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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Toward Rational Design of Supported Vanadia Catalysts of Lignin Conversion to Phenol

In sustainable chemical engineering, catalytic upgrading of lignocellulosic biomass has recently gained attention for producing renewable platform chemicals. To achieve maximal biomass utilization, upgrading the underutilized lignin components is essential. Among various catalysts for lignin upgrading, supported vanadia (V2O5) catalysts are promising because of their cost-effectiveness and tunability of either dopant metals or catalyst supports. Here, computational studies are conducted to derive rational design guidelines of supported V2O5 catalysts for accomplishing the high catalytic activity of lignin upgrading to phenol, a key compound for producing bioplastics and biofuel blendstocks. Guaiacol was used as the model compound since it comprises the highest portion of depolymerized lignin. Computational mechanistic studies for the catalytic guaiacol conversion to phenol were performed for the V2O5 catalysts on Titania (TiO2) and silica (SiO2) to explain higher experimental phenol yields on V2O5/SiO2 than V2O5/TiO2. The hydrogen migration from the methoxy group to the aryl ring was identified as a rate-determining step, and the overall activation energies on the two catalysts were compared. A structural analysis was carried out for the catalysts and rate-determining transition states to gain further insights from mechanistic studies. It was concluded that the tilt angle of the aryl group in the hydrogen migration transition state is a key descriptor determining the catalytic activity of phenol formation. These features correlate well with activation energies and experimental phenol yields, indicating that they provide design guidelines for supported metal catalysts for lignin upgrading before experiments.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗
DOE OSTI2023

Kinetic model describing self-limiting CO 2 diffusion in supported amine adsorbents

A reaction–diffusion shrinking core model describing the decay in diffusivity of supported amine sorbents upon CO 2 sorption under both simulated direct air capture and point source capture conditions is described. The decay in CO 2 diffusivity is associated with crosslinking in the aminopolymer samples and general pore blockage in the amino-silane derived samples, which occurs as CO 2 is adsorbed. The model is used to extract four kinetic parameters that govern the CO 2 uptake kinetics and working capacity: an apparent reaction rate constant, an initial effective diffusivity, and two dimensionless decay parameters. Ideally, an initially reaction limited system would allow for direct determination of the intrinsic reaction rate constant; however, sorption experiments suggest mass transfer resistances related to gas mixing, external boundary layers and intraparticle diffusion are present. Reaction rate constants are determined and agree well with theoretical values predicted with the Eyring equation parameterized using density functional theory energies from literature sources. The kinetic performance is expressed as the average effective diffusivity as a function of average conversion, which can be correlated to the dispersion of sorption sites on the support and the morphology of the active sorbent phase. Four supports are impregnated or grafted with amines, SBA-15, single-walled zeolite nanotubes (ZNT), Syloid SiO 2 , and γ-Al 2 O 3 . Due to its pore structure, γ-Al 2 O 3 supported amines can be modeled at the μm scale or at the nm scale, where the shell balance is on the μm-sized macroporous particle aggregate or on the nm-sized amine film on the surface of the Al 2 O 3 nanoparticles, which comprise the spherical particle aggregates. Faster diffusion rates are maintained under 400 ppm rather than 10% CO 2 due to a slower reaction rate giving a slower decay in diffusivity. In conclusion, this work provides a first principles kinetic analysis of CO 2 sorption where previous models are semi-empirical and use arbitrary kinetic parameters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Development of ceria-supported metal-oxide (MO x /CeO 2 ) catalysts via a one-pot chemical vapor deposition (OP-CVD) technique: Structure and reverse water gas shift reaction study

Current synthesis techniques for metal oxide (MO x )-supported catalysts have certain limitations of undesired target loading, ineffective dispersion of active species over the surface, uncontrolled particle size of active species, and complicated synthesis steps. Here, we developed a one-pot chemical vapor deposition (OP-CVD) methodology; by using which a solid metal precursor forms a vapor in a controlled condition and gets supported over the surrounding matrix. The theoretical stability followed by experimental validation using TGA is crucial for selecting the metal precursors. Three simple steps viz. premixing, dispersion, and rapid fixation by calcination are involved in the catalyst development via the OP-CVD approach. This study solely focused on the synthesis of 3d transition MO x over ceria support. The physicochemical characterizations of the prepared catalysts were performed by XRD, ICP-OES, SEM-EDX, CO pulse chemisorption, XANES, and EXAFS analyses to understand the crystal structure of involved species, target metal loading, dispersion, and particle size and prove the feasibility and viability of OP-CVD. The prepared catalysts were further tested for reverse water gas shift (RWGS) reaction to link their structural information with activity. The RWGS reaction data showed that the CO activity and CO selectivity were metal - and metal precursor-dependent. Higher CO activity of > 0.1 mol/h g-cat was observed for Cu and Co-based catalysts, with CO selectivity of ~100 %. This study provides an opportunity to produce efficient supported catalysts in a convenient way, providing effective catalytic activity.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Uncovering the factors that can support and impede post-disaster EIA practice in developing countries: The case of Aceh Province, Indonesia

The close relationship between environmental degradation and the occurrence and severity of disaster events has in recent years raised the profile of environmental assessment (EA) in the disaster management field. EA has been identified as a potentially supportive tool in the global effort to reduce disaster risk. As a component of this, attention has been brought specifically to the importance of the application of EA in the aftermath of disaster events in order to help prevent recurrence and promote sustainability. At the same time, however, it has also been recognised that post-disaster environments may be unfavourable to such practices. Looking at the practice of environmental impact assessment (EIA), this paper reports on a study which sought to identify more specifically the factors which can both support and hinder such practice following disaster events in a developing country context. Analysing the situation in Aceh Province, Indonesia, after the impact of two tsunamigenic earthquakes in late 2004 and early 2005, it is concluded that if EIA is to have a central role in the post-disaster period, pre-disaster preparation could be a key. -- Highlights: • Close relationship between environmental degradation and occurrence/severity of disaster events has raised profile of EA. • EA as a potentially supportive tool in the global effort to reduce disaster risk • Application of EA in the aftermath of disaster events to help prevent recurrence and promote sustainability • The paper looks at factors which can both support and hinder EA following disaster events in a developing country context. • We analyse the situation in Aceh Province, Indonesia, after the impact of two tsunamigenic earthquakes in 2004 and 2005.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2015

Decentralized control of units in smart grids for the support of renewable energy supply

Due to the significant environmental impact of power production from fossil fuels and nuclear fission, future energy systems will increasingly rely on distributed and renewable energy sources (RES). The electrical feed-in from photovoltaic (PV) systems and wind energy converters (WEC) varies greatly both over short and long time periods (from minutes to seasons), and (not only) by this effect the supply of electrical power from RES and the demand for electrical power are not per se matching. In addition, with a growing share of generation capacity especially in distribution grids, the top-down paradigm of electricity distribution is gradually replaced by a bottom-up power supply. This altogether leads to new problems regarding the safe and reliable operation of power grids. In order to address these challenges, the notion of Smart Grids has been introduced. The inherent flexibilities, i.e. the set of feasible power schedules, of distributed power units have to be controlled in order to support demand–supply matching as well as stable grid operation. Controllable power units are e.g. combined heat and power plants, power storage systems such as batteries, and flexible power consumers such as heat pumps. By controlling the flexibilities of these units we are particularly able to optimize the local utilization of RES feed-in in a given power grid by integrating both supply and demand management measures with special respect to the electrical infrastructure. In this context, decentralized systems, autonomous agents and the concept of self-organizing systems will become key elements of the ICT based control of power units. In this contribution, we first show how a decentralized load management system for battery charging/discharging of electrical vehicles (EVs) can increase the locally used share of supply from PV systems in a low voltage grid. For a reliable demand side management of large sets of appliances, dynamic clustering of these appliances into uniformly controlled appliance sets is necessary. We introduce a method for self-organized clustering for this purpose and show how control of such clusters can affect load peaks in distribution grids. Subsequently, we give a short overview on how we are going to expand the idea of self-organized clusters of units into creating a virtual control center for dynamic virtual power plants (DVPP) offering products at a power market. For an efficient organization of DVPPs, the flexibilities of units have to be represented in a compact and easy to use manner. We give an introduction how the problem of representing a set of possibly 10{sup 100} feasible schedules can be solved by a machine-learning approach. In summary, this article provides an overall impression how we use agent based control techniques and methods of self-organization to support the further integration of distributed and renewable energy sources into power grids and energy markets. - Highlights: • Distributed load management for electrical vehicles supports local supply from PV. • Appliances can self-organize into so called virtual appliances for load control. • Dynamic VPPs can be controlled by extensively decentralized control centers. • Flexibilities of units can efficiently be represented by support-vector descriptions.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2021

A refined design concept for sulfur-tolerant Pd catalyst supported on zeolite by shape-selective exclusion and hydrogen spillover for hydrogenation of aromatics

Sulfur poisoning of noble metal catalysts has been a major challenge for decades. This work demonstrates the superior sulfur tolerance of a hybrid zeolite-supported Pd catalyst for hydrogenation of tetralin containing benzothiophene. The hybrid catalyst consists of Pd supported on a large-pore acidic zeolite Y (Pd/HY) and a small-pore zeolite A without (Pd/HA) or with surface metal passivation by chemical vapor deposition of SiO 2 (SiO 2 -Pd/HA) and with potassium ion exchange (SiO 2 -Pd/KA). Pd/HY is very active for tetralin hydrogenation but quickly deactivates after exposure to benzothiophene at high concentration of 100 ppm sulfur. The SiO 2 -coated Pd/HA shows no activity for tetralin hydrogenation, but continues to activate H 2 and serve as a source of hydrogen spillover from Pd/HA since these metal sites are protected from thiophenic sulfur due to size-selective exclusion. Adding K ion-exchanged and SiO 2 -coated catalyst SiO 2 -Pd/KA to Pd/HY is even more effective for enhancing sulfur tolerance, both for tetralin hydrogenation and for isomerization of cis-decalin to trans-decalin in the presence of benzothiophene. The turnover frequencies (TOF) of all the catalysts are similar at the exposed sulfur/Pd atomic ratio of around 0.5. With further increase in sulfur/Pd ratio, rapid decline in TOF was observed on Pd/HY, but SiO 2 -Pd/KA + Pd/HY hybrid catalyst shows a significantly higher TOF than that over Pd/HY, even though SiO 2 -Pd/KA or SiO 2 -Pd/HA alone shows no TOF for tetralin hydrogenation. Even after high-dose poisoning at 400 ppm sulfur, the SiO 2 -Pd/KA + Pd/HY hybrid recovered activity more quickly than SiO 2 -Pd/HA + Pd/HY, while the latter in turn is much better than Pd/HY alone. These results point to the higher activity for hydrogen spillover from SiO 2 -Pd/KA where Pd metal sites are protected from not only thiophenic sulfur but also inorganic sulfur H 2 S by shape-selective exclusion. The present work further establishes the validity of shape-selective exclusion and hydrogen spillover in the design concept proposed for a sulfur-tolerant bimodal acidic zeolite-supported metal catalyst for hydrogenation of naphthalene [C.S. Song, Chemtech, 29 (1999) 26–30], and refines the design concept further for limiting the size of small pore in hybrid catalysts to~3 Å for restricting access of H 2 S but allowing entrance of H 2 . Further, this refined design concept is applicable to other supported monometallic and bimetallic catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Supported molybdenum oxides for the aldol condensation reaction of acetaldehyde

The (retro-)aldol condensation reaction is an important chemical transformation in the upgrading of biomass-derived compounds into fuels and valuable specialty chemicals. In this study, we found that supported molybdenum oxide (MoO x ) catalysts were active and selective for the aldol condensation of acetaldehyde to crotonaldehyde under steady-state reactor conditions. Through a combination of transmission electron microscopy (TEM), ultraviolet–visible (UV–VIS) diffuse reflectance spectroscopy, Fourier transform infrared (FTIR) spectroscopy of adsorbed pyridine, and steady-state reactor testing, we determined that highly dispersed MoO x has a strong interaction with a γ-Al 2 O 3 support resulting in optimal catalyst performance at low weight loadings. In contrast, MoO x particles supported on SiO 2 have a weaker interaction with the support, resulting in a monotonic relationship between Mo loading and aldol condensation activity. The Lewis acid site density and strength are important parameters for predicting aldol condensation activity across all samples. The concentration of weak acid sites had a poor correlation with aldol condensation activity, most likely because these sites are too weak to activate acetaldehyde for the reaction. Medium and strong acid sites both had good correlations to aldol condensation activity. Results from X-ray absorption near edge structure (XANES) and acetaldehyde temperature programmed desorption (TPD) indicated that partially reduced MoO x was more active for aldol condensation, but pretreatment in reducing or oxidizing environments had no significant effect on steady-state catalytic activity. Finally, characterization of spent catalyst samples through temperature programmed oxidation (TPO) and thermogravimetric analysis (TGA) revealed that catalysts with high densities of strong acid sites tended to form more carbonaceous deposits on the surface over the course of the reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Nanostructured carbon electrocatalyst supports for intermediate-temperature fuel cells: Single-walled versus multi-walled structures

It is unknown if nanostructured carbons possess the requisite electrochemical stability to be used as catalyst supports in the cathode of intermediate-temperature solid acid fuel cells (SAFCs) based on the CsH2PO4 electrolyte. To investigate this application, single-walled carbon nanohorns (SWNHs) and multi-walled carbon nanotubes (MWNTs) were used as supports for Pt catalysts in SAFCs operating at 250 °C. SWNH-based cathodes display greater maximum activity than their MWNT-based counterparts at a cell voltage of 0.8 V, but are unstable in the SAFC cathode as a consequence of electrochemical carbon corrosion. MWNT-based cells are resistant to this effect and capable of operation for at least 160 h at 0.6 V and 250 °C. Cells fabricated with nanostructured carbon supports are more active (52 mA cm -1 vs. 28 mA cm -1 at 0.8 V) than state-of-the-art carbon-free formulations while simultaneously displaying enhanced Pt utilization (40 mA mgPt -1 vs. 16 mA mgPt -1 at 0.8 V). Finally, these results suggest that MWNTs are a viable support material for developing stable, high-performance, low-cost air electrodes for solid-state electrochemical devices operating above 230 °C.

25 ENERGY STORAGE↗
DOE OSTI2011

TPR investigations on the reducibility of Cu supported on Al{sub 2}O{sub 3}, zeolite Y and SAPO-5

Reducibility of Cu supported on Al{sub 2}O{sub 3}, zeolite Y and silicoaluminophosphate SAPO-5 has been investigated in dependence on the Cu content using a method combining conventional temperature programmed reduction (TPR) by hydrogen with reoxidation in N{sub 2}O followed by a second the so-called surface-TPR (s-TPR). The method enables discrimination and a quantitative estimation of the Cu oxidation states +2, +1 and 0. The quantitative results show that the initial oxidation state of Cu after calcination in air at 400 deg. C, independent on the nature of the support, is predominantly +2. Cu{sup 2+} supported on Al{sub 2}O{sub 3} is quantitatively reduced by hydrogen to metallic Cu{sup 0}. Comparing the TPR of the samples calcined in air and that of samples additionally pre-treated in argon reveals that in zeolite Y and SAPO-5 Cu{sup 2+} cations are stabilized as weakly and strongly forms. In both systems, strongly stabilized Cu{sup 2+} ions are not auto-reduced by pre-treatment in argon at 650 deg. C, but are reduced in hydrogen to form Cu{sup +}. The weakly stabilized Cu{sup 2+} ions, in contrast, may be auto-reduced by pre-treatment in argon at 650 deg. C forming Cu{sup +} but are reduced in hydrogen to metallic Cu{sup 0}. - Graphical Abstract: TPR, TPR-(act), s-TPR and s-TPR-(act) profiles of (1.36)Cu/SAPO-5 (A), (4.55)Cu/SAPO-5 (B) and (9.19)Cu/SAPO-5 (C) samples. The intensities of TCD signals in (A) and (B) are multiplied by 4.5 and 2, respectively. Highlights: > Cu supported on SAPO-5, alumina and zeolite Y was investigated by TPR and s-TPR. > Cu oxidation states can be discriminated and quantitatively determined. > In zeolite Y and SAPO-5 Cu{sup 2+} cations are stabilized at weak and strong forms. > Strongly stabilized Cu{sup 2+} cannot be auto-reduced in argon at 650 deg. C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Dispersion states and acid properties of SiO{sub 2}-supported Nb{sub 2}O{sub 5}

Nb{sub 2}O{sub 5}/SiO{sub 2} samples were prepared by the incipient-wetness impregnation method using niobium oxalate aqueous solution. The microstructure and dispersion process of the niobia species supported on SiO{sub 2} were characterized by means of power X-ray diffraction (XRD), laser Raman spectroscopy (LRS), and UV–vis diffuse reflectance spectroscopy (UV–vis DRS). The acid properties were investigated by the method of Hammett indicator and Pyridine adsorption infrared (Py-IR) spectroscopy. The results showed that the dispersion process of Nb{sub 2}O{sub 5} was performed by consuming surface hydroxyl groups of the amorphous SiO{sub 2} support. The aggregation of niobia species led to the formation of microcrystalline particles, so that there was no a clear monolayer dispersion capacity for Nb{sub 2}O{sub 5} supported on amorphous SiO{sub 2}. Furthermore, the catalytic activities of the as-prepared samples were evaluated by the condensation reaction of iso-butene (IB) and iso-butyraldehyde (IBA) to form 2,5-dimethyl-2,4-hexadiene (DMHD). The catalytic activities of the as-prepared samples for the condensation and their acid properties were strongly affected by the dispersion states. - Graphical abstract: The acid amount and strength of Nb{sub 2}O{sub 5}/SiO{sub 2} samples varied with the increase of Nb{sub 2}O{sub 5} loading. The catalytic activities of the as-prepared samples for the condensation and their acid properties were strongly affected by the dispersion states. - Highlights: • The dispersed process of Nb{sub 2}O{sub 5} was completed by consuming surface hydroxyl groups of SiO{sub 2}. • XRD quantitative phase analysis is not applicable for oxides dispersing on amorphous support. • The catalytic activity of Nb{sub 2}O{sub 5}/SiO{sub 2} is closely related to the dispersion state of SiO{sub 2}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Ligand-tailored single-site silica supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction

A successive anchoring of Ti(NMe{sub 2}){sub 4}, cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1′-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on silica was conducted by SOMC strategy in moderate conditions. The silica, monitored by in-situ Fourier transform infrared spectroscopy (in-situ FT-IR), was pretreated at different temperatures (200, 500 and 800 °C). The ligand tailored silica-supported titanium complexes were characterized by in-situ FT-IR, {sup 13}C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) and elemental analysis in detail, verifying that the surface titanium species are single sited. The catalytic activity of the ligand tailored single-site silica supported titanium complexes was evaluated by a cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the dehydroxylation temperatures of silica and the configuration of the ligands. - Graphical abstract: The ligand-tailored silica supported “single site” titanium complexes were synthesized by SOMC strategy and fully characterized. Their catalytic activity were evaluated by benzaldehyde silylcyanation. - Highlights: • Single-site silica supported Ti active species was prepared by SOMC technique. • O-donor ligand tailored Ti surface species was synthesized. • The surface species was characterized by XPS, {sup 13}C CP-MAS NMR, XANES etc. • Catalytic activity of the Ti active species in silylcyanation reaction was evaluated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Characterization of supported TiO{sub 2}-based catalysts green-prepared and employed for photodegradation of malodorous DMDS

Graphical abstract: Display Omitted Highlights: ► We prepare rutile-TiO{sub 2} based catalysts using a simple and eco-efficient method. ► TiO{sub 2} based catalysts coated on supporting materials have large BET surface areas. ► Supported TiO{sub 2} based catalysts efficiently degrade malodorous DMDS. -- Abstract: Titanium dioxide (TiO{sub 2})-based catalysts coated onto two supporting materials (Pyrex glass beads and porous polypropylene fibers) in laboratory have been prepared and characterized. A modified preparation process at low temperature involving the addition of distilled water, aqueous ammonia, and ferrous sulfate, respectively, was used to enhance the spontaneous precipitation of three TiO{sub 2}-based catalysts. The Brunauer–Emmett–Teller surface area of three catalysts was ranged from 160.1 to 202.7 m{sup 2}/g. The surface morphology of three catalysts was identified by a scanning electron microscopy equipped with an X-ray energy dispersive spectrometer. The photocatalytic degradation of dimethyldisulfide was investigated using the supported TiO{sub 2}-based catalysts. The original dimethyldisulfide almost was degraded within 2 h. A similar photocatalytic activity on degrading dimethyldisulfide was demonstrated in comparison with commercial catalysts. Simplicity, low cost, low energy consumption, and solvent-free are the advantages of this proposed method which can be used to photodecompose environmental organic pollutants effectively without heat treatment.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Facile morphology controllable synthesis of PtPd nanorods on graphene-multiwalled carbon nanotube hybrid support as efficient electrocatalysts for oxygen reduction reaction

Highlights: • G–M hybrid was prepared by a novel modified Hummers method followed by thermal annealing. • G–M was verified to be more efficient as the electrocatalyst support compared with G. • Ultrathin PtPd alloy nanorods were supported on the G–M hybrid. • The electrochemical activity of PtPd NRs/G–M outperforms the commercial Pt/C. - Abstract: One-dimensional (1D) anisotropic platinum-based nanorods are particularly attractive electrocatalysts for oxygen reduction reaction (ORR) owing to the inherent structural advantages. In this work, we report the growth of ultrathin PtPd alloy nanorods (3–4 nm) on Graphene-Multiwalled carbon nanotube (G–M) hybrid support via a facile surfactant-free and template-free method as the efficient electrocatalyst for ORR. The as-synthesized PtPd NRs/G–M catalyst exhibits more excellent activity and better durability toward ORR than Pt NRs/G and Pt NRs/G–M catalysts. Noteworthily, it shows an outstanding half-wave potential of 0.810 V and mass activity of 49.5 mA mg{sup –1} at 0.85 V, which are 30 mV and 2.1 times higher than those of commercial 40 wt% Pt/C (JM40) catalyst, respectively. After the accelerated durability tests (ADTs), it also maintains superior stability than JM40. The superior performance is attributed to the combination of the advantageous 1D morphological motif and the synergistic effect with G–M support.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Syntheses of gold supported on metal oxides and their application in organic transformations

Herein, we report a general and straightforward synthesis method for gold supported on mesoporous and microporous metal oxides. Supported materials, in general, show higher crystallinity compare to unsupported systems as verified through powder X-ray diffraction (XRD). Also, through XRD, most of the metal is observed to be in its oxide form, whereas the gold support was found to be in its metallic state, which has been further confirmed from TEM. In terms of surface area, the catalyst was not found to follow any trend. Morphology wise, there are no changes observed after doping except in few cases. Combined results from XRD, X-ray fluorescence spectroscopy, Auger, and X-ray photoelectron spectroscopy suggest that gold is mainly in the bulk and very little (0.04% in case of gold doped calcium oxide) or non (in case of gold doped mixed manganese-cerium oxide) on the surface. The presence of Au (0) 4f peaks in XPS further confirms the metallic state of the gold. Oxides of indium, magnesium and calcium have been studied for the organic transformation reactions. An enhancement in activity and product selectivity was observed in the case of the gold supported catalysts. Indium serves as a great catalyst for C–C coupling and electrophilic aromatic substitution reactions and gives >99% conversion. Interestingly, 88% selectivity for C–C coupling and >99% selectivity for aromatic substitution have been achieved at 100 °C and room temperature respectively. Magnesium and calcium give Knoevenagel condensation products. At room temperature with very low catalyst loading, >99% conversion and selectivity were observed for the Knoevenagel reaction with as high as 35.30 TOF. Finally, a mechanism for the C–C coupling reaction has been proposed based on these results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Water-gas shift reaction on alumina-supported Pt-CeO x catalysts prepared by supercritical fluid deposition

Alumina-supported platinum catalysts, both with and without ceria, were prepared by supercritical fluid deposition and evaluated for activity for water-gas shift reaction. The organometallic precursor, platinum(II) acetylacetonate, was deposited from solution in supercritical carbon dioxide. Analysis of the catalysts by high resolution scanning transmission electron microscopy indicated that platinum was present in the form of highly dispersed metal nanoparticles. Pretreatment of the alumina-supported ceria in hydrogen prior to the deposition of the platinum precursor resulted in more platinum nucleated on ceria than non-pretreated alumina-supported ceria but varied in both particle size and structure. The ceria-containing catalyst that was not pretreated exhibited a more uniform particle size, and the Pt particles were encapsulated in crystalline ceria. Reaction rate measurements showed that the catalyst was more active for water-gas shift, with reaction rates per mass of platinum that exceeded most literature values for water-gas shift reaction on Pt-CeO x catalysts. The high activity was attributed to the significant fraction of platinum/ceria interfacial contact. We found that these results show the promise of supercritical fluid deposition as a scalable means of synthesizing highly active supported metal catalysts that offer efficient utilization of precious metals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Impact of different catalysis supported by oyster shells on the pyrolysis of tyre wastes in a single and a double fixed bed reactor

Highlights: • An innovative way in the disposal of tyre wastes with energy recovery by pyrolysis is proposed. • Performance of catalysts is improved by spreading them over layers of oyster shells. • One or two levels of supported catalytic beds may favor the quantity and/or the calorific value of the pyrolysis by-products. - Abstract: The treatment and disposal of tyres from vehicles has long been of considerable environmental importance. Studies have been undertaken to reduce their environmental impact. In this study, an alternative gas was produced from automobile tyre wastes by the means of a controlled pyrolysis. To do so, a novel catalytic system was designed with the aim of increasing the rate of conversion and improving the quality of the pyrolysis products. This work aimed also to reduce the severity of the overall reactions, by using powder catalysts (MgO, Al{sub 2}O{sub 3}, CaCO{sub 3}, and zeolite ZSM-5) uniformly distributed on two layers of oyster shells (OS) particles. The catalyst/tyres mass ratio was kept for all the tests at 1/30. The pyrolysis reactor was maintained at 500 °C and the influence of each catalyst and of the number of shell beds (0, 1 or 2), on the yield and composition of the derived products, was examined. The gas yields could contribute by 1.2% of total consumption in Tunisia. Furthermore, some combinations could upgrade the derived gas and made it possible to use it as such or with the minimum of post-treatment. It was found that, with the use of supported catalyst, the gas produced is 45% greater compared to classical thermal pyrolysis. The Heating value of the produced gas was also improved by the use of supported catalysts; it was found 16% greater with the use of Al{sub 2}O{sub 3}/OS compared to non-catalytic pyrolysis. When compared to the gas obtained from only one catalytic supported bed, the sulfur content was reduced by 80% with the use of CaCO{sub 3}/OS on two catalytic beds.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2026

Regioselective Hydrosilylation Catalysis with Supported Well-Defined Pt(0) Complexes: Effects of Surface Anions and Phosphenium Ligands

Achieving stable, selective single-atom catalysts is challenging because localsurface-site structures are difficult to control. Surface organometallic chemistry and organic−inorganic hybrid materials offer partial solutions, but applications to supporting zero-valent metals are limited. We demonstrate that well-defined, ionically bound N-heterocyclic phosphenium ([NHP] + ) ligands can be generated on silylium-functionalized sulfated zirconia ([ i Pr 3 Si][SZO]). These surface-bound [NHP][SZO] ligands coordinate Pt(0) centers, forming [(NHP)Pt(0)L][SZO] precatalysts that are highly active for alkyne hydrosilylation. Systematic studies reveal that sterically bulky aromatic ligands enhance regioselectivity, achieving performances comparable to molecular Pt catalysts. Further, more-coordinating anions support more-regioselective precatalysts; therefore, SZO supports more-selective species than weaker-coordinating Al(OC(CF 3 ) 3 ) 3 - functionalized silica, a trend confirmed by molecular analogues. These results demonstrate that both the ligand and support control catalytic behavior and enable solid-state structure− activity relationships.

Catalysts↗
DOE OSTI2021

Impact of Hydration on Supported V 2 O 5 /TiO 2 Catalysts as Explored by Magnetic Resonance Spectroscopy

Supported vanadium oxide catalysts are important industrial materials for a wide array of chemical transformations. The condition of surface hydration is of particular interest as a reflection of the state of a freshly manufactured catalysts prior to its activation in catalytic reactors or under conditions of photocatalysis where surface vandia are exposed to moisture. Under such conditions, the surface vanadia species undergo structural changes as evidenced by 51 V MAS NMR in this study. For low surface vanadia densities on titania, a modest trend towards the formation of dimeric and oligomeric vanadia species was observed under hydrated conditions when compared to the corresponding dehydrated catalyst, which contains a large abundance of monomeric vanadia species. The incorporation of tungsten oxide to the V 2 O 5 /TiO 2 catalyst with low surface vanadia density, however, is found to better stabilize the surface vanadia species on the titania support upon hydration than its tungsta-free counterpart. This stabilization is not an intrinsic property of more extensively oligomerized surface vanadia species in the presence of tungsten oxide, evidenced by conditions of high concentrations of surface vanadia oligomers on titania that exhibit dramatic structural changes upon hydration. At high surface vanadia coverage under hydrated environments, the simultaneous observation of crystalline V 2 O 5 nanoparticles and a mobile phase of surface vanadia species is apparent, where vanadia species are dissolved in the thin hydration layer on the titania support. These new findings have broad implications on the behavior of other metal oxide species on high surface oxide supports under hydrated conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗