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At least 613 records · Page 34

Scalable Synthesis of Pt/SrTiO 3 Hydrogenolysis Catalysts in Pursuit of Manufacturing-Relevant Waste Plastic Solutions

Here, an improved hydrothermal synthesis for shape-controlled, size-controlled 60 nm SrTiO 3 nanocuboid (STO NC) supports, which facilitates the scalable creation of platinum nanoparticles catalyst supported on STO (Pt/STO) for the chemical conversion of waste polyolefins, is reported herein. This synthetic method: 1) produces STO NC supports with average sizes ranging from 25 – 80 nm with narrow size distributions 2) demonstrates how SrCO 3 formation and variation in solution pH prevent the formation of STO NCs, and 3) establishes that STO nucleation prior to the hydrothermal treatment favors nanocuboid formation. The updated hydrothermal synthesis was scaled-up and conducted in a 4L batch reactor, resulting in STO NCs of comparable size and morphology (m = 22.5 g, d avg = 58.6 ± 16.2 nm) to those synthesized under standard hydrothermal conditions in a lab-scale 125 mL autoclave reactor. Size-controlled STO NCs, ranging in roughly 10 nm increments from the 25 nm to 80 nm, were used to support Pt deposited through strong electrostatic adsorption (SEA), a practical and scalable solution-based method. Using SEA techniques and a STO support with an average size of 39.3 ± 6.3 nm, a Pt/STO catalyst with 3.6 wt% Pt was produced and used for high-density polyethylene hydrogenolysis under previously-reported conditions (170 psi H 2 , 300°C, 96h; final product: M w = 2400, Ð = 1.03). As a well-established model system for studying the behavior of heterogeneous catalysts and their supports in reactions, the Pt/STO system detailed in this work presents a unique opportunity to simultaneously convert waste plastic into commercially-viable products while gaining fundamental insight into the mechanism of polyethylene hydrogenolysis.

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Nanoscale Spatial Distribution of Supported Nanoparticles Controls Activity and Stability in Powder Catalysts for CO Oxidation and Photocatalytic H 2 Evolution

Here we discuss, supported metal nanoparticles are essential components of high-performing catalysts, and their structures are intensely researched. In comparison, nanoparticle spatial distribution in powder catalysts is conventionally not quantified, and the influence of this collective property on catalyst performance remains poorly investigated. Here, we demonstrate a general colloidal self-assembly method to control uniformity of nanoparticle spatial distribution on common industrial powder supports. We quantify distributions on the nanoscale using image statistics and show that the type of nanospatial distribution determines not only the stability, but also the activity of heterogeneous catalysts. Widely investigated systems (Au–TiO 2 for CO oxidation thermocatalysis and Pd–TiO 2 for H 2 evolution photocatalysis) were used to showcase the universal importance of nanoparticle spatial organization. Spatially and temporally resolved microkinetic modeling revealed that nonuniformly distributed Au nanoparticles suffer from local depletion of surface oxygen, and therefore lower CO oxidation activity, as compared to uniformly distributed nanoparticles. Nanoparticle spatial distribution also determines the stability of Pd–TiO 2 photocatalysts, because nonuniformly distributed nanoparticles sinter while uniformly distributed nanoparticles do not. This work introduces new tools to evaluate and understand catalyst collective (ensemble) properties in powder catalysts, which thereby pave the way to more active and stable heterogeneous catalysts.

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CO oxidation over a ligand coordinated single site Rh catalyst: identification of the active complex

Single atom catalysis has evolved as a promising strategy to enhance atom utilization efficiency, lower reaction temperatures, and control reaction pathways in heterogeneous catalytic reactions. An important challenge using supported single atom catalysts is the stability of metal single atoms during reactions. Here, we present an approach to stabilize single rhodium atoms on a titania support via a metal–ligand coordination strategy. We explore the reaction activity and mechanism of CO oxidation, as well as the stability under oxidative reaction conditions. Kinetic studies suggest that, with an excess of oxygen in the feed gas, oxygen activation is more facile on defective titania surfaces than on pristine titania surfaces. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis shows that on the pristine titania surface, the 1,10-phenanthroline-5,6-dione (PDO) coordinated Rh catalyst (Rh–PDO/TiO 2 ) catalyzes CO oxidation via the formation of carbonate-like species, which is similar to what occurs on Rh nanoparticle catalysts. However, on the defective titania surface, no carbonate species form for Rh–PDO/def-TiO 2 . The supported Rh–ligand catalysts are also shown to be very stable in such a reaction environment at elevated temperatures, potentially allowing for wide applications.

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Unraveling the Intermediate Reaction Complexes and Critical Role of Support-Derived Oxygen Atoms in CO Oxidation on Single-Atom Pt/CeO 2

CeO 2 -supported Pt single-atom catalysts have been extensively studied due to their relevance in automobile emission control and for the fundamental understanding of CeO 2 -based catalysts. Though CeO 2 -supported Pt nanoparticles are often more active than their single-atom counterparts, the former could easily redisperse to Pt single atom under oxidizing diesel conditions. Therefore, to maximize the reactivity of every Pt atom, it is important to fully understand the reaction mechanism of CeO 2 -supported Pt single atoms. Here, we report a CO oxidation study on a Pt/CeO 2 single-atom catalyst, where we can account for all of the neighbors using in situ and operando spectroscopy techniques and microcalorimetric measurements. Coupled with density functional theory calculations, we present a comprehensive picture of the dynamics of the surface species, the role of surface intermediates, and explain the observed reaction kinetics. We started with a catalyst containing exclusively single atoms and used in situ/operando spectroscopy to provide evidence for their stability during the reaction and to identify the Pt 1 complexes before and during the reaction and their binding to CO. The results reveal that in the precatalyst, Pt is present as Pt(O) 4 on the CeO 2 (111) step edge sites, but during CO oxidation, we find that two Pt 1 complexes coexist, representing two states of the same active site in the reaction cycle. The dominant state/complex remains Pt(O) 4 , which adsorbs CO very weakly as shown by CO microcalorimetry. The second, minority state/complex, Pt(CO)(O) 3 is generated through the reaction of Pt(O) 4 with CO, and CO is bound strongly to Pt 1 . Labile oxygen adatoms from the CeO 2 surface play a major role in the regeneration of Pt(O) 4 either directly from Pt(O) 3 or by reaction with the strongly adsorbed CO in Pt(CO)(O) 3 . We show that the formation of an oxygen vacancy and generation of a labile O* are not barrierless, which explains the long lifetime of Pt(CO)(O) 3 and its detectability despite being a minority complex. The results help to develop a comprehensive view of the dynamic evolution of Pt 1 complexes along the reaction cycle and provide mechanistic insights to guide the design of Pt-based single-atom catalysts.

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Assessing the Role of Interfacial and Metal Sites in Pt/TiO2-Catalyzed Acetic Acid Hydrodeoxygenation

Thermochemical conversion of biomass to produce drop-in quality biofuels typically involves hydrodeoxygenation (HDO) steps following catalytic fast pyrolysis (CFP) to remove excess oxygen and create a more stable bio-oil product. HDO involves co-feeding the CFP vapor-phase product and H2 gas over a bi-functional catalyst. Reducible metal oxide-supported noble-metal catalysts (e.g., Pt/TiO2) are promising materials for HDO chemistry, with recent work aiming to elucidate the role of various Pt/TiO2 actives sites (i.e., Pt-metal, TiO2-support, Pt-TiO2-interfacial sites) in the competing desired deoxygenation and undesired decarboxylation/decarbonylation reactions for important classes of CFP vapor model compounds. Carboxylic acids are one important class of bio-derived compounds that has not been studied extensively for HDO on Pt/TiO2, particularly at the atomic level. Past experimental work evaluating Pt/C and Pt/TiO2 catalysts for acetic acid HDO (AA-HDO) demonstrated selectivity toward C-C and C-O bond-dissociation products, respectively. This work utilizes atomic-scale modeling to discern the role of Pt-metal and Pt-TiO2-interfacial sites in promoting key C-C bond-breaking, C-O bond-breaking, and (de)hydrogenation steps in AA-HDO. Using Pt(111) and Pt-TiO2-interface surface models, adsorption and reaction energetics calculated by density functional theory provide fundamental insights into the role of interfacial sites and oxygen vacancies in promoting desired deoxygenation pathways over undesired decarboxylation/decarbonylation pathways.

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

New Mechanistic and Reaction Pathway Insights for Oxidative Coupling of Methane (OCM) over Supported Na 2 WO 4 /SiO 2 Catalysts

Abstract The complex structure of the catalytic active phase, and surface‐gas reaction networks have hindered understanding of the oxidative coupling of methane (OCM) reaction mechanism by supported Na 2 WO 4 /SiO 2 catalysts. The present study demonstrates, with the aid of in situ Raman spectroscopy and chemical probe (H 2 ‐TPR, TAP and steady‐state kinetics) experiments, that the long speculated crystalline Na 2 WO 4 active phase is unstable and melts under OCM reaction conditions, partially transforming to thermally stable surface Na‐WO x sites. Kinetic analysis via temporal analysis of products (TAP) and steady‐state OCM reaction studies demonstrate that ( i ) surface Na‐WO x sites are responsible for selectively activating CH 4 to C 2 H x and over‐oxidizing CH y to CO and ( ii ) molten Na 2 WO 4 phase is mainly responsible for over‐oxidation of CH 4 to CO 2 and also assists in oxidative dehydrogenation of C 2 H 6 to C 2 H 4 . These new insights reveal the nature of catalytic active sites and resolve the OCM reaction mechanism over supported Na 2 WO 4 /SiO 2 catalysts.

Sourav, Sagar↗

New Mechanistic and Reaction Pathway Insights for Oxidative Coupling of Methane (OCM) over Supported Na 2 WO 4 /SiO 2 Catalysts

Abstract The complex structure of the catalytic active phase, and surface‐gas reaction networks have hindered understanding of the oxidative coupling of methane (OCM) reaction mechanism by supported Na 2 WO 4 /SiO 2 catalysts. The present study demonstrates, with the aid of in situ Raman spectroscopy and chemical probe (H 2 ‐TPR, TAP and steady‐state kinetics) experiments, that the long speculated crystalline Na 2 WO 4 active phase is unstable and melts under OCM reaction conditions, partially transforming to thermally stable surface Na‐WO x sites. Kinetic analysis via temporal analysis of products (TAP) and steady‐state OCM reaction studies demonstrate that ( i ) surface Na‐WO x sites are responsible for selectively activating CH 4 to C 2 H x and over‐oxidizing CH y to CO and ( ii ) molten Na 2 WO 4 phase is mainly responsible for over‐oxidation of CH 4 to CO 2 and also assists in oxidative dehydrogenation of C 2 H 6 to C 2 H 4 . These new insights reveal the nature of catalytic active sites and resolve the OCM reaction mechanism over supported Na 2 WO 4 /SiO 2 catalysts.

Sourav, Sagar↗

Integration of a high oxygen permeability ionomer into polymer electrolyte membrane fuel cell cathodes for high efficiency and power density

In this work, we present a study on the integration of a high oxygen permeability ionomer (HOPI) with high durability carbon supported platinum (Pt/C) catalysts to prepare cathode catalyst layers (CCLs) for polymer electrolyte membrane fuel cells (PEMFCs). A key motivation is the production of PEMFCs with high efficiency and durability for heavy-duty fuel cell vehicles. Our results from integrating a pre-commercial HOPI with robust, state-of-the-art catalysts with medium and low surface area carbon supports show significant increases in specific activities (67% increase over the standard commercial ionomer) at low current densities and reduced oxygen (O 2 ) transport resistances (R O2 ’s) at high current densities, enabling both higher efficiency and peak power density. The reduction in the R O2 with the HOPI is most significant at low relative humidity (RH), due to its more rigid backbone structure resisting compaction at lower water contents. In our ink optimization analysis, we show that the HOPI in this study achieves its peak performance with an ionomer to carbon ratio (I/C) of 0.6 and a moderately alcohol-rich ink solvent when fabricating catalyst layers by the decal method with an automatic wet film coater.

08 HYDROGEN↗

Electronic modulation of metal-support interactions improves polypropylene hydrogenolysis over ruthenium catalysts

Abstract Ruthenium (Ru) is the one of the most promising catalysts for polyolefin hydrogenolysis. Its performance varies widely with the support, but the reasons remain unknown. Here, we introduce a simple synthetic strategy (using ammonia as a modulator) to tune metal-support interactions and apply it to Ru deposited on titania (TiO 2 ). We demonstrate that combining deuterium nuclear magnetic resonance spectroscopy with temperature variation and density functional theory can reveal the complex nature, binding strength, and H amount. H 2 activation occurs heterolytically, leading to a hydride on Ru, an H + on the nearest oxygen, and a partially positively charged Ru. This leads to partial reduction of TiO 2 and high coverages of H for spillover, showcasing a threefold increase in hydrogenolysis rates. This result points to the key role of the surface hydrogen coverage in improving hydrogenolysis catalyst performance.

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Constructing Highly Durable Fuel Cell Catalysts Through Integrating Graphitic Shell‐Protected Composite Carbon Support with Gaseous Co Deposition‐Driven PtCo Intermetallics

Metal dissolution, nanoparticle agglomeration, and carbon support corrosion cause significant performance degradation of current PtCo catalysts under acidic and oxidative oxygen reduction reaction. Here, in this study, an integrated strategy is presented to design high-performance Pt 3 Co intermetallic catalysts by regulating gaseous Co deposition-driven diffusion into Pt nanoparticles supported on a composite carbon. The composite carbon is derived from ZIF-8/polyaniline, consisting of a high-surface-area (HSC) core and a protective graphitic shell (GS), which is employed to design 40 wt.% Pt/HSC@GS catalyst. The corresponding membrane electrode assemblies (MEAs) can maintain 1.09 A cm −2 at 0.7 V (20. 7% loss) after 10 000 cycles (1.0–1.5 V for carbon stability) and 1.15 A cm −2 (16.1% loss) after 150 000 cycles (0.60–0.95 V for catalyst stability). A ordered Pt 3 Co intermetallic is synthesized via a gaseous Co-deposition process, which yields a homogeneous Co-rich layer onto the Pt nanoparticles on the composite support, thereby facilitating Co diffusion into Pt crystal during subsequent ordering annealing to form the ordered intermetallic structure. This gaseous deposition leads to a thin carbon layer on PtCo nanoparticles, inhibiting particle growth during the annealing and mitigating Co dissolution under dynamic electrochemical conditions. The PtCo catalyst achieves impressive MEA performance and long-term durability (1.45 A cm −2 at 0.7 V after 120 000 cycles) under heavy-duty conditions.

30 DIRECT ENERGY CONVERSION↗

Crowded supported metal atoms on catalytically active supports may compromise intrinsic activity: A case study of dual-site Pt/α-MoC catalysts

Increasing the surface population of supported catalytic sites, assuming these sites are stable, is considered a straightforward approach to improving the overall catalytic performance. Here, we report an exception represented by the Pt/α-MoC catalysts featuring atomically dispersed Pt. The Pt/α-MoC catalysts display very high activity for the reverse water gas shift reaction with near 100% CO selectivity for CO 2 :H 2 ratios from 0.25 to 4 and from 250 to 400 °C. Despite the excellent performance, the intrinsic activity per Pt-centric catalytic center declines as the Pt loading increases from 0.1 to 1.0 wt%. With the dispersed Pt evolving from isolated atoms to fully exposed ensembles, the shrinking inter-Pt-atom space impedes CO 2 activation at the critical Pt-Mo interfaces, where the Pt shall temporarily take the -O intermediates. The Pt, even as atomically dispersed without noticeable sintering, is underutilized in such a crowded state. This caution for high-loading catalyst design is translational to other systems where the direct catalytic roles of the supports are crucial.

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Catalyst for water splitting

Methods for producing a carbon-free, PGM-free support for PGM catalyst. The catalytic material comprises PGM metals disposed on a carbon-free support which is catalytic but free of PGM.

Chong, Lina↗

Performance Evaluation of Staged Bosch Process for CO2 Reduction to Produce Life Support Consumables

Utilizing carbon dioxide to produce water and hence oxygen is critical for sustained manned missions in space, and to support both NASA's cabin Atmosphere Revitalization System (ARS) and In-Situ Resource Utilization (ISRU) concepts. For long term missions beyond low Earth orbit, where resupply is significantly more difficult and costly, open loop ARS, like Sabatier, consume inputs such as hydrogen. The Bosch process, on the other hand, has the potential to achieve complete loop closure and is hence a preferred choice. However, current single stage Bosch reactor designs suffer from a large recycle penalty due to slow reaction rates and the inherent limitation in approaching thermodynamic equilibrium. Developmental efforts are seeking to improve upon the efficiency (hence reducing the recycle penalty) of current single stage Bosch reactors which employ traditional steel wool catalysts. Precision Combustion, Inc. (PCI), with support from NASA, has investigated the potential for utilizing catalysts supported over short-contact time Microlith substrates for the Bosch reaction to achieve faster reaction rates, higher conversions, and a reduced recycle flows. Proof-of-concept testing was accomplished for a staged Bosch process by splitting the chemistry in two separate reactors, first being the reverse water-gas-shift (RWGS) and the second being the carbon formation reactor (CFR) via hydrogenation and/or Boudouard. This paper presents the results from this feasibility study at various operating conditions. Additionally, results from two 70 hour durability tests for the RWGS reactor are discussed.

Vilekar, Saurabh A.↗

A Study of How LaFeO 3 and CaTiO 3 Supports Affect the Oxidation, Hydrogenation, and Methane Steam Reforming Activity of Pt and Ni Catalysts

The structure and catalytic properties of Pt and Ni supported on thin films of LaFeO 3 and CaTiO 3 , prepared by Atomic Layer Deposition (ALD), were investigated. X-Ray diffraction (XRD) and scanning transmission electron microscopy (STEM) show that reduction at 1073 K causes Pt-Fe intermetallic compound formation for Pt/LaFeO 3 . For Pt/CaTiO 3 , 1073-K reduction induces local decomposition of the CaTiO 3 with migration of Ti to the Pt. Reduced Pt/LaFeO 3 and Pt/CaTiO 3 exhibited CO-oxidation activity similar to that for Pt supported on MgAl 2 O 4 but were much less active for propane oxidation and hydrogenation of 1-hexene and toluene. In contrast, Ni/CaTiO 3 behaved similarly to a conventional supported Ni catalyst for the methane-steam-reforming (MSR) and 1-hexene hydrogenation. There was also no evidence for local decomposition of the perovskite in the vicinity of the Ni particles. Furthermore, the results obtained in this study demonstrate that metal-perovskite interactions that affect reactivity are specific to each component.

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Polymer Entrapment Flash Pyrolysis for the Preparation of Nanoscale Iridium-Free Oxygen Evolution Electrocatalysts

This paper describes the use of a new polymer entrapment flash pyrolysis (PEFP) method for making nanoscale yttrium ruthenate (Y 2 Ru 2 O 7-δ ) electrocatalysts. Here, this approach effectively reduced the synthesis temperature of phase-pure pyrochlore catalysts from 1000 °C to 550 °C, and greatly suppressed the sintering of catalyst particles. The supported nanocrystalline Y 2 Ru 2 O 7-δ catalysts showed enhanced activity towards oxygen evolution reaction (OER) in acidic electrolyte and were stable at 1.50 V for the comparative study (>20 h) under the current density of 10 mA/cm 2 geo in chronopotentiometry testing. This is equivalent to an overpotential value of 270 mV, about half of that of the reference IrO 2 catalyst. X-ray absorption spectroscopy (XAS) and transmission electron microscopy (TEM) analysis showed that the high-surface-area Y 2 Ru 2 O 7-δ catalyst had an oxygen-deficient structure. This study provides a route to the synthesis of fine ceramic (or oxide)-based electrocatalysts for making high-performing electrocatalysts.

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Role of Silica Support in Phosphoric Acid Catalyzed Production of p -Xylene from 2,5-Dimethylfuran and Ethylene

p-Xylene is a commodity chemical of industrial importance for terephthalic acid production, for which renewable sourcing from naturally abundant lignocellulosic biomass is highly desired. Previous work demonstrated that phosphoric acid stabilized on siliceous zeolite supports (e.g., P-BEA, P-SPP) exhibits high selectivity toward p-xylene (>97%) from 2,5-dimethylfuran (DMF) and ethylene. However, the effect of the support and the contribution of heterogeneous versus homogeneous phosphoric acid on the observed catalytic behavior in the solvated reaction system have not been addressed. Here, we determine the phosphoric acid catalytic activity for DMF conversion and its selectivity to p-xylene when it is supported on a silica support as well as in the absence of a support. Specifically, phosphoric acid catalysis was studied in three different scenarios: (1) phosphoric acid was added in the liquid reaction mixture in the absence of any solid support, (2) phosphoric acid was added in the liquid reaction mixture along with inert silica support including siliceous zeolite (i.e., allowing for phosphoric acid–support assembly to proceed in the reaction mixture), and (3) phosphoric acid was first impregnated on the siliceous zeolite support and then the preassembled supported phosphoric acid catalyst was added in the liquid reaction mixture. We found that the reaction rate and selectivity to p-xylene are different in the above scenarios reflecting the effect of the solid support on the catalytic performance of phosphoric acid. In scenario 1, a low concentration of phosphoric acid (1.7 mM) in the absence of any solid support exhibited high selectivity to p-xylene (80% selectivity to p-xylene at 60% conversion of DMF), which decreased with increasing acid concentration. The selectivity to p-xylene and activity of phosphoric acid significantly increased by adding a silica support into the reaction system (scenario 2). Furthermore, this improvement was attributed to phosphoric acid partial association with the surface of the silica support under the reaction conditions (in situ catalyst assembly). Phosphoric acid predeposited on siliceous zeolite supports (e.g., P-BEA, P-SPP) synthesized via impregnation prior to the reaction (scenario 3) catalyzed the reaction heterogeneously without noticeable leaching and exhibited the highest activity and selectivity to p-xylene, suggesting an important role of the silica support and the need to ensure that phosphoric acid acts as a heterogeneous catalyst in order to accomplish selective conversion of DMF to p-xylene.

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