Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “catalyst characterization”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,261 records · Page 70
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

X-ray spectroscopic characterization of Co(IV) and metal–metal interactions in Co 4 O 4 : Electronic structure contributions to the formation of high-valent states relevant to the oxygen evolution reaction

In this paper, the formation of high-valent states is a key factor in making highly active transition metal-based catalysts of the oxygen-evolving reaction (OER). These high oxidation states will be strongly influenced by the local geometric and electronic structures of the metal ion, which is difficult to study due to spectroscopically active and complex backgrounds, short lifetimes, and limited concentrations. Here, we use a wide range of complementary X-ray spectroscopies coupled to DFT calculations to study Co 4 O 4 cubanes, which provide insight into the high-valent Co(IV) centers responsible for the activity of molecular and heterogeneous OER catalysts. The combination of X-ray absorption and 1s3p resonant inelastic X-ray scattering (Kβ RIXS) allow Co(IV) to be isolated and studied against a spectroscopically active Co(III) background. Co K- and L-edge X-ray absorption data allow for a detailed characterization of the 3d-manifold of effectively localized Co(IV) centers and provide a direct handle on the ligand field environment and covalency of the t 2g -based redox active molecular orbital. Kβ RIXS is also shown to provide a powerful probe of Co(IV), and specific spectral features are sensitive to the degree of oxo-mediated metal-metal coupling across Co 4 O 4 . Guided by the data, calculations show electron-hole delocalization can actually oppose Co(IV) formation. Computational extension of Co 4 O 4 to CoM 3 O 4 structures (M = redox-inactive metal) defines electronic structure contri-butions to Co(IV) formation. Redox activity is shown to be linearly related to covalency, and M(III) oxo inductive effects on Co(IV) oxo bonding can tune the covalency of high-valent sites over a large range and thereby tune E 0 over hundreds of mVs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Degradation of Congo Red dye by a Fe 2 O 3 @CeO 2 -ZrO 2 /Palygorskite composite catalyst: Synergetic effects of Fe 2 O 3

A newly designed Fe 2 O 3 @CeO 2 -ZrO 2 /Palygorskite heterogeneous Fenton catalyst with high degradation efficiency toward Congo Red (CR) is reported in this paper. The iron oxide (Fe 2 O 3 ) was used as the originator of hydroxyl radicals ( OH), CeO 2 -ZrO 2 was used as an efficient matrix of Fe 2 O 3 to enhance the oxidation performance, and the Palygorskite (Pal) played the role of substrate and adsorbent. A synergetic effect of the catalyst was realized by enhancing the adsorption capacity and dispersibility of CeO 2 -ZrO 2 and Fe 2 O 3 nanoparticles, and also due to charge transfer between these two species. The products were characterized by XRD, FTIR, SEM, TEM, XPS, VSM and nitrogen adsorption-desorption isotherms. The catalytic activities were evaluated in terms of many reaction parameters. The removal efficiency of CR was up to 95% on Fe 2 O 3 @CeO 2 -ZrO 2 /Pal under optimized conditions (Pal accounted for 30% of the catalyst mass fraction and Ce/Zr atoms molar ratio = 8:2, T = 30 °C, pH = 3.4, 4 g L -1 catalyst, 40 mM H 2 O 2 and 500 mg/L CR), the product also has shown good reusability. Both α-Fe 2 O 3 and CeO 2 -ZrO 2 played important roles in the generation of hydroxyl radicals, which determined the catalytic efficiency of the composite catalyst. Fe 2 O 3 @CeO 2 -ZrO 2 /Pal was proven to be a promising candidate in the field of heterogeneous Fenton catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Active Sites in the Dealuminated Beta Zeolite-Supported Cobalt Catalyst for Non-Oxidative Ethane Dehydrogenation

Dispersed metal species in siliceous zeolites have been actively studied for non-oxidative dehydrogenation of ethane (NDE). Fundamental insights into the dynamics of metal species in zeolites under reaction conditions have rarely been explored. Herein, we report an atomic level understanding of the dynamics and activity of cobalt (Co) sites in dealuminated Beta zeolite (DeAl-BEA) for NDE during induction and reaction conditions with extensive characterization techniques such as diffuse reflectance UV–vis, solid state nuclear magnetic resonance and X-ray photoelectron, X-ray diffraction along with in situ Fourier transform infrared and X-ray absorption spectroscopy. For a catalyst with 0.5 mass % Co loading, tetrahedral Co 2+ mononuclear sites, di-coordinated to the zeolite framework and with two silanol groups in vicinity (i.e., (≡SiO) 2 Co(HO–Si≡) 2 ), form upon exposure to hydrogen during induction and persist through the NDE reaction. Increasing the Co loading to 3.0 mass % yielded Co sites with similar electronic and coordination structures but slightly elongated Co–O bonds. Upon cooling to room temperature, the Co sites persisted in the same coordination environment, though the disappearance of a feature in the Co K-edge near-edge region revealed changes in the active site’s electronic structure coinciding with modest shifts in bond lengths. The electronic structure and activity of (≡SiO) 2 Co(HO–Si≡) 2 sites were studied comparatively to a few other hypothetical Co 2+ coordination structures, using electronic structure calculations and microkinetic simulations. The simulations showed that NDE is controlled by β-hydride elimination following C–H bond activation and that Co-sites possessing flexibility because of neighboring silanol defects are more active. Interestingly, dinuclear Co–O–Co sites (i.e., (≡SiO)Co(HO–Si≡) 2 –O–(HO–Si≡) 2 Co(≡SiO)) were more active than the mononuclear (≡SiO) 2 Co(HO–Si≡) 2 sites because of favorable hydrogen bonding with the vicinal silanol groups. In conclusion, the present study bridges the gap between the knowledge acquired by ex-situ characterizations and the active sites under the reaction conditions in alkane dehydrogenation chemistry.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Cerium migration during PEM fuel cell accelerated stress testing

Cerium is a radical scavenger which improves polymer electrolyte membrane (PEM) fuel cell durability. During operation, however, cerium rapidly migrates in the PEM and into the catalyst layers (CLs). In this work, membrane electrode assemblies (MEAs) were subjected to accelerated stress tests (ASTs) under different humidity conditions. Cerium migration was characterized in the MEAs after ASTs using X-ray fluorescence. During fully humidified operation, water flux from cell inlet to outlet generated in-plane cerium gradients. Conversely, cerium profiles were flat during low humidity operation, where in-plane water flux was negligible, however, migration from the PEM into the CLs was enhanced. Humidity cycling resulted in both in-plane cerium gradients due to water flux during the hydration component of the cycle, and significant migration into the CLs. Fluoride and cerium emissions into effluent cell waters were measured during ASTs and correlated, which signifies that ionomer degradation products serve as possible counter-ions for cerium emissions. Fluoride emission rates were also correlated to final PEM cerium contents, which indicates that PEM degradation and cerium migration are coupled. Lastly, it is proposed that cerium migrates from the PEM due to humidification conditions and degradation, and is subsequently stabilized in the CLs by carbon catalyst supports.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2025

Visualizing Size-Dependent Dynamics of CeO 2-δ {100}-Supported CoO x Nanoparticles Under CO 2 Hydrogenation Conditions

Carbon dioxide is a major greenhouse gas. In order to optimize processes focused on its chemical valorization, one needs detailed information about the effects of CO 2 and/or CO 2 /H 2 mixtures on the structure and morphology of metal/oxide catalysts. Here, in this study, the evolution of a catalyst with cobalt supported on CeO 2 -cube nanostructures under CO 2 hydrogenation conditions was investigated by using a set of in situ characterization techniques (X-ray absorption fine structure, X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy, and environmental transmission electron microscopy (TEM)). The {100} facets of the ceria support displayed an unexpectedly high stability due to strong interactions with the aggregates of cobalt oxide. A significant influence of interfacial bonding between CoO x and CeO 2-δ {100} is evident through a clear preference in the orientation of CoO x nanoparticles (NPs) with respect to the substrate. For initially reduced Co/CeO 2 -cube nanostructures, a kinetically controlled oxidation of cobalt upon the introduction of CO 2 was observed during the early stages of CO 2 hydrogenation. Environmental TEM revealed the size-dependent morphological behavior of cobalt oxide NPs due to strong interactions with the CeO 2 {100} surface. When the environment was switched from H 2 to a mixture of H 2 and CO 2 at 250 °C, small CoO x NPs (in the largest dimension < 2.5 nm) rapidly transformed from a pyramidal three-dimensional (3D) form to a planar, monatomic layer attached to the concurrently oxidized CeO 2-δ {100} surface. This maximizes the number of sites available for the binding of CO 2 or reaction intermediates. The shape transformation reflected the oxophilic character of cobalt and strong metal–support interactions. The removal of CO 2 from the gas phase led to a reduction of the cobalt oxide NPs by hydrogen and a reversible two-dimensional → 3D transformation. In contrast, no significant morphological changes, apart from further oxidation, were observed for big CoO x NPs (in the largest dimension > 3 nm). These trends are not seen for nanoparticles of noble metals. The observed morphological and structural changes in the small CoO x NPs affected the stability of reaction intermediates and modified the selectivity of the CoO x /CeO 2 catalyst system for methane production.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Entropy-stabilized single-atom Pd catalysts via high-entropy fluorite oxide supports

Single-atom catalysts (SACs) have attracted considerable attention in the catalysis community. However, fabricating intrinsically stable SACs on traditional supports (N-doped carbon, metal oxides, etc.) remains a formidable challenge, especially under high-temperature conditions. Here, we report a novel entropy-driven strategy to stabilize Pd single-atom on the high-entropy fluorite oxides (CeZrHfTiLa)O x (HEFO) as the support by a combination of mechanical milling with calcination at 900 °C. Characterization results reveal that single Pd atoms are incorporated into HEFO (Pd1@HEFO) sublattice by forming stable Pd–O–M bonds (M = Ce/Zr/La). Compared to the traditional support stabilized catalysts such as Pd@CeO 2 , Pd 1 @HEFO affords the improved reducibility of lattice oxygen and the existence of stable Pd–O–M species, thus exhibiting not only higher low-temperature CO oxidation activity but also outstanding resistance to thermal and hydrothermal degradation. This work therefore exemplifies the superiority of high-entropy materials for the preparation of SACs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

One-step lignocellulose depolymerization and saccharification to high sugar yield and less condensed isolated lignin

The cost of sugar production remains a key challenge in future lignocellulosic biorefineries. We demonstrate that ZnBr 2 , an inexpensive inorganic salt, provides nearly theoretical yields of glucose and xylose in one-step from poplar wood at 85 °C and short reaction times at molten salt hydrate (MSH) conditions without an acid. Catalytic depolymerization of the isolated MSH lignin, using a CoS 2 catalyst, yields 17% phenol-like monomers compared to only 1% produced from the acidified MSH lignin. Reductive catalytic fractionation of MSH lignin over Ru/C resulted in two times higher total monomer yield compared to the AMSH lignin. Both the lignin samples were characterized using 2D HSQC NMR and the thioacidolysis method. Thioacidolysis studies reveal 8.4% and 1.8% of β-O-4 linkages in MSH and acidified MSH lignin, respectively. Thermodynamic modeling and 13 C NMR spectroscopy indicate that the effectiveness of this catalyst arises from the strong interaction of the Lewis acidic zinc cation (Zn 2+ ) with the coordinated water molecules resulting in hydrolysis of the metal aquo complex and to the salt-driven increase in the H + activity coefficient. Techno-economic analysis demonstrates that despite being slower, the ZnBr 2 MSH media has cost advantages, compared to conventional hydrolysis and even to the LiBr and ZnBr 2 AMSH, due to the higher quality of lignin.

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

Unravelling the origin of reaction-driven aggregation and fragmentation of atomically dispersed Pt catalyst on ceria support

Metal–support interaction plays a crucial role in governing the stability and activity of atomically dispersed platinum catalysts on ceria support. The migration and aggregation of platinum atoms during the catalytic reaction leads to the redistribution of active sites. In this study, by utilizing a multimodal characterization scheme, we observed the aggregation of platinum atoms at high temperatures under reverse water gas shift reaction conditions and the subsequent fragmentation of platinum clusters, forming “single atoms” upon cooling. Theoretical simulations of both effects uncovered the roles of carbon monoxide binding on perimeter Pt sites in the clusters and hydrogen coverage in the aggregation and fragmentation mechanisms. Finally, this study highlights the complex effects of adsorbate and supports interactions with metal sites in Pt/ceria catalysts that govern their structural transformations under in situ conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Novel Biocomposites Based on Sunflower Oil and Alfa Fibers as Renewable Resources

The aim of this work is to develop biocomposites based on modified sunflower oil as resin and short natural fibers from Alfa plants (Stipa tenacissima) as reinforcement. Epoxidized sunflower oil (ESFO) was chemically modified via acrylation reaction to obtain acrylated epoxidized sunflower oil resin (AESFO). The AESFO resin was then copolymerized with styrene as co-monomer in the presence of boron trifluoride (BF{sub 3}) as cationic initiator and cobalt octoate (Co) as catalyst. Experimental conditions of this modification were optimized by varying styrene, Co and BF{sub 3} wt%. The styrene was varied from 30, 40 to 50 wt% while the catalyst (Co) was varied from 0, 0.01, 0.02 to 0.03 wt%. Two different percents of BF{sub 3} were considered: 0.5 and 1 wt%. The prepared samples were evaluated according to their appearance and then characterized in terms of tensile properties (stress at break, Young’s modulus and elongation at break) to determine the best ratio of styrene/BF{sub 3}/Co. Alfa fibers, used as bio-reinforcement, were treated with a 5% NaOH solution and characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and thermo gravimetric analysis (TGA). Biocomposites were prepared by using untreated (UAF) and treated Alfa fibers (TAF) at a ratio of 5 wt% and characterized in terms of tensile properties and morphology by SEM. The best results were obtained with TAF. Then, the ratio of TAF was varied (5, 7.5 and 10 wt%) and the tensile and thermal properties of the biocomposites were characterized. The results showed that the best results were obtained with the ratio of 7.5 wt%.

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

Demonstration of photoreactor platform for on-sun unassisted photoelectrochemical hydrogen generation with tandem III–V photoelectrodes

Photoelectrochemical (PEC) water splitting is a direct solar-driven technology that converts solar energy to storable chemical energy in the form of hydrogen. In addition to semiconductor and catalyst development for improved photoelectrodes, designing reactors for testing and operation of PEC systems under inherently dynamic outdoor solar illumination is necessary to further the commercial viability of PEC technology. Herein, we present a versatile photoreactor system mounted on a solar tracker for outdoor PEC testing and demonstrate unassisted PEC water splitting under real world on-sun conditions. GaInP 2 /GaAs tandem absorber photoelectrodes with a MoS 2 catalyst were fabricated and exhibit >8% solar-to-hydrogen efficiency. On-sun efficiency and stability of the photoelectrodes were characterized on both sunny and partly cloudy days with continuous monitoring of insolation and weather conditions. Furthermore, the versatile photoreactor and outdoor PEC testing capabilities and methods presented here can accelerate the development of other solar fuel generating systems and technologies.

solar fuels↗
DOE OSTI2019

Synthesis and Characterization of Acridinium Dyes for Photoredox Catalysis

Photoredox catalysis is a rapidly evolving platform for synthetic methods development. The prominent use of acridinium salts as a sustainable option for photoredox catalysts has driven the development of more robust and synthetically useful versions based on this scaffold. However, more complicated syntheses, increased cost, and limited commercial availability have hindered the adoption of these catalysts by the greater synthetic community. By utilizing the direct conversion of a xanthylium salt into the corresponding acridinium as the key transformation, we present an efficient and scalable preparation of the most synthetically useful acridinium reported to date. This divergent strategy also enabled the preparation of a suite of novel acridinium dyes, allowing for a systematic investigation of substitution effects on their photophysical properties.

Chemistry↗
DOE OSTI2016

Controlled growth of ultrathin Mo 2 C superconducting crystals on liquid Cu surface

Exhibiting thickness-dependent change in the critical temperature (T c ) for the onset of superconductivity, Mo 2 C is an important new member in the family of two-dimensional atomic crystals. Controllable growth in terms of morphology and thickness is necessary to elucidate its intrinsic properties at the 2D limit. Here we demonstrate the chemical vapor deposition of ultrathin Mo 2 C crystals on liquid Cu surface where the morphology of the crystals can be controlled by tuning the carbon supersaturation. A unique staggered carbon vacancy ordering is discovered in Mo 2 C crystals having particular geometries. Thickness engineering of the crystal can be achieved by controlling the thickness of the Cu catalyst layer, which affords a facile route to grow ultrathin 2D samples. Ultrathin Mo 2 C crystals so obtained, have been characterized using aberration corrected scanning transmission electron microscopy annular dark field imaging, where the co-existence of both AA and AB stacking modes is observed. The high crystallinity of the Mo 2 C crystals synthesized in this work is attested by its characteristic sharp superconducting transition.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Manufacturing Process of Electrode Films

Rotating disk electrode (RDE) experiments form a key experimental characterization technique for measuring electrocatalyst performance and durability. While standard RDE testing protocols have been documented, it has been noted that catalyst film quality can skew measurements. Furthermore, the impact of relative humidity on drying is studied in an effort to produce consistent, high quality catalyst films for RDE experiments, which shows that high quality catalyst films can be manufactured repeatedly in a controlled environment, such as inside an environmental chamber as described.

08 HYDROGEN↗
DOE OSTI2020

Microanalytical Approaches to Characterizing REE in Appalachian Basin Underclays

The search for a reliable U.S. domestic source of rare earth elements (REE) is necessary to support the demand of advanced energy applications (e.g., catalysts, electronics, magnets). Sedimentary deposits may be sources for selectively recovering REE and critical metals—specifically the interbedded seat rock, or underclay, that underlies or forms the floor of a coal seam. This material is often a major component of coal waste fines and refuse and thus readily available. This study examines several Appalachian Basin underclays associated with actively mined coal seams as potential feedstocks for the REE. Multimodal microanalytical electron microscopy (SEM, FIB-SEM, EMPA) synchrotron-based µXRF, and image processing techniques are coupled with detailed elemental and mineral data to classify the 2D and 3D petrophysical properties of the materials. The REE contents of Appalachian Basin underclays were measured from 235–399 ppm and predominantly observed as discrete REE-bearing minerals such as monazite and xenotime on the order of 10–100 µm in size. These REE-bearing minerals typically accounted for less than 1% of the scanned areas and volumes under SEM and FIB-SEM analysis, with the exception of regions enriched in crandallite. Synchrotron-based µXRF elemental maps further identified several REE deposition environments in different underclays, including micro-scale (10–100 µm) light REEs co-localizing with Ca and P, micro-scale heavy REEs with Fe, and large-scale light REEs (>200 µm) co-localizing with Sr, Ba, Ca and P.

36 MATERIALS SCIENCE↗
NASA NTRS1973

Study of the zinc-silver oxide battery system

Theoretical and experimental models for the evaluation of current distribution in flooded, porous electrodes are discussed. An approximation for the local current distribution function was derived for conditions of a linear overpotential, a uniform concentration, and a very conductive matrix. By considering the porous electrode to be an analog of chemical catalyst structures, a dimensionless performance parameter was derived from the approximated current distribution function. In this manner the electrode behavior was characterized in terms of an electrochemical Thiele parameter and an effectiveness factor. It was shown that the electrochemical engineering approach makes possible the organizations of theoretical descriptions and of practical experience in the form of dimensionless parameters, such as the electrochemical Thiele parameters, and hence provides useful information for the design of new electrochemical systems.

Nanis, L.↗
DOE OSTI2014

Production of biodiesel from vegetable oils; Producción de biodiesel a partir de aceites vegetales

One of the major impacts that humans have had on the world is the consequence of the use of natural resources of the planet, whose purpose has been the energy supply for economic and technological development. This economic development has caused an increase in the demand for goods and services in industrialized countries, and in turn has led to an increase in per capita consumption of energy worldwide. For this reason, it is very important to develop new energy alternatives to reduce the actual dependence on petroleum and, at the same time, reduce the impact of emissions of greenhouse gases to the environment. An alternative to using fossil fuels is biodiesel, which is biodegradable, eco-friendly, and represents an economical source of energy. Biodiesel may be produced by the transesterification reaction of new or used vegetable oils (for example sunflower, corn, or olive oil) with a short chain alcohol (methanol) in the presence of a catalyst (NaOH). In the present work we have synthesized biodiesel from these three types of vegetable oils that have been subsequently characterized. Different chemical tests have been used to ensure the quality of the biodiesel obtained. The results indicate that sunflower oil provided better efficiency biodiesel, followed by corn and olive oils. CO 2 emissions that could affect the environment were, in all cases, less than 4.1%.

09 BIOMASS FUELS↗
DOE OSTI2016

Fe doped TiO{sub 2} photocatalyst for the removal of As(III) under visible radiation and its potential application on the treatment of As-contaminated groundwater

Highlights: • Incorporation of Fe in TiO{sub 2} lattice extended absorption to visible light region. • TiO{sub 2}–Fe 1.0 in anatase crystalline form was synthesized by sol–gel method. • TiO{sub 2}–Fe 1.0 showed the highest photocatalytic activity for As(III) oxidation. • TiO{sub 2}–Fe 1.0 had the highest adsorption capacity for the removal of generated As(V). • TiO{sub 2}–Fe is a promising material on the treatment of As contaminated groundwater. - Abstract: The Fe doped TiO{sub 2} catalyst was evaluated under visible radiation for As(III) removal. The TiO{sub 2}–Fe was synthesized by sol–gel technique at 0.0, 1.0, 2.5, 5.0 and 10.0 wt% iron doping concentrations. The semiconductors were characterized by X-ray diffraction, diffuse reflectance UV–vis, Raman spectroscopy, nitrogen physisorption, SEM–EDS and potentiometric titration for point of zero charge determination. The photocatalytic oxidation of As(III) was assessed in aqueous suspension contained 5 mg L{sup −1} As(III) at pH 7 with 0.25 g L{sup −1} catalyst loading. The incorporation of iron ions in TiO{sub 2} lattice extended the absorption to visible light region and create surface oxygen vacancies which favor photocatalytic oxidation reaction of As(III) using a small doping amount of Fe (1.0 wt%) in TiO{sub 2} powder. Additionally, TiO{sub 2}–Fe 1.0 showed the highest adsorption capacity for As(V) removal compared to sol–gel TiO{sub 2} and P25 indicating that this catalyst is a promising material for As contaminated groundwater treatment.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Understanding Structure–Property Relationships of MoO 3 -Promoted Rh Catalysts for Syngas Conversion to Alcohols

Rh-based catalysts have shown promise for the direct conversion of syngas to higher oxygenates. Although improvements in higher oxygenate yield have been achieved by combining Rh with metal oxide promoters, details of the structure of the promoted catalyst and the role of the promoter in enhancing catalytic performance are not well understood. In this work, we show that MoO 3 -promoted Rh nanoparticles form a novel catalyst structure in which Mo substitutes into the Rh surface, leading to both a 66-fold increase in turnover frequency and an enhancement in oxygenate yield. By applying a combination of atomically controlled synthesis, in situ characterization, and theoretical calculations, we gain an understanding of the promoter-Rh interactions that govern catalytic performance for MoO 3 -promoted Rh. We use atomic layer deposition to modify Rh nanoparticles with monolayer-precise amounts of MoO 3 , with a high degree of control over the structure of the catalyst. Through in situ X-ray absorption spectroscopy, we find that the atomic structure of the catalytic surface under reaction conditions consists of Mo–OH species substituted into the surface of the Rh nanoparticles. Furthermore, using density functional theory calculations, we identify two roles of MoO 3 : first, the presence of Mo–OH in the catalyst surface enhances CO dissociation and also stabilizes a methanol synthesis pathway not present in the unpromoted catalyst; and second, hydrogen spillover from Mo–OH sites to adsorbed species on the Rh surface enhances hydrogenation rates of reaction intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗