethering, enabling fast (t < 10 s) covalent functionalization of graphene. This strategy is highly versatile and works with many carbon-based materials including graphene deposited on silicon, plastic, and quartz as well as highly oriented pyrolytic graphite.

Kinetics and equilibria of redox systems at temperatures as low as 300°C

NASA Astrophysics Data System (ADS)

Burkhard, Dorothee J. M.; Ulmer, Gene C.

1995-05-01

ZrO 2 oxygen sensors, gas mixtures, and conventional solid buffers have been used for decades to either control or measure oxygen fugacity (ƒ O 2) at high temperatures. In dry systems below ca. 700°C these techniques were used cautiously, if at all, due to doubt that there was any equilibration at lower temperatures. We have re-investigated these three types of redox systems in a study where each system (two different Y 2O 3ZrO 2 cells, four different gas mixtures, and four different dry solid buffers) was simultaneously cross-checked with the other to temperatures below 300°C and compared to JANAF data, extrapolated down to low temperatures. Steady and reproducible readings were observed down to T ≤ 300°C, from which we infer fast kinetics for all three systems. Specifically, we find equilibration of various CO 2H 2 gas mixtures over the entire temperature range and to much lower temperature than previously predicted. We assign the reactivity (decomposition) of CO 2 at low T to the catalytic action of Pt, whereby chemisorption of H 2 on the platinum surface enhances the reactivity with CO 2. This catalytic reactivity is diminished over time due to a long-term irreversible reaction of Pt with H 2. Subsequent embrittling and aging after prolonged exposure to H 2 explains erroneously high emf readings. Oxygen sensing of ZrO 2 cells is linear in 1/ T-log ƒ O 2 space and Nernstian at high temperatures. However, for cells with a specific and complex trace element chemistry, one may observe a non-Nernstian behavior in the low T range, i.e., below 470° or lower, probably caused by partially blocked O 2- migration, dependent on the H 2 content in the gas mixture. Linearity and reproducibility of this deviation still allows, however, a useable calibration. Solid buffers of the metal-metal oxide type are known to alloy with noble metals and we therefore used AgPd electrodes, for consistency in all studies, including (IW), (IM), (FMQ), and (NNO). Whereas (IW) and (IM) can be used in the temperature range of consideration, (FMQ) and (NNO) react sluggishly. Complex defect structure of (FMQ) and age alteration of Ni surfaces by chemisorption of oxygen and/or AgNi alloying of (NNO) may be the reason. Fast kinetics and successful redox sensing of CO 2H 2 gas mixtures, of ZrO 2 cells and of at least some solid buffers are therefore promising for future research on low- T redox equilibria.

Effective Removal of Tetracycline from Aqueous Solution by Organic Acid-Coated Magnetic Nanoparticles.

PubMed

Guo, Liang; Liang, Yuyan; Chen, Xuelan; Xu, Wei; Wu, Kesheng; Wei, Hua; Xiong, Yonghua

2016-03-01

Self-assembled iron oxide nanocomposites are good magnetic nano-adsorbents that can be prepared using simple methods. Four types of organic acid-functionalised (oleic acid, undecenoic acid, caprylic acid or hexanoic acid) magnetic nanoparticles (MNPs) were synthesised through a one-pot chemisorption method for the removal of tetracycline (TC) from aqueous solution. The undecenoic acid-coated MNPs (UA-MNPs) exhibited the highest adsorption efficiency and can be easily retrieved with a low-gradient magnetic separator (0.4 Tesla) at pH 5.0 aqueous solution. The TC adsorption process on the UA-MNPs followed the Langmuir isotherm and the maximum adsorption capacities increased from 86.96 mg g(-1) to 222.2 mg g(-1) with the increase in temperature from 288 K to 318 K. The kinetics of adsorption fits pseudo-second-order model perfectly with a rate constant, 5.946 g mg(-1) min(-1) at 298 K. The positive values of the enthalpy (AH) and the negative value of the free energy (AG) indicated an endothermic and spontaneous adsorption process of TC on the UA-MNPs. Moreover, the UA-MNPs possessed excellent ability to adsorb the other three major types of TC antibiotics, including chlortetracycline, oxytetracycline and doxycycline.

Designing the Rashba spin texture by adsorption of inorganic molecules

NASA Astrophysics Data System (ADS)

Friedrich, Rico; Caciuc, Vasile; Bihlmayer, Gustav; Atodiresei, Nicolae; Blügel, Stefan

We present an approach in which we show that the spin texture of a surface Rashba system can be adjusted by the adsorption of molecules. By selecting physisorbed and chemisorbed inorganic molecules on the BiAg2/Ag(111) surface alloy we demonstrate from ab initio that both the spin-orbit splitting and the spin direction of Rashba-split surface states can be controlled selectively. The physisorption of NH3 gives rise to a slightly enhanced outward buckling of the surface Bi which enlarges the magnitude of the Rashba splitting. On the contrary, the weak chemisorption of BH3 defines a strong inward relaxation of the surface Bi. This causes the occupied Rashba split state to shift into Ag bulk states. In addition a new Rashba splitting is created in an unoccupied state upon BH3 adsorption. Most importantly, in contrast to the clean surface in case of the BH3-BiAg2/Ag(111) system the out-of-plane spin polarization is significantly larger than the in-plane one. We gratefully acknowledge financial support from the Volkswagen-Stiftung through the Optically Controlled Spin Logic project and SFB 1238 (Project C01).

Catalytic performance of V2O5-MoO3/γ-Al2O3 catalysts for partial oxidation of n-hexane1

NASA Astrophysics Data System (ADS)

Mahmoudian, R.; Khodadadi, Z.; Mahdavi, Vahid; Salehi, Mohammed

2016-01-01

In the current study, a series of V2O5-MoO3 catalyst supported on γ-Al2O3 with various V2O5 and MoO3 loadings was prepared by wet impregnation technique. The characterization of prepared catalysts includes BET surface area, powder X-ray diffraction (XRD), and oxygen chemisorptions. The partial oxidation of n-hexane by air over V2O5-MoO3/γ-Al2O3 catalysts was carried out under flow condition in a fixed bed glass reactor. The effect of V2O5 loading, temperature, MoO3 loading, and n-hexane LHSV on the n-hexane conversion and the product selectivity were investigated. The partial oxygenated products of n-hexane oxidation were ethanol, acetic anhydride, acetic acid, and acetaldehyde. The 10% V2O5-1%MoO3/γ-Al2O3 was found in most active and selective catalyst during partial oxidation of n-hexane. The results indicated that by increasing the temperature, the n-hexane conversion increases as well, although the selectivity of the products passes through a maximum by increasing the temperature.

Fast response of sprayed vanadium pentoxide (V2O5) nanorods towards nitrogen dioxide (NO2) gas detection

NASA Astrophysics Data System (ADS)

Mane, A. A.; Suryawanshi, M. P.; Kim, J. H.; Moholkar, A. V.

2017-05-01

The V2O5 nanorods have been successfully spray deposited at optimized substrate temperature of 400 °C onto the glass substrates using vanadium trichloride (VCl3) solution of different concentrations. The effect of solution concentration on the physicochemical and NO2 gas sensing properties of sprayed V2O5 nanorods is studied at different operating temperatures and gas concentrations. The XRD study reveals the formation of V2O5 having an orthorhombic symmetry. The FE-SEM micrographs show the nanorods-like morphology of V2O5. The AFM micrographs exhibit a well covered granular surface topography. For direct allowed transition, the band gap energy values are found to be decreased from 2.45 eV to 2.42 eV. The nanorods deposited with 30 mM solution concentration shows the maximum response of 24.2% for 100 ppm NO2 gas concentration at an operating temperature of 200 °C with response and recovery times of 13 s and 140 s, respectively. Finally, the chemisorption mechanism of NO2 gas on the V2O5 nanorods is discussed.

Role of surfaces and interfaces in controlling the mechanical properties of metallic alloys.

PubMed

Lee, Won-Jong; Chia, Wen-Jui; Wang, Jinliu; Chen, Yanfeng; Vaynman, Semyon; Fine, Morris E; Chung, Yip-Wah

2010-11-02

This article explores the subtle effects of surfaces and interfaces on the mechanical properties of bulk metallic alloys using three examples: environmental effects on fatigue life, hydrogen embrittlement effects on the ductility of intermetallics, and the role of coherent precipitates in the toughness of steels. It is demonstrated that the marked degradation of the fatigue life of metals is due to the strong chemisorption of adsorbates on exposed slip steps that are formed during fatigue deformation. These adsorbates reduce the reversibility of slip, thus accelerating fatigue damage in a chemically active gas environment. For certain intermetallic alloys such as Ni(3)Al and Ni(3)Fe, the ductility depends on the ambient gas composition and the atomic ordering in these alloys, both of which govern the complex surface chemical reactions taking place in the vicinity of crack tips. Finally, it is shown that local stresses at a coherent precipitate-matrix interface can activate dislocation motion at low temperatures, thus improving the fracture toughness of bulk alloys such as steels at cryogenic temperatures. These examples illustrate the complex interplay between surface chemistry and mechanics, often yielding unexpected results.

Mechanochemical Association Reaction of Interfacial Molecules Driven by Shear.

PubMed

Khajeh, Arash; He, Xin; Yeon, Jejoon; Kim, Seong H; Martini, Ashlie

2018-05-29

Shear-driven chemical reaction mechanisms are poorly understood because the relevant reactions are often hidden between two solid surfaces moving in relative motion. Here, this phenomenon is explored by characterizing shear-induced polymerization reactions that occur during vapor phase lubrication of α-pinene between sliding hydroxylated and dehydroxylated silica surfaces, complemented by reactive molecular dynamics simulations. The results suggest that oxidative chemisorption of the α-pinene molecules at reactive surface sites, which transfers oxygen atoms from the surface to the adsorbate molecule, is the critical activation step. Such activation takes place more readily on the dehydroxylated surface. During this activation, the most strained part of the α-pinene molecules undergoes a partial distortion from its equilibrium geometry, which appears to be related to the critical activation volume for mechanical activation. Once α-pinene molecules are activated, association reactions occur between the newly attached oxygen and one of the carbon atoms in another molecule, forming ether bonds. These findings have general implications for mechanochemistry because they reveal that shear-driven reactions may occur through reaction pathways very different from their thermally induced counterparts and specifically the critical role of molecular distortion in such reactions.

The effect of fluoroalkylsilanes on tribological properties and wettability of Si-DLC coatings

NASA Astrophysics Data System (ADS)

Bystrzycka, E.; Prowizor, M.; Piwoński, I.; Kisielewska, A.; Batory, D.; Jędrzejczak, A.; Dudek, M.; Kozłowski, W.; Cichomski, M.

2018-03-01

Silicon-containing diamond-like carbon (Si-DLC) coatings were prepared on silicon wafers by Radio Frequency Plasma Enhanced Chemical Vapor Deposition (RF-PECVD) method using methane/hexamethyl-disiloxane atmosphere. Herein, we report that Si-DLC coatings can be effectively modified by fluoroalkylsilanes which results in significant enhancement of frictional and wettability properties. Two types of fluoroalkylsilanes differing in the length of fluorocarbon chains were deposited on Si-DLC coatings with the use of Vapor Phase Deposition (VPD) method. The chemical composition of Si-DLC coatings and effectiveness of modification with fluoroalkylsilanes were confirmed by Fourier Transform Infrared Spectroscopy (FTIR) and x-ray Photoelectron Spectroscopy (XPS). Frictional properties in microscale were investigated with the use of ball-on-flat apparatus operating at millinewton (mN) load range. It was found that the presence of silicon enhances the chemisorption of fluoroalkylsilanes on Si-DLC coatings by creating adsorption anchoring centers. In consequence, a decrease of adhesion and an increase of hydrophobicity along with a decrease of coefficient of friction were observed. Experimental results indicate, that tribological properties are correlated with dispersive and acid-base components of the surface free energy as well as with the work of adhesion.

Hydrogen Doping into MoO3 Supports toward Modulated Metal-Support Interactions and Efficient Furfural Hydrogenation on Iridium Nanocatalysts.

PubMed

Xie, Lifang; Chen, Ting; Chan, Hang Cheong; Shu, Yijin; Gao, Qingsheng

2018-03-16

As promising supports, reducible metal oxides afford strong metal-support interactions to achieve efficient catalysis, which relies on their band states and surface stoichiometry. In this study, in situ and controlled hydrogen doping (H doping) by means of H 2 spillover was employed to engineer the metal-support interactions in hydrogenated MoO x -supported Ir (Ir/H-MoO x ) catalysts and thus promote furfural hydrogenation to furfuryl alcohol. By easily varying the reduction temperature, the resulting H doping in a controlled manner tailors low-valence Mo species (Mo 5+ and Mo 4+ ) on H-MoO x supports, thereby promoting charge redistribution on Ir and H-MoO x interfaces. This further leads to clear differences in H 2 chemisorption on Ir, which illustrates its potential for catalytic hydrogenation. As expected, the optimal Ir/H-MoO x with controlled H doping afforded high activity (turnover frequency: 4.62 min -1 ) and selectivity (>99 %) in furfural hydrogenation under mild conditions (T=30 °C, PH2 =2 MPa), which means it performs among the best of current catalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Role of RuO2(100) in surface oxidation and CO oxidation catalysis on Ru(0001).

PubMed

Flege, Jan Ingo; Lachnitt, Jan; Mazur, Daniel; Sutter, Peter; Falta, Jens

2016-01-07

We have studied the oxidation of the Ru(0001) surface by in situ microscopy during exposure to NO2, an efficient source of atomic oxygen, at elevated temperatures. In a previous investigation [Flege et al., Phys. Rev. B: Condens. Matter Mater. Phys., 2008, 78, 165407], at O coverages exceeding 1 monolayer, using the combination of intensity-voltage (I(V)) low-energy electron microscopy (LEEM) and multiple scattering calculations for the (00) beam in the very-low-energy range (E≤ 50 eV) we identified three surface components during the initial Ru oxidation: a (1 × 1)-O chemisorption phase, the RuO2(110) oxide phase, and a surface oxide structure characterized by a trilayer O-Ru-O stacking. Here, we use dark-field LEEM imaging and micro-illumination low-energy electron diffraction in the range of 100 to 400 eV to show that this trilayer phase is actually a RuO2(100)-(1 × 1) phase with possibly mixed O and Ru surface terminations. This identification rationalizes the thermodynamic stability of this phase at elevated temperatures and is consistent with the observation of catalytic activity of the phase in CO oxidation.

Molecular Self-Assembly Driven by London Dispersion Forces

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

Li, Guo; Cooper, Valentino R; Cho, Jun-Hyung

2011-01-01

The nature and strength of intermolecular interactions are crucial to a variety of kinetic and dynamic processes at surfaces. Whereas strong chemisorption bonds are known to facilitate molecular binding, the importance of the weaker yet ubiquitous van der Waals (vdW) interactions remains elusive in most cases. Here we use first-principles calculations combined with kinetic Monte Carlo simulations to unambiguously demonstrate the vital role that vdW interactions play in molecular self-assembly, using styrene nanowire growth on silicon as a prototypical example. We find that, only when the London dispersion forces are included, accounting for the attractive parts of vdW interactions, canmore » the effective intermolecular interaction be reversed from being repulsive to attractive. Such attractive interactions, in turn, ensure the preferred growth of long wires under physically realistic conditions as observed experimentally. We further propose a cooperative scheme, invoking the application of an electric field and the selective creation of Si dangling bonds, to drastically improve the ordered arrangement of the molecular structures. The present study represents a significant step forward in the fundamental understanding and precise control of molecular self-assembly guided by London dispersion forces.« less

Kinetic studies of the stability of Pt for No oxidation: effect of sulfur and long-term aging.

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

Pazmino, J. H.; Miller, J. T.; Mulla, S. S.

2011-01-01

The stability of Pt catalysts for NO oxidation was analyzed by observing the effect of pre-adsorbed sulfur on the reaction kinetics using a series of Pt/SBA-15 catalysts with varying Pt particle sizes (ca 2-9 nm). Our results indicate that sulfur addition did not influence catalyst deactivation of any of the Pt catalysts, resulting in unchanged turnover rates (TOR) and reaction kinetics. The presence of sulfur on Pt was confirmed by X-ray absorption fine structure spectroscopy (EXAFS) under reducing environments. However, exposure of the catalyst to NO oxidation conditions displaced sulfur from the first coordination shell of Pt, yielding Pt-O bondsmore » instead. Re-reduction fully recovered the Pt-S backscattering, implying that sulfur remained near the Pt under oxidizing conditions. X-ray photoelectron spectroscopy (XPS) and chemisorption measurements confirmed the presence of sulfur near platinum. The invariance of the NO oxidation reaction to sulfur poisoning is explained by sulfur displacement to interfacial sites and/or sulfur binding on kinetically irrelevant sites. Formation of Pt oxides remains as the main source of catalyst deactivation as observed by kinetic and X-ray absorption spectroscopy (XAS) measurements.« less

Carbon monoxide detection of chemisorbed oxygen in coal and other carbonaceous materials

USGS Publications Warehouse

Hinckley, C.C.; Wiltowski, T.; Wiltowska, T.; Ellison, D.W.; Shiley, R.H.; Wu, L.

1990-01-01

The oxidation of carbon monoxide by mildly oxidized and devolatilized coal samples was studied thermogravimetrically. The oxidation was attributed to oxygen chemisorbed on inorganic components of the coals. The reaction of CO with pyrite producing carbonyl sulphide, OCS, accompanied the oxidation. A mechanism for CO oxidation is proposed in which active oxygen chemisorbed on the inorganic components of the coal directly oxidized CO to CO2, and facilitates the chemisorption of CO on the coal as carbonate. A factor, ?? = ( 11 14) [1 - ( Wn Wc)], was derived where Wn is the sample weight loss not attributed to OCS formation, and Wc is the estimated weight of evolved CO2. This quantity is proportional to the fraction of CO2 produced by the direct oxidation of CO, and was used to compare the coal samples studied. Samples of an Illinois No. 5 coal yielded average ?? values of 0.7 and those of an Illinois No. 6 coal yielded values of 0.6, indicating that in these cases, the majority of CO2 produced came from the direct oxidation of CO. The results obtained for the coal samples are compared with a selection of carbonaceous samples for which the proposed mechanism does not apply. ?? 1990.

Application of Organophosphonic Acids by One-Step Supercritical CO2 on 1D and 2D Semiconductors: Toward Enhanced Electrical and Sensing Performances.

PubMed

Bhartia, Bhavesh; Bacher, Nadav; Jayaraman, Sundaramurthy; Khatib, Salam; Song, Jing; Guo, Shifeng; Troadec, Cedric; Puniredd, Sreenivasa Reddy; Srinivasan, Madapusi Palavedu; Haick, Hossam

2015-07-15

Formation of dense monolayers with proven atmospheric stability using simple fabrication conditions remains a major challenge for potential applications such as (bio)sensors, solar cells, surfaces for growth of biological cells, and molecular, organic, and plastic electronics. Here, we demonstrate a single-step modification of organophosphonic acids (OPA) on 1D and 2D structures using supercritical carbon dioxide (SCCO2) as a processing medium, with high stability and significantly shorter processing times than those obtained by the conventional physisorption-chemisorption method (2.5 h vs 48-60 h).The advantages of this approach in terms of stability and atmospheric resistivity are demonstrated on various 2D materials, such as indium-tin-oxide (ITO) and 2D Si surfaces. The advantage of the reported approach on electronic and sensing devices is demonstrated by Si nanowire field effect transistors (SiNW FETs), which have shown a few orders of magnitude higher electrical and sensing performances, compared with devices obtained by conventional approaches. The compatibility of the reported approach with various materials and its simple implementation with a single reactor makes it easily scalable for various applications.

Niobium Nitride Nb4N5 as a New High‐Performance Electrode Material for Supercapacitors

PubMed Central

Cui, Houlei; Zhu, Guilian; Liu, Xiangye; Liu, Fengxin; Xie, Yian; Yang, Chongyin; Lin, Tianquan; Gu, Hui

2015-01-01

Supercapacitors suffer either from low capacitance for carbon or derivate electrodes or from poor electrical conductivity and electrochemical stability for metal oxide or conducting polymer electrodes. Transition metal nitrides possess fair electrical conductivity but superior chemical stability, which may be desirable candidates for supercapacitors. Herein, niobium nitride, Nb4N5, is explored to be an excellent capacitive material for the first time. An areal capacitance of 225.8 mF cm−2, with a reasonable rate capability (60.8% retention from 0.5 to 10 mA cm−2) and cycling stability (70.9% retention after 2000 cycles), is achieved in Nb4N5 nanochannels electrode with prominent electrical conductivity and electrochemical activity. Faradaic pseudocapacitance is confirmed by the mechanistic studies, deriving from the proton incorporation/chemisorption reaction owing to the copious +5 valence Nb ions in Nb4N5. Moreover, this Nb4N5 nanochannels electrode with an ultrathin carbon coating exhibits nearly 100% capacitance retention after 2000 CV cycles, which is an excellent cycling stability for metal nitride materials. Thus, the Nb4N5 nanochannels are qualified for a candidate for supercapacitors and other energy storage applications. PMID:27980920

Electricity from Coal Combustion: Improving the hydrophobicity of oxidized coals

NASA Astrophysics Data System (ADS)

Seehra, Mohindar; Singh, Vivek

2011-03-01

To reduce pollution and improve efficiency, undesirable mineral impurities in coals are usually removed in coal preparation plants prior to combustion first by crushing and grinding coals followed by gravity separation using surfactant aided water flotation. However certain coals in the US are not amendable to this process because of their poor flotation characteristics resulting in a major loss of an energy resource. This problem has been linked to surface oxidation of mined coals which make these coals hydrophilic. In this project, we are investigating the surface and water flotation properties of the eight Argonne Premium (AP) coals using x-ray diffraction, IR spectroscopy and zeta potential measurements. The role of the surface functional groups, (phenolic -OH and carboxylic -COOH), produced as a result of chemisorptions of O2 on coals in determining their flotation behavior is being explored. The isoelectric point (IEP) in zeta potential measurements of good vs. poor floaters is being examined in order to improved the hydrophobicity of poor floating coals (e.g. Illinois #6). Results from XRD and IR will be presented along with recent findings from zeta potential measurements, and use of additives to improve hydrophobicity. Supported by USDOE/CAST, Contract #DE-FC26-05NT42457.

Characterization of Hydrogen Interactions with δ-Pu using Electronic Structure Theory

NASA Astrophysics Data System (ADS)

Taylor, Christopher D.; Hernandez, Sarah C.

2012-02-01

The generalized gradient approximation to density functional theory was used to study surface, bulk, defect, and reaction states of hydrogen in δ-Pu. The quasi-disordered anti-ferromagnetic arrangement gave a volume of 24.1 å^3 and a bulk modulus of 48.1 GPa for δ-Pu, in reasonable agreement with the experimental values of 24.9 å^3 and 30-35 GPa. This arrangement was thus subsequently used for all calculations. We have determined that hydrogen interactions with δ-Pu are exothermic in character at all levels ranging from dissociative chemisorption to interstitial absorption, the formation of hydrogen-vacancy complexes, and generation of a hydride phase. The exothermic character of these interactions appears to be the reason for the rapid hydriding reaction, which has been determined experimentally to be essentially a barrierless process. The anionic character is observed to be retained. Our studies also indicate that vacancies do not appear to be strong traps for hydrogen, since the interstitial absorption sites are exothermic in nature. We will propose a scheme by which hydrogen interacts with Pu. Results will be compared with previous studies in the literature where available.

Orientation-free and differentially pumped addition of a low-flux reactive gas beam to a surface analysis system.

PubMed

Harthcock, Colin; Jahanbekam, Abdolreza; Eskelsen, Jeremy R; Lee, David Y

2016-11-01

We describe an example of a piecewise gas chamber that can be customized to incorporate a low flux of gas-phase radicals with an existing surface analysis chamber for in situ and stepwise gas-surface interaction experiments without any constraint in orientation. The piecewise nature of this gas chamber provides complete angular freedom and easy alignment and does not require any modification of the existing surface analysis chamber. In addition, the entire gas-surface system is readily differentially pumped with the surface chamber kept under ultra-high-vacuum during the gas-surface measurements. This new design also allows not only straightforward reconstruction to accommodate the orientation of different surface chambers but also for the addition of other desired features, such as an additional pump to the current configuration. Stepwise interaction between atomic oxygen and a highly ordered pyrolytic graphite surface was chosen to test the effectiveness of this design, and the site-dependent O-atom chemisorption and clustering on the graphite surface were resolved by a scanning tunneling microscope in the nm-scale. X-ray photoelectron spectroscopy was used to further confirm the identity of the chemisorbed species on the graphite surface as oxygen.

Investigation Of A Tin-Lithium Alloy As A Liquid Plasma-Facing Material

NASA Astrophysics Data System (ADS)

Sandefur, Heather; Ruzic, David; Kolasinski, Robert; Buchenauer, Dean; Sandia National Laboratories Collaboration; University of Illinois Collaboration

2017-10-01

Sn-Li is a low melting-point alloy that has been identified as a material with favorable performance in plasma material interaction studies. While lithium is a low Z material with a demonstrated ability to absorb impinging ions, pure lithium is plagued by high evaporation rates in the liquid phase. The Sn-Li alloy is a more stable alternative that provides a lower rate of evaporative flux due to the high vapor pressure of tin. In the liquid phase, the bulk segregation of lithium to the surface of the material has also been observed. While the alloy is of considerable interest, little data has been collected on its surface chemistry in a plasma environment. In order to expand the existing body of knowledge in this area, samples of an 80 percent Sn-20 percent Li alloy were prepared and analyzed in order to assess the surface composition and degree of lithium segregation in the liquid phase. The Angle-Resolved Ion Energy Spectrometer (ARIES) at Sandia National Laboratories was used to probe the surfaces of the alloy using the low energy ion scattering method. The lithium coverage at the surface was measured, and the material's affinity for hydrogen chemisorption was investigated.

Exploring the low friction of diamond-like carbon films in carbon dioxide atmosphere by experiments and first-principles calculations

NASA Astrophysics Data System (ADS)

Huo, Lei; Wang, Shunhua; Pu, Jibin; Sun, Junhui; Lu, Zhibin; Ju, Pengfei; Wang, Liping

2018-04-01

The friction behavior and the mechanism of DLC films in CO2 atmosphere are rarely explored, which is a significant obstacle for the potential practical application of DLC films in primarily CO2 environment. Here, the experiments and first-principles calculations are performed to simultaneously investigate this theme. We find that DLC films in CO2 atmosphere exhibit astoundingly low friction coefficient compared with in ambient air and vacuum atmospheres. The XPS and Raman spectrums demonstrate the possibly activation of CO2 molecule in the shearing interfaces, which may be critical for the low friction of DLC films in CO2 atmosphere. The calculated results reveal that the lactone groups can easily form during the horizontally chemisorption of CO2 molecule on the DLC surface, which is energetic and is a favorable process under the interfacial stress. Because of the presence of the lone-pairs of the lactone group, the lactone-terminated surfaces appear to be responsible for the low friction of DLC films in CO2 atmosphere. The studies may open up the possibility for DLC films usage in Mars applications.

Adsorption of Azo-Dye Orange II from Aqueous Solutions Using a Metal-Organic Framework Material: Iron- Benzenetricarboxylate

PubMed Central

Rojas García, Elizabeth; López Medina, Ricardo; May Lozano, Marcos; Hernández Pérez, Isaías; Valero, Maria J.; Maubert Franco, Ana M.

2014-01-01

A Metal-Organic Framework (MOF), iron-benzenetricarboxylate (Fe(BTC)), has been studied for the adsorptive removal of azo-dye Orange II from aqueous solutions, where the effect of various parameters was tested and isotherm and kinetic models were suggested. The adsorption capacities of Fe(BTC) were much higher than those of an activated carbon. The experimental data can be best described by the Langmuir isotherm model (R2 > 0.997) and revealed the ability of Fe(BTC) to adsorb 435 mg of Orange II per gram of adsorbent at the optimal conditions. The kinetics of Orange II adsorption followed a pseudo-second-order kinetic model, indicating the coexistence of physisorption and chemisorption, with intra-particle diffusion being the rate controlling step. The thermodynamic study revealed that the adsorption of Orange II was feasible, spontaneous and exothermic process (−25.53 kJ·mol−1). The high recovery of the dye showed that Fe(BTC) can be employed as an effective and reusable adsorbent for the removal of Orange II from aqueous solutions and showed the economic interest of this adsorbent material for environmental purposes. PMID:28788289

Plasmon-resonant nanorods as multimodal agents for two-photon luminescent imaging and photothermal therapy

NASA Astrophysics Data System (ADS)

Huff, Terry B.; Hansen, Matthew N.; Tong, Ling; Zhao, Yan; Wang, Haifeng; Zweifel, Daniel A.; Cheng, Ji-Xin; Wei, Alexander

2007-02-01

Plasmon-resonant gold nanorods have outstanding potential as multifunctional agents for image-guided therapies. Nanorods have large absorption cross sections at near-infrared (NIR) frequencies, and produce two-photon luminescence (TPL) when excited by fs-pulsed laser irradiation. The TPL signals can be detected with single-particle sensitivity, enabling nanorods to be imaged in vivo while passing through blood vessels at subpicomolar concentrations. Furthermore, cells labeled with nanorods become highly susceptible to photothermal damage when irradiated at plasmon resonance, often resulting in a dramatic blebbing of the cell membrane. However, the straightforward application of gold nanorods for cell-specific labeling is obstructed by the presence of CTAB, a cationic surfactant carried over from nanorod synthesis which also promotes their nonspecific uptake into cells. Careful exchange and replacement of CTAB can be achieved by introducing oligoethyleneglycol (OEG) units capable of chemisorption onto nanorod surfaces by in situ dithiocarbamate formation, a novel method of surface functionalization. Nanorods with a dense coating of methyl-terminated OEG chains are shielded from nonspecific cell uptake, whereas nanorods functionalized with folate-terminated OEG chains accumulate on the surface of tumor cells overexpressing their cognate receptor, with subsequent delivery of photoinduced cell damage at low laser fluence.

DFT study on the adsorption of diethyl, ethyl methyl, and dimethyl ethers on the surface of gallium doped graphene

NASA Astrophysics Data System (ADS)

Shokuhi Rad, Ali; Sani, Emad; Binaeian, Ehsan; Peyravi, Majid; Jahanshahi, Mohsen

2017-04-01

In this study, we used density functional theory (DFT) to search on the adsorption properties of three important compounds of ether family; diethyl ether (DEE), ethyl methyl ether (EME), and dimethyl ether (DME) on the surface of Gallium doped graphene (GaG). We used three functionals (B3LYP, wb97xd, and MPW1PW91) for optimization and calculation of adsorption energy. After fully optimization, we scrutinized on the charge allocations on the adsorbed ethers as well as GaG (at the area of interaction) based on natural bond orbitals (NBO). Besides, we have calculated the amount of charge transfer upon adsorption of each analyte. We revel that GaG is an ideal adsorbent for chemisorption of all above-mentioned ethers. There is a little difference between the values of adsorption; -123.5, -120, and -118.3 kJ/mol (based on wb97xd) for DEE, EME, and DME, respectively. We found significant changes in the electronic structure of both adsorbent and adsorbate upon adsorption. Moreover, results of charge analyses confirm GaG is a p-type semiconductor.

Preparation of NiCoP Hollow Quasi-Polyhedra and Their Electrocatalytic Properties for Hydrogen Evolution in Alkaline Solution.

PubMed

Li, Yapeng; Liu, Jindou; Chen, Chen; Zhang, Xiaohua; Chen, Jinhua

2017-02-22

Double metal phosphide (NiCoP) with hollow quasi-polyhedron structure was prepared by acidic etching and precipitation of ZIF-67 polyhedra and further phosphorization treatment with NaH 2 PO 2 . The morphology and microstructure of NiCoP quasi-polyhedron and its precursors were investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and a micropore and chemisorption analyzer. Electrocatalytic properties were examined by typical electrochemical methods, such as linear sweep voltammetry, cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy in 1.0 M KOH aqueous solution. Results reveal that, compared with CoP hollow polyhedra, NiCoP hollow quasi-polyhedra exhibit better electrochemical properties for hydrogen evolution with a low onset overpotential of 74 mV and a small Tafel slope of 42 mV dec -1 . When the current density is 10 mA cm -2 , the corresponding overpotential is merely 124 mV, and 93% of its electrocatalytic activity can be maintained for 12 h. This indicates that NiCoP with hollow quasi-polyhedron structure, bimetallic merit, and low cost may be a good candidate as electrocatalyst in the practical application of hydrogen evolution.

Revealing the Adsorption Mechanisms of Nitroxides on Ultrapure, Metallicity-Sorted Carbon Nanotubes

PubMed Central

2014-01-01

Carbon nanotubes are a natural choice as gas sensor components given their high surface to volume ratio, electronic properties, and capability to mediate chemical reactions. However, a realistic assessment of the interaction of the tube wall and the adsorption processes during gas phase reactions has always been elusive. Making use of ultraclean single-walled carbon nanotubes, we have followed the adsorption kinetics of NO2 and found a physisorption mechanism. Additionally, the adsorption reaction directly depends on the metallic character of the samples. Franck–Condon satellites, hitherto undetected in nanotube–NOx systems, were resolved in the N 1s X-ray absorption signal, revealing a weak chemisorption, which is intrinsically related to NO dimer molecules. This has allowed us to identify that an additional signal observed in the higher binding energy region of the core level C 1s photoemission signal is due to the C=O species of ketene groups formed as reaction byproducts . This has been supported by density functional theory calculations. These results pave the way toward the optimization of nanotube-based sensors with tailored sensitivity and selectivity to different species at room temperature. PMID:24404865

Electronic properties and reactivity of Pt-doped carbon nanotubes.

PubMed

Tian, Wei Quan; Liu, Lei Vincent; Wang, Yan Alexander

2006-08-14

The structures of the (5,5) single-walled carbon nanotube (SWCNT) segments with hemispheric carbon cages capped at the ends (SWCNT rod) and the Pt-doped SWCNT rods have been studied within density functional theory. Our theoretical studies find that the hemispheric cages introduce localized states on the caps. The cap-Pt-doped SWCNT rods can be utilized as sensors because of the sensitivity of the doped Pt atom. The Pt-doped SWCNT rods can also be used as catalysts, where the doped Pt atom serves as the enhanced and localized active center on the SWCNT. The adsorptions of C(2)H(4) and H(2) on the Pt atom in the Pt-doped SWCNT rods reveal different adsorption characteristics. The adsorption of C(2)H(4) on the Pt atom in all of the three Pt-doped SWCNT rods studied (cap-end-doped, cap-doped, and wall-doped) is physisorption with the strongest interaction occurring in the middle of the sidewall of the SWCNT. On the other hand, the adsorption of H(2) on the Pt atom at the sidewall of the SWCNT is chemisorption resulting in the decomposition of H(2), and the adsorption of H(2) at the hemispheric caps is physisorption.

Time-independent quantum dynamics for diatom-surface scattering

NASA Astrophysics Data System (ADS)

Saalfrank, Peter; Miller, William H.

1993-06-01

Two time-independent quantum reactive scattering methods, namely, the S-matrix Kohn technique to compute the full S-matrix, and the absorbing boundary Green's function method to compute cumulative reaction probabilities, are applied here to the case of diatom-surface scattering. In both cases a discrete variable representation for the operators is used. We test the methods for two- and three-dimensional uncorrugated potential energy surfaces, which have been used earlier by Halstead et al. [J. Chem. Phys. 93, 2359 (1990)] and by Sheng et al. [J. Chem. Phys. 97, 684 (1992)] in studies of H2 dissociating on metal substrates with theoretical techniques different from those applied here. We find overall but not always perfect agreement with these earlier studies. Based on ab initio data and experiment, a new, six-dimensional potential energy surface for the dissociative chemisorption of H2 on Ni(100) is proposed. Two- and three-dimensional cuts through the new potential are performed to illustrate special dynamical aspects of this particular molecule-surface reaction: (i) the role of corrugation effects, (ii) the importance of the ``cartwheel'' rotation of H2, and (iii) the role of the ``helicopter'' degree of freedom for the adsorbing molecule.

Investigation of the Interaction between Perovskite Films with Moisture via in Situ Electrical Resistance Measurement.

PubMed

Hu, Long; Shao, Gang; Jiang, Tao; Li, Dengbing; Lv, Xinlin; Wang, Hongya; Liu, Xinsheng; Song, Haisheng; Tang, Jiang; Liu, Huan

2015-11-18

Organometal halide perovskites have recently emerged as outstanding semiconductors for solid-state optoelectronic devices. Their sensitivity to moisture is one of the biggest barriers to commercialization. In order to identify the effect of moisture in the degradation process, here we combined the in situ electrical resistance measurement with time-resolved X-ray diffraction analysis to investigate the interaction of CH3NH3PbI(3-x)Cl(x) perovskite films with moisture. Upon short-time exposure, the resistance of the perovskite films decreased and it could be fully recovered, which were ascribed to a mere chemisorption of water molecules, followed by the reversible hydration into CH3NH3PbI(3-x)Cl(x)·H2O. Upon long-time exposure, however, the resistance became irreversible due to the decomposition into PbI2. The results demonstrated the formation of monohydrated intermediate phase when the perovskites interacted with moisture. The role of moisture in accelerating the thermal degradation at 85 °C was also demonstrated. Furthermore, our study suggested that the perovskite films with fewer defects may be more inherently resistant to moisture.

Sodium-promoted Pd/TiO2 for catalytic oxidation of formaldehyde at ambient temperature.

PubMed

Zhang, Changbin; Li, Yaobin; Wang, Yafei; He, Hong

2014-05-20

Catalytic oxidation of formaldehyde (HCHO) to CO2 at ambient conditions is of great interest for indoor HCHO purification. Here, we report that sodium-doped Pd/TiO2 is a highly effective catalyst for the catalytic oxidation of HCHO at room temperature. It was observed that Na doping has a dramatic promotion effect on the Pd/TiO2 catalyst and that nearly 100% HCHO conversion could be achieved over the 2Na-Pd/TiO2 catalyst at a GHSV of 95000 h(-1) and HCHO inlet concentration of 140 ppm at 25 °C. The mechanism of the Na-promotion effect was investigated by using Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), CO chemisorption, Temperature-programmed reduction by H2 (H2-TPR), X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption of O2 (O2-TPD) methods. The results showed that Na species addition can induce and further stabilize a negatively charged and well-dispersed Pd species, which then facilitates the activation of H2O and chemisorbed oxygen, therefore resulting in the high performance of the 2Na-Pd/TiO2 catalyst for the ambient HCHO destruction.

Synergistic Effect of Superhydrophobicity and Oxidized Layers on Corrosion Resistance of Aluminum Alloy Surface Textured by Nanosecond Laser Treatment.

PubMed

Boinovich, Ludmila B; Emelyanenko, Alexandre M; Modestov, Alexander D; Domantovsky, Alexandr G; Emelyanenko, Kirill A

2015-09-02

We report a new efficient method for fabricating a superhydrophobic oxidized surface of aluminum alloys with enhanced resistance to pitting corrosion in sodium chloride solutions. The developed coatings are considered very prospective materials for the automotive industry, shipbuilding, aviation, construction, and medicine. The method is based on nanosecond laser treatment of the surface followed by chemisorption of a hydrophobic agent to achieve the superhydrophobic state of the alloy surface. We have shown that the surface texturing used to fabricate multimodal roughness of the surface may be simultaneously used for modifying the physicochemical properties of the thick surface layer of the substrate itself. Electrochemical and wetting experiments demonstrated that the superhydrophobic state of the metal surface inhibits corrosion processes in chloride solutions for a few days. However, during long-term contact of a superhydrophobic coating with a solution, the wetted area of the coating is subjected to corrosion processes due to the formation of defects. In contrast, the combination of an oxide layer with good barrier properties and the superhydrophobic state of the coating provides remarkable corrosion resistance. The mechanisms for enhancing corrosion protective properties are discussed.

Detection of free nickel monocarbonyl, NiCO: rotational spectrum and structure.

PubMed

Yamazaki, Emi; Okabayashi, Toshiaki; Tanimoto, Mitsutoshi

2004-02-04

Unsaturated transition metal carbonyls are important in processes such as organometallic synthesis, homogeneous catalysis, and photochemical decomposition of organometallics. In particular, a metal monocarbonyl offers a zeroth-order model for interpreting the chemisorption of a CO molecule on a metal surface in catalytic activation processes. Quite large numbers of theoretical papers have appeared which predict spectroscopic and structural properties of transition metal carbonyls. The nickel monocarbonyl NiCO has been one of the metal carbonyls most extensively studied by the theoretical calculations. At least 50 theoretical studies have been published on this simplest transition metal carbonyl up to the present time. However, experimental evidence of NiCO is much more sparse than theoretical predictions, and the actual structure of NiCO has never been determined by any experimental methods. This Communication reports the first preparation of free nickel monocarbonyl and observation of its rotational transitions. The NiCO molecule was generated by the sputtering reaction of a Ni cathode in the presence of CO. The accurate bond lengths of Ni-C and C-O were experimentally determined from isotopic data and were compared with the theoretical predictions for the first time.

Biocompatible Materials Based on Self-Assembling Peptides on Ti25Nb10Zr Alloy: Molecular Structure and Organization Investigated by Synchrotron Radiation Induced Techniques.

PubMed

Secchi, Valeria; Franchi, Stefano; Santi, Marta; Vladescu, Alina; Braic, Mariana; Skála, Tomáš; Nováková, Jaroslava; Dettin, Monica; Zamuner, Annj; Iucci, Giovanna; Battocchio, Chiara

2018-03-07

In this work, we applied advanced Synchrotron Radiation (SR) induced techniques to the study of the chemisorption of the Self Assembling Peptide EAbuK16, i.e., H-Abu-Glu-Abu-Glu-Abu-Lys-Abu-Lys-Abu-Glu-Abu-Glu-Abu-Lys-Abu-Lys-NH₂ that is able to spontaneously aggregate in anti-parallel β-sheet conformation, onto annealed Ti25Nb10Zr alloy surfaces. This synthetic amphiphilic oligopeptide is a good candidate to mimic extracellular matrix for bone prosthesis, since its β-sheets stack onto each other in a multilayer oriented nanostructure with internal pores of 5-200 nm size. To prepare the biomimetic material, Ti25Nb10Zr discs were treated with aqueous solutions of EAbuK16 at different pH values. Here we present the results achieved by performing SR-induced X-ray Photoelectron Spectroscopy (SR-XPS), angle-dependent Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy, FESEM and AFM imaging on Ti25Nb10Zr discs after incubation with self-assembling peptide solution at five different pH values, selected deliberately to investigate the best conditions for peptide immobilization.

Adsorption of small molecules on the [Zn-Zn]2+ linkage in zeolite. A DFT study of ferrierite

NASA Astrophysics Data System (ADS)

Benco, Lubomir

2017-02-01

In zeolites monovalent Zn(I) forms a sub-nano particles [Zn-Zn]2+ stabilized in rings of the zeolite framework, which exhibit interesting catalytic properties. This work reports on adsorption properties of [Zn-Zn]2+ particles in zeolite ferrierite investigated for a set of probing diatomic (N2, O2, H2, CO, NO) and triatomic (CO2, N2O, NO2, H2O) molecules using dispersion-corrected DFT. Three [Zn-Zn]2+ sites are compared differing in the location and stability. On all sites molecules form physisorbed clusters with the molecule connected on-top of the Zn-Zn linkage. In physisorbed clusters adsorption induces only slight change of bonding and the geometry of the Zn-Zn linkage. Some molecules can form stable chemisorbed clusters in which the molecule is integrated between two Zn+ cations. The sandwich-like chemisorption causes pronounced changes of bonding and can lead to the transfer of the electron density between two Zn+ cations and to a change of the oxidation state. The knowledge of bonding of small molecules can help understanding of the mechanism of conversion reactions catalyzed by sub-nano [Zn-Zn] particles.

Arsenic removal in aqueous solution by a novel Fe-Mn modified biochar composite: Characterization and mechanism.

PubMed

Lin, Lina; Qiu, Weiwen; Wang, Di; Huang, Qing; Song, Zhengguo; Chau, Henry Wai

2017-10-01

The aim of this study was to develop a cost-effective method for As removal from aqueous systems. To this end, pristine biochar (BC) was impregnated with Fe-Mn oxides and a comparative analysis was conducted on the adsorption capacities of BC, Fe-Mn binary oxide (FMO), and Fe/Mn modified biochar (FMBC). The ferromanganese oxides increased the specific surface areas of BC. FMBC presented greater adsorption of As (Q max = 8.25mgg -1 ) than FMO and BC. Energy dispersive spectrometer analysis and electron microscope scanning revealed numerous pores of FMBC with the existence of Fe-Mn oxide using. Distinguished binding energy shifting of the As3d, Fe2p, O1s, and Mn2p3/2 regions after As sorption were found, indicating that Mn(III) oxidation and interaction of oxygen-containing function groups in the FMBC promoted the conversion of As(III) to As(V). Furthermore, chemisorption was found to be the main mechanism for As sorption on FMBC. Thus, the results suggest that FMBC could be used as an inexpensive and highly efficient adsorbent for As removal from water environment. Copyright © 2017 Elsevier Inc. All rights reserved.

Removal of arsenic from water using manganese (III) oxide: Adsorption of As(III) and As(V).

PubMed

Babaeivelni, Kamel; Khodadoust, Amid P

2016-01-01

Removal of arsenic from water was evaluated with manganese (III) oxide (Mn2O3) as adsorbent. Adsorption of As(III) and As(V) onto Mn2O3 was favorable according to the Langmuir and Freundlich adsorption equilibrium equations, while chemisorption of arsenic occurred according to the Dubinin-Radushkevich equation. Adsorption parameters from the Langmuir, Freundlich, and Temkin equations showed a greater adsorption and removal of As(III) than As(V) by Mn2O3. Maximum removal of As(III) and As(V) occurred at pH 3-9 and at pH 2, respectively, while removal of As(V) in the pH range of 6-9 was 93% (pH 6) to 61% (pH 9) of the maximum removal. Zeta potential measurements for Mn2O3 in As(III) was likely converted to As(V) solutions indicated that As(III) was likely converted to As(V) on the Mn2O3 surface at pH 3-9. Overall, the effective Mn2O3 sorbent rapidly removed As(III) and As(V) from water in the pH range of 6-9 for natural waters.

Niobium Nitride Nb4N5 as a New High-Performance Electrode Material for Supercapacitors.

PubMed

Cui, Houlei; Zhu, Guilian; Liu, Xiangye; Liu, Fengxin; Xie, Yian; Yang, Chongyin; Lin, Tianquan; Gu, Hui; Huang, Fuqiang

2015-12-01

Supercapacitors suffer either from low capacitance for carbon or derivate electrodes or from poor electrical conductivity and electrochemical stability for metal oxide or conducting polymer electrodes. Transition metal nitrides possess fair electrical conductivity but superior chemical stability, which may be desirable candidates for supercapacitors. Herein, niobium nitride, Nb 4 N 5 , is explored to be an excellent capacitive material for the first time. An areal capacitance of 225.8 mF cm -2 , with a reasonable rate capability (60.8% retention from 0.5 to 10 mA cm -2 ) and cycling stability (70.9% retention after 2000 cycles), is achieved in Nb 4 N 5 nanochannels electrode with prominent electrical conductivity and electrochemical activity. Faradaic pseudocapacitance is confirmed by the mechanistic studies, deriving from the proton incorporation/chemisorption reaction owing to the copious +5 valence Nb ions in Nb 4 N 5 . Moreover, this Nb 4 N 5 nanochannels electrode with an ultrathin carbon coating exhibits nearly 100% capacitance retention after 2000 CV cycles, which is an excellent cycling stability for metal nitride materials. Thus, the Nb 4 N 5 nanochannels are qualified for a candidate for supercapacitors and other energy storage applications.

Post-synthetic halide conversion and selective halogen capture in hybrid perovskites† †Electronic supplementary information (ESI) available. CCDC 1048945–1048947. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc01135c

PubMed Central

Solis-Ibarra, D.; Smith, I. C.

2015-01-01

Reaction with halogen vapor allows us to post-synthetically exchange halides in both three- (3D) and two-dimensional (2D) organic–inorganic metal-halide perovskites. Films of 3D Pb–I perovskites cleanly convert to films of Pb–Br or Pb–Cl perovskites upon exposure to Br2 or Cl2 gas, respectively. This gas–solid reaction provides a simple method to produce the high-quality Pb–Br or Pb–Cl perovskite films required for optoelectronic applications. Reactivity with halogens can be extended to the organic layers in 2D metal-halide perovskites. Here, terminal alkene groups placed between the inorganic layers can capture Br2 gas through chemisorption to form dibromoalkanes. This reaction's selectivity for Br2 over I2 allows us to scrub Br2 to obtain high-purity I2 gas streams. We also observe unusual halogen transfer between the inorganic and organic layers within a single perovskite structure. Remarkably, the perovskite's crystallinity is retained during these massive structural rearrangements. PMID:29218171

Treatment of crude oil-contaminated water with chemically modified natural fiber

NASA Astrophysics Data System (ADS)

Onwuka, Jude Chinedu; Agbaji, Edith Bolanle; Ajibola, Victor Olatunji; Okibe, Friday Godwin

2018-06-01

The dependence of Nigerian Government on foreign technology for oil spill cleanup in its water bodies does not add local content value in the development of the Nation's economy. Acetylation of natural cellulose gives a material with high sorption capacity for oil in water. This research investigates crude oil sorption from water using acetylated and unacetylated lignocellulose. Oil palm empty fruit bunch (OPEFB) and cocoa pod (CP) were acetylated under mild conditions. The acetylated (modified) and unacetylated (unmodified) sorbents were used to sorb oil from water, and their sorption capacities and mechanisms were compared. Paired t test showed there was significant difference in the sorption capacities of modified and unmodified sorbents. Sorption of oil from water was found to be time and concentration dependent. Equilibrium studies showed that CP has higher sorption capacity than OPEFB and acetylation enhanced the crude sorption capacities of the sorbents. Crude oil sorption from water is a monolayer process that might have progressed from multilayer processes. Kinetic studies showed that sorption of crude oil by the sorbents was diffusion-controlled with the aid of physisorption and chemisorption mechanisms. Fourier transform infrared and scanning electron microscope analyses showed clear evidence of successful acetylation and oil sorption.

Mechanism of Hydrophilicity by Radiation-Induced Surface Activation

NASA Astrophysics Data System (ADS)

Honjo, Yoshio; Furuya, Masahiro; Takamasa, Tomoji; Okamoto, Koji

When a metal oxide is irradiated by gamma rays, the irradiated surface becomes hydrophilic. This surface phenomenon is called as radiation-induced surface activation (RISA) hydrophilicity. In order to investigate gamma ray-induced and photoinduced hydrophilicity, the contact angles of water droplets on a titanium dioxide surface were measured in terms of irradiation intensity and time for gamma rays of cobalt-60 and for ultraviolet rays. Reciprocals of the contact angles increased in proportion to the irradiation time before the contact angles reached its super-hydrophilic state. The irradiation time dependency is equal to each other qualitatively. In addition, an effect of ambient gas was investigated. In pure argon gas, the contact angle remains the same against the irradiation time. This clearly indicates that certain humidity is required in ambient gas to take place of RISA hydrophilicity. A single crystal titanium dioxide (100) surface was analyzed by X-ray photoelectron spectrometry (XPS). After irradiation with gamma rays, a peak was found in the O1s spectrum, which indicates the adsorption of dissociative water to a surface 5-fold coordinate titanium site, and the formation of a surface hydroxyl group. We conclude that the RISA hydrophilicity is caused by chemisorption of the hydroxyl group on the surface.

Inhibition of calcite precipitation by natural organic material: Kinetics, mechanism, and thermodynamics

USGS Publications Warehouse

Lin, Y.-P.; Singer, P.C.; Aiken, G.R.

2005-01-01

The inhibition of calcite precipitation by natural organic material (NOM) in solutions seeded with calcite was investigated using a pH-stat system. Experiments were carried out using three NOMs with different physical/chemical properties. For each of the materials, inhibition was found to be more effective at lower carbonate/calcium ratios and lower pH values. The reduction in the precipitation rate could be explained by a Langmuir adsorption model using a conditional equilibrium constant. By identification of the type of site on the NOM molecules that is involved in the adsorption reaction, the "conditional" equilibrium constants obtained at different solution compositions converged to a single "nonconditional" value. The thermodynamic data determined at 25??C and 1 atm suggest that the interaction between NOM molecules and the calcite surface is chemisorptive in nature and that adsorption is an endothermic reaction driven by the entropy change. The greatest degree of inhibition was observed for the NOM with the highest molecular weight and aromatic carbon content. For a given type of NOM, the degree of inhibition of calcite precipitation was dictated by the balance between the enthalpy change and the entropy change of the adsorption reaction. ?? 2005 American Chemical Society.

Variable (Tg, Ts) Measurements of Alkane Dissociative Sticking Coefficients

NASA Astrophysics Data System (ADS)

Valadez, Leticia; Dewitt, Kristy; Abbott, Heather; Kolasinski, Kurt; Harrision, Ian

2006-03-01

Dissociative sticking coefficients S(Tg, Ts) for CH4 and C2H6 on Pt(111) have been measured as a function of gas temperature (Tg) and surface temperature (Ts) using an effusive molecular beam. Microcanonical unimolecular rate theory (MURT) was employed to extract transition state characteristics [e.g., E0(CH4) = 52.5±3.5 kJ/mol-1 and E0(C2H6) = 26.5±3 kJ/mol-1]. MURT allows our S(Tg, Ts) values to be directly compared to other supersonic molecular beam and thermal equilibrium sticking measurements. The S(Tg, Ts) depend strongly on Ts, however, only for CH4 is a strong Tg dependence observed. The fairly weak Tg dependence for C2H6 suggests that vibrational mode specific behavior and/or molecular rotations play stronger roles in the dissociative chemisorption of C2H6 than they do for CH4. Interestingly, thermal S(Tg=Ts) predictions based on MURT modeling of our CH4/Pt(111) data are three orders of magnitude higher than recent thermal equilibrium measurements on supported Pt nanocrystallite catalysts [J. M. Wei, E. Iglesia, J. Phys. Chem. B 108, 4094 (2004)].

Modified Ni-Cu catalysts for ethanol steam reforming

NASA Astrophysics Data System (ADS)

Dan, M.; Mihet, M.; Almasan, V.; Borodi, G.; Katona, G.; Muresan, L.; Lazar, M. D.

2013-11-01

Three Ni-Cu catalysts, having different Cu content, supported on γ-alumina were synthesized by wet co-impregnation method, characterized and tested in the ethanol steam reforming (ESR) reaction. The catalysts were characterized for determination of: total surface area and porosity (N2 adsorption - desorption using BET and Dollimer Heal methods), Ni surface area (hydrogen chemisorption), crystallinity and Ni crystallites size (X-Ray Diffraction), type of catalytic active centers (Hydrogen Temperature Programmed Reduction). Total surface area and Ni crystallites size are not significantly influenced by the addition of Cu, while Ni surface area is drastically diminished by increasing of Cu concentration. Steam reforming experiments were performed at atmospheric pressure, temperature range 150-350°C, and ethanol - water molar ration of 1 at 30, using Ar as carrier gas. Ethanol conversion and hydrogen production increase by the addition of Cu. At 350°C there is a direct connection between hydrogen production and Cu concentration. Catalysts deactivation in 24h time on stream was studied by Transmission Electron Microscopy (TEM) and temperature-programmed reduction (TPR) on used catalysts. Coke deposition was observed at all studied temperatures; at 150°C amorphous carbon was evidenced, while at 350°C crystalline, filamentous carbon is formed.

Tailoring density and optical and thermal behavior of gold surfaces and nanoparticles exploiting aromatic dithiols.

PubMed

Bruno, Giovanni; Babudri, Francesco; Operamolla, Alessandra; Bianco, Giuseppe V; Losurdo, Maria; Giangregorio, Maria M; Hassan Omar, Omar; Mavelli, Fabio; Farinola, Gianluca M; Capezzuto, Pio; Naso, Francesco

2010-06-01

Self-assembled monolayers (SAMs) derived of 4-methoxy-terphenyl-3'',5''-dimethanethiol (TPDMT) and 4-methoxyterphenyl-4''-methanethiol (TPMT) have been prepared by chemisorption from solution onto gold thin films and nanoparticles. The SAMs have been characterized by spectroscopic ellipsometry, Raman spectroscopy and atomic force microscopy to determine their optical properties, namely the refractive index and extinction coefficient, in an extended spectral range of 0.75-6.5 eV. From the analysis of the optical data, information on SAMs structural organization has been inferred. Comparison of SAMs generated from the above aromatic thiols to well-known SAMs generated from the alkanethiol dodecanethiol revealed that the former aromatic SAMs are densely packed and highly vertically oriented, with a slightly higher packing density and a absence of molecular inclination in TPMT/Au. The thermal behavior of SAMs has also been monitored using ellipsometry in the temperature range 25-500 degrees C. Gold nanoparticles functionalized by the same aromatic thiols have also been discussed for surface enhanced Raman spectroscopy applications. This study represents a step forward tailoring the optical and thermal behavior of surfaces as well as nanoparticles.

Improved Structural Design and CO 2 Capture of Porous Hydroxy-Rich Polymeric Organic Frameworks

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

Kidder, Michelle K.; Earl, Lyndsey D.; de Almeida, Valmor F.

2016-04-16

Polymeric organic frameworks (POFs) are tunable and robust porous materials with potential applications for gas capture, catalysis, and separations technologies. A series of new porous POFs have been synthesized from the reaction of phloroglucinol or resorcinol derivatives with aryl aldehyde precursors. The monomers have various molecular shapes including linear, bent, trigonal, and tetrahedral geometries. Depending on the size and geometric matching of the monomers, the polymers are dominantly microporous with some mesoporous character or they are non-porous. In addition to standard spectroscopic and surface characterization, the materials were screened as adsorbents for carbon dioxide capture at low pressure (0-1 bar).more » The best performing material (POF 1D) has a CO 2 capture capacity of 9.0 wt. % (2.04 mmol g -1) at 298 K and 1 bar which is comparable to other polymeric organic frameworks. Isosteric heats of adsorption for POF 1A, POF 2A, and POF 2B were found to be dependent on the weight percent of CO 2 adsorbed: this suggests there are both chemisorptive and physisorptive components of CO 2 capture by the POFs.« less

Chemically Modified Polyvinyl Chloride for Removal of Thionine Dye (Lauth’s Violet)

PubMed Central

Silva, Cleuzilene V.; Royer, Betina; Rodrigues Filho, Guimes; Cerqueira, Daniel A.; Assunção, Rosana M. N.

2017-01-01

The chemical modification of hydrophobic polymer matrices is an alternative way to elchange their surface properties. The introduction of sulfonic groups in the polymer changes the surface properties such as adhesion, wettability, catalytic ability, and adsorption capacity. This work describes the production and application of chemically modified polyvinyl chloride (PVC) as adsorbent for dyes removal. Chemical modification of PVC was evaluated by infrared spectroscopy and elemental analysis, which indicated the presence of sulfonic groups on PVC. The chemically modified PVC (PVCDS) showed an ion exchange capacity of 1.03 mmol−1, and efficiently removed the thionine dye (Lauth’s violet) from aqueous solutions, reaching equilibrium in 30 min. The adsorption kinetics was better adjusted for a pseudo second order model. This result indicates that the adsorption of thionine onto PVCDS occurs by chemisorption. Among the models for the state of equilibrium, SIPS and Langmuir exhibited the best fit to the experimental results and PVCDS showed high adsorption capacities (370 mg−1). Thus, it is assumed that the system presents homogeneous characteristics to the distribution of active sites. The modification promoted the formation of surface characteristics favorable to the dye adsorption by the polymer. PMID:29137158

Speciation of adsorbates on surface of solids by infrared spectroscopy and chemometrics.

PubMed

Vilmin, Franck; Bazin, Philippe; Thibault-Starzyk, Frédéric; Travert, Arnaud

2015-09-03

Speciation, i.e. identification and quantification, of surface species on heterogeneous surfaces by infrared spectroscopy is important in many fields but remains a challenging task when facing strongly overlapped spectra of multiple adspecies. Here, we propose a new methodology, combining state of the art instrumental developments for quantitative infrared spectroscopy of adspecies and chemometrics tools, mainly a novel data processing algorithm, called SORB-MCR (SOft modeling by Recursive Based-Multivariate Curve Resolution) and multivariate calibration. After formal transposition of the general linear mixture model to adsorption spectral data, the main issues, i.e. validity of Beer-Lambert law and rank deficiency problems, are theoretically discussed. Then, the methodology is exposed through application to two case studies, each of them characterized by a specific type of rank deficiency: (i) speciation of physisorbed water species over a hydrated silica surface, and (ii) speciation (chemisorption and physisorption) of a silane probe molecule over a dehydrated silica surface. In both cases, we demonstrate the relevance of this approach which leads to a thorough surface speciation based on comprehensive and fully interpretable multivariate quantitative models. Limitations and drawbacks of the methodology are also underlined. Copyright © 2015 Elsevier B.V. All rights reserved.

Adsorption mechanism of SF6 decomposed species on pyridine-like PtN3 embedded CNT: A DFT study

NASA Astrophysics Data System (ADS)

Cui, Hao; Zhang, Xiaoxing; Chen, Dachang; Tang, Ju

2018-07-01

Metal-Nx embedded CNT have aroused considerable attention in the field of gas interaction due to their strong catalytic behavior, which provides prospective scopes for gas adsorption and sensing. Detecting SF6 decomposed species in certain devices is essential to guarantee their safe operation. In this work, we performed DFT method and simulated the adsorption of three SF6 decomposed gases (SO2, SOF2 and SO2F2) onto the PtN3 embedded CNT surface, in order to shed light on its adsorption ability and sensing mechanism. Results suggest that the CNT embedded with PtN3 center has strong interaction with these gas molecules, leading to high hybridization between Pt dopant and active atoms inner gas molecules. These interactions are assumed to be chemisorption due to the remarkable Ead and QT, thus resulting in dramatic deformations in electronic structure of PtN3-CNT near the Fermi level. Furthermore, the electronic redistribution cause the conductivity increase of proposed material in three systems, based on frontier molecular orbital theory. Our calculations attempt to suggest novel sensing material that are potentially employed in detection of SF6 decomposed components.

Selective hydrogenation of phenol to cyclohexanone over Pd@CN (N-doped porous carbon): Role of catalyst reduction method

NASA Astrophysics Data System (ADS)

Hu, Shuo; Yang, Guangxin; Jiang, Hong; Liu, Yefei; Chen, Rizhi

2018-03-01

Selective phenol hydrogenation is a green and sustainable technology to produce cyclohexanone. The work focused on investigating the role of catalyst reduction method in the liquid-phase phenol hydrogenation to cyclohexanone over Pd@CN (N-doped porous carbon). A series of reduction methods including flowing hydrogen reduction, in-situ reaction reduction and liquid-phase reduction were designed and performed. The results highlighted that the reduction method significantly affected the catalytic performance of Pd@CN in the liquid-phase hydrogenation of phenol to cyclohexanone, and the liquid-phase reduction with the addition of appropriate amount of phenol was highly efficient to improve the catalytic activity of Pd@CN. The influence mechanism was explored by a series of characterizations. The results of TEM, XPS and CO chemisorption confirmed that the reduction method mainly affected the size, surface composition and dispersion of Pd in the CN material. The addition of phenol during the liquid-phase reduction could inhibit the aggregation of Pd NPs and promote the reduction of Pd (2+), and then improved the catalytic activity of Pd@CN. The work would aid the development of high-performance Pd@CN catalysts for selective phenol hydrogenation.

Biomass-based magnetic fluorescent nanoparticles: One-step scalable synthesis, application as drug carriers and mechanism study.

PubMed

Li, Lei; Wang, Feijun; Shao, Ziqiang

2018-03-15

A biomass-based magnetic fluorescent nanoparticle (MFNPs) was successively in situ synthesized via a one-step high-gravity approach, which constructed by a magnetic core of Fe 3 O 4 nanoparticles, the fluorescent marker of carbon dots (CDs), and shells of chitosan (CS). The obtained MFNPs had a 10 nm average diameter and narrow particle size distribution, low cytotoxicity, superior fluorescent emission and superparamagnetic properties. The encapsulating and release 5-fluorouracil experiments confirmed that the introduction of CS/CDs effectively improved the drug loading capacity. Mechanism and kinetic studies proved that: (i) the monolayer adsorption was the main sorption mode under the studied conditions; (ii) the whole adsorption process was controlled by intra-liquid diffusion mass transfer and governed by chemisorption; and (iii) the release process was controlled by Fickian diffusion. These results demonstrated this method to one-step continuously produce MFNPs and the construction of non-toxic nanostructure possessed great superiority in currently Nano-delivery systems, which would show high application value in targeted drug delivery, magnetic fluid hyperthermia treatment, magnetic resonance imaging (MRI), in vitro testing and relative research. Copyright © 2017 Elsevier Ltd. All rights reserved.

Water dissociating on rigid Ni(100): A quantum dynamics study on a full-dimensional potential energy surface

NASA Astrophysics Data System (ADS)

Liu, Tianhui; Chen, Jun; Zhang, Zhaojun; Shen, Xiangjian; Fu, Bina; Zhang, Dong H.

2018-04-01

We constructed a nine-dimensional (9D) potential energy surface (PES) for the dissociative chemisorption of H2O on a rigid Ni(100) surface using the neural network method based on roughly 110 000 energies obtained from extensive density functional theory (DFT) calculations. The resulting PES is accurate and smooth, based on the small fitting errors and the good agreement between the fitted PES and the direct DFT calculations. Time dependent wave packet calculations also showed that the PES is very well converged with respect to the fitting procedure. The dissociation probabilities of H2O initially in the ground rovibrational state from 9D quantum dynamics calculations are quite different from the site-specific results from the seven-dimensional (7D) calculations, indicating the importance of full-dimensional quantum dynamics to quantitatively characterize this gas-surface reaction. It is found that the validity of the site-averaging approximation with exact potential holds well, where the site-averaging dissociation probability over 15 fixed impact sites obtained from 7D quantum dynamics calculations can accurately approximate the 9D dissociation probability for H2O in the ground rovibrational state.

Kinetic characteristics of Cu (II) adsorption on nano(poly)-cumulene

NASA Astrophysics Data System (ADS)

Babkin, Alexander; Neskoromnaya, Elena; Burakova, Irina; Kucherova, Ananstasia; Burakov, Alexander; Mkrtchyan, Elina

2017-11-01

The present paper considers the possibility of using a new type of nanocarbon materials for sorption - polycumulene modified with "Taunit-M" carbon nanotubes or graphene nanoplatelets. To evaluate the efficiency of these novel nanomodified materials as sorbents, the following studies were carried out: 1) determination of the optimum pH value to perform static batch sorption experiments, 2) identification of the onset of equilibrium for the adsorption of heavy metal ions (on the example of Cu(II) ions), and 3) elucidation of kinetic adsorption mechanisms. As a result of implementation of kinetic models such as external and internal diffusion, as well as pseudo-first- and pseudo-second-order and Elovich (to determine the contribution of chemisorption), rate constants for the Cu(II) adsorption were estimated. It was noted that the absorption process occurs in a mixed-diffusion mode with the influence of the limiting factor - "sorbate-sorbate" chemical interaction. The equilibrium time was found to be 45 min at the sorption capacity values of about 30.71 mg g-1 (in the case of the material containing carbon nanotubes) and about 24.7 mg g-1 (in the case of the material containing graphene nanoplatelets).

Reaction of hydrogen with Ag(111): binding states, minimum energy paths, and kinetics.

PubMed

Montoya, Alejandro; Schlunke, Anna; Haynes, Brian S

2006-08-31

The interaction of atomic and molecular hydrogen with the Ag(111) surface is studied using periodic density functional total-energy calculations. This paper focuses on the site preference for adsorption, ordered structures, and energy barriers for H diffusion and H recombination. Chemisorbed H atoms are unstable with respect to the H(2) molecule in all adsorption sites below monolayer coverage. The three-hollow sites are energetically the most favorable for H chemisorption. The binding energy of H to the surface decreases slightly up to one monolayer, suggesting a small repulsive H-H interaction on nonadjacent sites. Subsurface and vacancy sites are energetically less favorable for H adsorption than on-top sites. Recombination of chemisorbed H atoms leads to the formation of gas-phase H(2) with no molecular chemisorbed state. Recombination is an exothermic process and occurs on the bridge site with a pronounced energy barrier. This energy barrier is significantly higher than that inferred from experimental temperature-programmed desorption (TPD) studies. However, there is significant permeability of H atoms through the recombination energy barrier at low temperatures, thus increasing the rate constant for H(2) desorption due to quantum tunneling effects, and improving the agreement between experiment and theory.

Photoinduced electron transfer through peptide-based self-assembled monolayers chemisorbed on gold electrodes: directing the flow-in and flow-out of electrons through peptide helices.

PubMed

Venanzi, Mariano; Gatto, Emanuela; Caruso, Mario; Porchetta, Alessandro; Formaggio, Fernando; Toniolo, Claudio

2014-08-21

Photoinduced electron transfer (PET) experiments have been carried out on peptide self-assembled monolayers (SAM) chemisorbed on a gold substrate. The oligopeptide building block was exclusively formed by C(α)-tetrasubstituted α-aminoisobutyric residues to attain a helical conformation despite the shortness of the peptide chain. Furthermore, it was functionalized at the C-terminus by a pyrene choromophore to enhance the UV photon capture cross-section of the compound and by a lipoic group at the N-terminus for linking to gold substrates. Electron transfer across the peptide SAM has been studied by photocurrent generation experiments in an electrochemical cell employing a gold substrate modified by chemisorption of a peptide SAM as a working electrode and by steady-state and time-resolved fluorescence experiments in solution and on a gold-coated glass. The results show that the electronic flow through the peptide bridge is strongly asymmetric; i.e., PET from the C-terminus to gold is highly favored with respect to PET in the opposite direction. This effect arises from the polarity of the Au-S linkage (Au(δ+)-S(δ-), junction effect) and from the electrostatic field generated by the peptide helix.

Interaction of epitaxial silicene with overlayers formed by exposure to Al atoms and O2 molecules.

PubMed

Friedlein, R; Van Bui, H; Wiggers, F B; Yamada-Takamura, Y; Kovalgin, A Y; de Jong, M P

2014-05-28

As silicene is not chemically inert, the study and exploitation of its electronic properties outside of ultrahigh vacuum environments require the use of insulating capping layers. In order to understand if aluminum oxide might be a suitable encapsulation material, we used high-resolution synchrotron photoelectron spectroscopy to study the interactions of Al atoms and O2 molecules, as well as the combination of both, with epitaxial silicene on thin ZrB2(0001) films grown on Si(111). The deposition of Al atoms onto silicene, up to the coverage of about 0.4 Al per Si atoms, has little effect on the chemical state of the Si atoms. The silicene-terminated surface is also hardly affected by exposure to O2 gas, up to a dose of 4500 L. In contrast, when Al-covered silicene is exposed to the same dose, a large fraction of the Si atoms becomes oxidized. This is attributed to dissociative chemisorption of O2 molecules by Al atoms at the surface, producing reactive atomic oxygen species that cause the oxidation. It is concluded that aluminum oxide overlayers prepared in this fashion are not suitable for encapsulation since they do not prevent but actually enhance the degradation of silicene.

TEMPO Monolayers on Si(100) Electrodes: Electrostatic Effects by the Electrolyte and Semiconductor Space-Charge on the Electroactivity of a Persistent Radical.

PubMed

Zhang, Long; Vogel, Yan Boris; Noble, Benjamin B; Gonçales, Vinicius R; Darwish, Nadim; Brun, Anton Le; Gooding, J Justin; Wallace, Gordon G; Coote, Michelle L; Ciampi, Simone

2016-08-03

This work demonstrates the effect of electrostatic interactions on the electroactivity of a persistent organic free radical. This was achieved by chemisorption of molecules of 4-azido-2,2,6,6-tetramethyl-1-piperdinyloxy (4-azido-TEMPO) onto monolayer-modified Si(100) electrodes using a two-step chemical procedure to preserve the open-shell state and hence the electroactivity of the nitroxide radical. Kinetic and thermodynamic parameters for the surface electrochemical reaction are investigated experimentally and analyzed with the aid of electrochemical digital simulations and quantum-chemical calculations of a theoretical model of the tethered TEMPO system. Interactions between the electrolyte anions and the TEMPO grafted on highly doped, i.e., metallic, electrodes can be tuned to predictably manipulate the oxidizing power of surface nitroxide/oxoammonium redox couple, hence showing the practical importance of the electrostatics on the electrolyte side of the radical monolayer. Conversely, for monolayers prepared on the poorly doped electrodes, the electrostatic interactions between the tethered TEMPO units and the semiconductor-side, i.e., space-charge, become dominant and result in drastic kinetic changes to the electroactivity of the radical monolayer as well as electrochemical nonidealities that can be explained as an increase in the self-interaction "a" parameter that leads to the Frumkin isotherm.

Spin Uncoupling in Chemisorbed OCCO and CO 2: Two High-Energy Intermediates in Catalytic CO 2 Reduction

DOE PAGES

Hedstrom, Svante; dos Santos, Egon Campos; Liu, Chang; ...

2018-05-08

Here, the production of useful compounds via the electrochemical carbon dioxide reduction reaction (CO2RR) is a matter of intense research. Although the thermodynamics and kinetic barriers of CO2RR are reported in previous computational studies, the electronic structure details are often overlooked. We study two important CO2RR intermediates: ethylenedione (OCCO) and CO 2 covalently bound to cluster and slab models of the Cu(100) surface. Both molecules exhibit a near-unity negative charge as chemisorbed, but otherwise they behave quite differently, as explained by a spin-uncoupling perspective. OCCO adopts a high-spin, quartetlike geometry, allowing two covalent bonds to the surface with an averagemore » gross interaction energy of –1.82 eV/bond. The energy cost for electronically exciting OCCO– to the quartet state is 1.5 eV which is readily repaid via the formation of its two surface bonds. CO 2, conversely, retains a low-spin, doubletlike structure upon chemisorption, and its single unpaired electron forms a single covalent surface bond of –2.07 eV. The 5.0 eV excitation energy to the CO 2 – quartet state is prohibitively costly and cannot be compensated for by an additional surface bond.« less

A Mechanistic Study of CO 2 Reduction at the Interface of a Gallium Phosphide (GaP) Surface using Core-level Spectroscopy

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

Flynn, Kristen

2015-08-18

Carbon dioxide (CO 2) emission into the atmosphere has increased tremendously through burning of fossil fuels, forestry, etc.. The increased concentration has made CO 2 reductions very attractive though the reaction is considered uphill. Utilizing the sun as a potential energy source, CO 2 has the possibility to undergo six electron and four proton transfers to produce methanol, a useable resource. This reaction has been shown to occur selectively in an aqueous pyridinium solution with a gallium phosphide (GaP) electrode. Though this reaction has a high faradaic efficiency, it was unclear as to what role the GaP surface played duringmore » the reaction. In this work, we aim to address the fundamental role of GaP during the catalytic conversion, by investigating the interaction between a clean GaP surface with the reactants, products, and intermediates of this reaction using X-ray photoelectron spectroscopy. We have determined a procedure to prepare atomically clean GaP and our initial CO 2 adsorption studies have shown that there is evidence of chemisorption and reaction to form carbonate on the clean surface at LN2 temperatures (80K), in contrast to previous theoretical calculations. These findings will enable future studies on CO 2 catalysis.« less

A Mechanistic Study of CO 2 Reduction at the Interface of a Gallium Phosphide (GaP) Surface using Core-level Spectroscopy - Oral Presentation

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

Flynn, Kristen

2015-08-19

Carbon dioxide (CO 2) emission into the atmosphere has increased tremendously through burning of fossil fuels, forestry, etc.. The increased concentration has made CO 2 reductions very attractive though the reaction is considered uphill. Utilizing the sun as a potential energy source, CO 2 has the possibility to undergo six electron and four proton transfers to produce methanol, a useable resource. This reaction has been shown to occur selectively in an aqueous pyridinium solution with a gallium phosphide (GaP) electrode. Though this reaction has a high faradaic efficiency, it was unclear as to what role the GaP surface played duringmore » the reaction. In this work, we aim to address the fundamental role of GaP during the catalytic conversion, by investigating the interaction between a clean GaP surface with the reactants, products, and intermediates of this reaction using X-ray photoelectron spectroscopy. We have determined a procedure to prepare atomically clean GaP and our initial CO 2 adsorption studies have shown that there is evidence of chemisorption and reaction to form carbonate on the clean surface at LN2 temperatures (80K), in contrast to previous theoretical calculations. These findings will enable future studies on CO 2 catalysis.« less

Chemically modified biochar produced from conocarpus waste increases NO3 removal from aqueous solutions.

PubMed

Usman, Adel R A; Ahmad, Mahtab; El-Mahrouky, Mohamed; Al-Omran, Abdulrasoul; Ok, Yong Sik; Sallam, Abdelazeem Sh; El-Naggar, Ahmed H; Al-Wabel, Mohammad I

2016-04-01

Biochar has emerged as a universal sorbent for the removal of contaminants from water and soil. However, its efficiency is lower than that of commercially available sorbents. Engineering biochar by chemical modification may improve its sorption efficiency. In this study, conocarpus green waste was chemically modified with magnesium and iron oxides and then subjected to thermal pyrolysis to produce biochar. These chemically modified biochars were tested for NO3 removal efficiency from aqueous solutions in batch sorption isothermal and kinetic experiments. The results revealed that MgO-biochar outperformed other biochars with a maximum NO3 sorption capacity of 45.36 mmol kg(-1) predicted by the Langmuir sorption model. The kinetics data were well described by the Type 1 pseudo-second-order model, indicating chemisorption as the dominating mechanism of NO3 sorption onto biochars. Greater efficiency of MgO-biochar was related to its high specific surface area (391.8 m(2) g(-1)) and formation of strong ionic complexes with NO3. At an initial pH of 2, more than 89 % NO3 removal efficiency was observed for all of the biochars. We conclude that chemical modification can alter the surface chemistry of biochar, thereby leading to enhanced sorption capacity compared with simple biochar.

Active chemisorption sites in functionalized ionic liquids for carbon capture.

PubMed

Cui, Guokai; Wang, Jianji; Zhang, Suojiang

2016-07-25

Development of novel technologies for the efficient and reversible capture of CO2 is highly desired. In the last decade, CO2 capture using ionic liquids has attracted intensive attention from both academia and industry, and has been recognized as a very promising technology. Recently, a new approach has been developed for highly efficient capture of CO2 by site-containing ionic liquids through chemical interaction. This perspective review focuses on the recent advances in the chemical absorption of CO2 using site-containing ionic liquids, such as amino-based ionic liquids, azolate ionic liquids, phenolate ionic liquids, dual-functionalized ionic liquids, pyridine-containing ionic liquids and so on. Other site-containing liquid absorbents such as amine-based solutions, switchable solvents, and functionalized ionic liquid-amine blends are also investigated. Strategies have been discussed for how to activate the existent reactive sites and develop novel reactive sites by physical and chemical methods to enhance CO2 absorption capacity and reduce absorption enthalpy. The carbon capture mechanisms of these site-containing liquid absorbents are also presented. Particular attention has been paid to the latest progress in CO2 capture in multiple-site interactions by amino-free anion-functionalized ionic liquids. In the last section, future directions and prospects for carbon capture by site-containing ionic liquids are outlined.

Effect of copper oxide concentration on the formation and persistency of environmentally persistent free radicals (EPFRs) in particulates.

PubMed

Kiruri, Lucy W; Khachatryan, Lavrent; Dellinger, Barry; Lomnicki, Slawo

2014-02-18

Environmentally persistent free radicals (EPFRs) are formed by the chemisorption of substituted aromatics on metal oxide surfaces in both combustion sources and superfund sites. The current study reports the dependency of EPFR yields and their persistency on metal loading in particles (0.25, 0.5, 0.75, 1, 2, and 5% CuO/silica). The EPFRs were generated through exposure of particles to three adsorbate vapors at 230 °C: phenol, 2-monochlorophenol (2-MCP), and dichlorobenzene (DCBz). Adsorption resulted in the formation of surface-bound phenoxyl- and semiquinoine-type radicals with characteristic EPR spectra displaying a g value ranging from ∼ 2.0037 to 2.006. The highest EPFR yield was observed for CuO concentrations between 1 and 3% in relation to MCP and phenol adsorption. However, radical density, which is expressed as the number of radicals per copper atom, was highest at 0.75-1% CuO loading. For 1,2-dichlorobenzene adsorption, radical concentration increased linearly with decreasing copper content. At the same time, a qualitative change in the radicals formed was observed--from semiquinone to chlorophenoxyl radicals. The two longest lifetimes, 25 and 23 h, were observed for phenoxyl-type radicals on 0.5% CuO and chlorophenoxyl-type radicals on 0.75% CuO, respectively.

Electron nanoprobe induced oxidation: A simulation of direct-write purification

DOE PAGES

Fowlkes, J. D.; Geier, B.; Lewis, B. B.; ...

2015-06-01

Electron beam direct-write has recently taken a large step forward with the advent of methods to purify deposits. This development has opened the door for future direct-write device prototyping and editing. In one such approach, an additional beam scanning procedure removes carbonaceous impurities via oxidation from metal–carbon deposits (e.g., PtC 5) in the presence of H 2O or O 2 after deposition. So far, critical aspects of the oxidation reaction remain unclear; experiments reveal clearly that electron stimulated oxidation drives the process yet it is not understood why H 2O purifies by a bottom-up mechanism while O 2 purifies frommore » the top-down. The simulation results presented here suggest that the chemisorption of dissolved O 2 at buried Pt nanoparticle surfaces controls purification in the top-down case while both the high relative solubility coupled with weak physisorption of H 2O explains the bottom-up process. Crucial too is the role that the carbonaceous contaminant itself has on the dissolution and diffusion of O 2 and H 2O. The results pave the way for simulation driven experiments where (1) the transient densification of the deposit can be accounted for in the initial deposit design stage and (2) the deposition and purification steps can be combined.« less

Investigation on the efficiency of treated Palm Tree waste for removal of organic pollutants

NASA Astrophysics Data System (ADS)

Azoulay, Karima; El HajjajiI, Souad; Dahchour, Abdelmalek

2017-04-01

Development of the industrial sector generates several problems of environmental pollution. This issue rises concern among scientific community and decision makers, in this work; we e interested in water resources polluted by the chemical substances, which can cause various problems of health. As an example, dyes generated by different industrial activities such as textile, cosmetic, metal plating, leather, paper and plastic sectors, constitute an important source of pollution. In this work, we aim at investigating the efficiency of palm tree waste for removal of dyes from polluted solution. Our work presents a double environmental aspect, on one hand it constitutes an attempt for valorization of Palm Tree waste, and on the other hand it provides natural adsorbent. The study focuses on the effectiveness of the waste in removing Methylene Bleu and Methyl Orange taken as models of pollutants from aqueous solution. Kinetics and isotherm experiments were conducted in order to determine the sorption behavior of the examined dye. The effects of initial dye and adsorbent concentrations are considered. The results indicate that the correlation coefficient calculated from pseudo-second order equation was higher than the other kinetic equations, indicating that equilibrium data fitted well with pseudo-second order model where adsorption process was chemisorption. The adsorption equilibrium was well described by Langmuir isotherm model.

Poultry manure as raw material for mercury adsorbents in gas applications

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

Klasson, K.T.; Lima, I.M.; Boihem, L.L.

2009-09-30

The quantity of poultry manure generated each year is large, and technologies that take advantage of the material should be explored. At the same time, increased emphasis on the reduction of mercury emissions from coal-fired electric power plants has resulted in environmental regulations that may, in the future, require application of activated carbons as mercury sorbents. The sorbents could be injected into the flue gas stream, where they could adsorb the mercury. The sorbents (now containing mercury) would be removed via filtration or other means from the flue gas. Our preliminary work has demonstrated that activated carbon made from poultrymore » manure can adsorb mercury from air with good efficiency. In laboratory experiments, an activated carbon made from turkey cake manure removed the majority of elemental mercury from a hot air stream. Other activated carbons made from chicken and turkey litter manure were also efficient. In general, unwashed activated carbons made from poultry manure were more efficient in removing mercury than their acid-washed counterparts. The results suggest that the adsorption of mercury was mainly due to chemisorption on the surface of the carbon. Other potential uses for the activated carbons are the removal of mercury from air and natural gas.« less

First-principles study on the structure and electronic property of gas molecules adsorption on Ge2Li2 monolayer

NASA Astrophysics Data System (ADS)

Hu, Yiwei; Long, Linbo; Mao, Yuliang; Zhong, Jianxin

2018-06-01

Using first-principles methods, we have studied the adsorption of gas molecules (CO2, CH4, H2S, H2 and NH3) on two dimensional Ge2Li2 monolayer. The adsorption geometries, adsorption energies, charge transfer, and band structures of above mentioned gas molecules adsorption on Ge2Li2 monolayer are analyzed. It is found that the adsorption of CO2 on Ge2Li2 monolayer is a kind of strong chemisorption, while other gas molecules such as CH4, H2S, H2 and NH3 are physisorption. The strong covalent binding is formed between the CO2 molecule and the nearest Ge atom in Ge2Li2 monolayer. This adsorption of CO2 molecule on Ge2Li2 monolayer leads to a direct energy gap of 0.304 eV. Other gas molecules exhibit mainly ionic binding to the nearest Li atoms in Ge2Li2 monolayer, which leads to indirect energy gap after adsorptions. Furthermore, it is found that the work function of Ge2Li2 monolayer is sensitive with the variation of adsorbents. Our results reveal that the Ge2Li2 monolayer can be used as a kind of nano device for gas molecules sensor.

Absorption of CO2 on Carbon-based Sensors: First-Principle Analysis

NASA Astrophysics Data System (ADS)

Tit, Nacir; Elezzi, Mohammed; Abdullah, Hasan; Bahlouli, Hocine; Yamani, Zain

We present first-principle investigation of the adsorption properties of CO and CO2 molecules on both graphene and carbon nano-tubes (CNTs) in presence of metal catalysis, mainly iron (Fe). The relaxations were carried out using the self-consistent-charge density-functional tight-binding (SCC-DFTB) code in neglect of heat effects. The results show the following: (1) Defected graphene is found to have high sensitivity and high selectivity towards chemisorption of CO molecules and weak physisorption with CO2 molecules. (2) In case of CNTs, the iron ``Fe'' catalyst plays an essential role in capturing CO2 molecules. The Fe ad-atoms on the surface of CNT introduce huge density of states at Fermi level, but the capture of CO2 molecules would reduce that density and consequently reduce conductivity and increase sensitivity. Concerning the selectivity, we have studied the sensitivity versus various gas molecules (such as: O2, N2, H2, H2O, and CO). Furthermore, to assess the effect of catalysis on sensitivity, we have studied the sensitivity of other metal catalysts (such as: Ni, Co, Ti, and Sc). We found that CNT-Fe is highly sensitive and selective towards detection of CO and CO2 molecules. CNT being conductive or semiconducting does not matter much on the adsorption properties.

Surface reaction of silicon chlorides during atomic layer deposition of silicon nitride

NASA Astrophysics Data System (ADS)

Yusup, Luchana L.; Park, Jae-Min; Mayangsari, Tirta R.; Kwon, Young-Kyun; Lee, Won-Jun

2018-02-01

The reaction of precursor with surface active site is the critical step in atomic layer deposition (ALD) process. We performed the density functional theory calculation with DFT-D correction to study the surface reaction of different silicon chloride precursors during the first half cycle of ALD process. SiCl4, SiH2Cl2, Si2Cl6 and Si3Cl8 were considered as the silicon precursors, and an NH/SiNH2*-terminated silicon nitride surface was constructed to model the thermal ALD processes using NH3 as well as the PEALD processes using NH3 plasma. The total energies of the system were calculated for the geometry-optimized structures of physisorption, chemisorption, and transition state. The order of silicon precursors in energy barrier, from lowest to highest, is Si3Cl8 (0.92 eV), Si2Cl6 (3.22 eV), SiH2Cl2 (3.93 eV) and SiCl4 (4.49 eV). Silicon precursor with lower energy barrier in DFT calculation showed lower saturation dose in literature for both thermal and plasma-enhanced ALD of silicon nitride. Therefore, DFT calculation is a promising tool in predicting the reactivity of precursor during ALD process.

Stable Carboxylate-Terminated Gold Surfaces Produced by Spontaneous Grafting of an Alkyl Tin Compound.

PubMed

Ortiz, Mayreli; Mehdi, Ahmed; Methivier, Christophe; Thorimbert, Serge; Hasenknopf, Bernold; O'Sullivan, Ciara K

2018-05-21

Self-assembled monolayers formed by chemisorption of thiolated molecules on gold surfaces are widely applied for biosensing. Moreover, and due to the low stability of thiol-gold chemistry, contributions to the functionalisation of gold substrates with linkers that provide a more stable platform for the immobilisation of electroactive or biological molecules are highly appreciated. In the work reported here, we demonstrate that a carboxylated organotin compound can be successfully grafted onto gold substrates to form a highly stable organic layer with reactivity for subsequent binding to an aminated molecule. A battery of techniques was used to characterise the surface chemistry. The grafted layer was used to anchor aminoferrocene and subjected to both thermostability tests and long term stability studies over the period of one year, demonstrating thermostability up to 90 oC and storage stability for at least 12 months when stored at 4 oC protected from light. The stable surface tethering of molecules on gold substrates can be exploited in a plethora of applications including molecular techniques such as solid-phase amplification and solid-phase melting curve analysis that require elevated temperature stability, as well as biosensors, which require long-term storage stability. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluation of carbon-based nanosorbents synthesised by ethylene decomposition on stainless steel substrates as potential sequestrating materials for nickel ions in aqueous solution.

PubMed

Lee, X J; Lee, L Y; Foo, L P Y; Tan, K W; Hassell, D G

2012-01-01

The present work covers the preparation of carbon-based nanosorbents by ethylene decomposition on stainless steel mesh without the use of external catalyst for the treatment of water containing nickel ions (Ni2+). The reaction temperature was varied from 650 to 850 degrees C, while reaction time and ethylene to nitrogen flow ratio were maintained at 30 min and 1:1 cm3/min, respectively. Results show that nanosorbents synthesised at a reaction temperature of 650 degrees C had the smallest average diameter (75 nm), largest BET surface area (68.95 m2/g) and least amount of impurity (0.98 wt.% Fe). A series of batch-sorption tests were performed to evaluate the effects of initial pH, initial metal concentration and contact time on Ni2+ removal by the nanosorbents. The equilibrium data fitted well to Freundlich isotherm. The kinetic data were best correlated to a pseudo second-order model indicating that the process was of chemisorption type. Further analysis by the Boyd kinetic model revealed that boundary layer diffusion was the controlling step. This primary study suggests that the prepared material with Freundlich constants compared well with those in the literature, is a promising sorbent for the sequestration of Ni2+ in aqueous solutions.

Adsorption and possible dissociation of glucose by the [BN fullerene-B6]- magnetic nanocomposite. In silico studies

NASA Astrophysics Data System (ADS)

Anota, E. Chigo; Villanueva, M. Salazar; Shakerzadeh, E.; Castro, M.

2018-02-01

The adsorption, activation and possible dissociation of the glucose molecule on the magnetic [BN fullerene-B6]- system is performed by means of density functional theory calculations. Three models of magnetic nanocomposites were inspected: i) pristine BN fullerene, BN fullerene functionalized with a magnetic B6 cluster which generates two structures: ii) pyramidal (P) and iii) triangular (T). Chemical interactions of glucose appear for all these cases; however, for the BNF:B6(T)—glucose system, the interaction generates an effect of dissociation on glucose, due to the magnetic effects, since it has high spin multiplicity. The latter nanocomposite shows electronic behavior like-conductor and like-semi-conductor for the P and T geometries, respectively. Intrinsic magnetism associated to values of 1.0 magneton bohr (µB) for the pyramidal and 5.0 µB for the triangular structure, high polarity, and low-chemical reactivity are found for these systems. These interesting properties make these functionalized fullerenes a good option for being used as nano-vehicles for drug delivery. These quantum descriptors remain invariant when the [BN]-fullerene and [BNF:B6 (P) or (T)]- nanocomposites are interacting with the glucose molecule. According to the determined adsorption energy, chemisorption regimes occur in both the phases: gas and aqueous medium.

Antisoiling technology: Theories of surface soiling and performance of antisoiling surface coatings

NASA Technical Reports Server (NTRS)

Cuddihy, E. F.; Willis, P. B.

1984-01-01

Physical examination of surfaces undergoing natural outdoor soiling suggests that soil matter accumulates in up to three distinct layers. The first layer involves strong chemical attachment or strong chemisorption of soil matter on the primary surface. The second layer is physical, consisting of a highly organized arrangement of soil creating a gradation in surface energy from a high associated with the energetic first layer to the lowest possible state on the outer surfce of the second layer. The lowest possible energy state is dictated by the physical nature of the regional atmospheric soiling materials. These first two layers are resistant to removal by rain. The third layer constitutes a settling of loose soil matter, accumulating in dry periods and being removed during rainy periods. Theories and evidence suggest that surfaces that should be naturally resistant to the formation of the first two-resistant layers should be hard, smooth, hydrophobic, free of first-period elements, and have the lowest possible surface energy. These characteristics, evolving as requirements for low-soiling surfaces, suggest that surfaces or surface coatings should be of fluorocarbon chemistry. Evidence for the three-soil-layer concept, and data on the positive performance of candidate fluorocarbon coatings on glass and transparent plastic films after 28 months of outdoor exposure, are presented.