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DOE OSTI2025

Enhancing durability and activity toward oxygen evolution reaction using single-site Re-doped NiFeO x catalysts at ampere-level

NiFeO x materials are known as among the most active catalysts toward oxygen evolution reaction (OER) for hydrogen generation in alkaline media. Nevertheless, the long-term durability of NiFeO x catalysts for OER is still too far to the industrial application. Herein, we prepared a NiFeReO x catalyst with single-site Re dopants and observed that the single-site Re dopants could significantly enhance the durability without compromising the activity. A cell voltage of 1.82 V without iR correction is noted at the current density of 3000 mA cm –2 in anion-exchange membrane water electrolyzer (AEMWE) with NiFeReO x catalyst, and a very small degradation is observed under 2000 and 1000 mA cm –2 , which remarkably outperforms the pristine NiFeO x . Additionally, the overpotential of 305 mV at 10 mA cm –2 is achieved with the NiFeReO x catalyst, which is lower than 50 mV compared with the pristine NiFeO x catalyst, together with a smaller Tafel slope of 54.3 mV dec -1 . The boosted OER durability and activity of the NiFeReO x catalyst could be attributed to the strong electron-withdrawing property of Re 7+ single atoms leading to the electronic structure optimization and stabilization of Ni/Fe active sites. Our insights propose a new path for designing NiFeO x catalysts with high durability and activity toward OER.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Dual aging pathways of Cu-SSZ-13 SCR catalysts: Hydrothermal vs. sulfur-induced deactivation

Hydrothermal aging (HTA) and chemical poisoning are two primary factors contributing to the real-world degradation of Cu-SSZ-13 SCR catalysts. Investigating field-returned samples offers valuable insights into performance degradation caused by these mechanisms. However, the simultaneous presence of both deactivation pathways complicates the isolation of their individual effects in post-mortem analyses. In this study, we separately prepared model Cu-SSZ-13 SCR catalysts subjected to hydrothermal-aging and sulfur-induced chemical poisoning. Using various characterization techniques, we elucidated the specific role of each aging process in catalyst deactivation and compared the results to real-world field-aged catalysts. Our findings show that hydrothermal aging at 650 °C for 100 h caused dealumination of the zeolite framework but no significant CuO x cluster formation. In contrast, sulfur aging (via sulfur exposure, calcination at 550 °C, and desulfation up to 750 °C) led to CuO x formation without any observable dealumination. On model catalysts, sulfur poisoning was found to reduce Cu mobility and the amount of active Cu sites, thus degrading catalyst activity. Although some activity was recovered upon desulfation, a portion of the initial catalyst activity remained irreversibly lost due to CuO x formation. We demonstrate that this occurs because sulfated species impede the ability of multi-nuclear Cu species (e.g., Cu dimers) to split back into their isolated form, leading to CuSO 4 -clusters that oxidatively desulfate to CuO x species. This degradation pathway explains the significant reduction in activity of field-aged samples, where substantial CuSO 4 -cluster accumulation leads to reduced active Cu and subsequent conversion to CuO x . Furthermore, the conclusions from model catalysts were extended directly to field-aged commercial samples, elucidating the decline in activity and chemical properties during field deployment.

Catalyst Deactivation↗

DOE OSTI2023

Understanding the dynamic evolution of atomically dispersed Cu catalyst for CO 2 electrochemical conversion using integrated XANES analysis and mechanistic studies

Direct electrochemical conversion of CO 2 to ethanol (CH 3 CH 2 OH) offers a promising strategy to lower CO 2 emission while storing energy from renewable electricity. Our recent study reported a carbon-supported atomically dispersed Cu catalyst that achieved the highest reported selectivity for CH 3 CH 2 OH formation (91%) at a relatively low potential (-0.6 V), however, the active site structure that is responsible for such high activity and selectivity has yet to be understood. Here, in this paper, we demonstrate a computational investigation combining X-ray absorption near edge structure (XANES) simulations and a mechanistic study via density functional theory (DFT) to understand the catalyst structures of this Cu catalyst during electrocatalysis and the corresponding reaction mechanisms of the key products. An integrated computational and experimental XANES analysis depicted the dynamic evolution of the catalytic site during electrocatalysis. The as-prepared, atomically dispersed Cu catalyst aggregates and forms metallic clusters/nanoparticles under electrochemical condition, which then break down to smaller oxidized clusters after electrocatalysis. The formed Cu clusters/nanoparticles showed distinct catalytic activity and selectivity as a function of particle size based on the mechanistic investigation using DFT, which is consistent with experimental observations for catalyst samples with different Cu loadings. This comprehensive study which combines experimental and computational XANES investigation, mechanistic study via DFT calculations, and experimental performance of the catalysts, provides unprecedented dynamic and mechanistic insights into the supported atomically dispersed metal catalysts for CO 2 reduction. Such strategy and details gained can further guide discovery of novel catalyst materials for CO 2 electrochemical reduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

High efficiency of isopropanol combustion over cobalt oxides modified ZSM-5 zeolite membrane catalysts on paper-like stainless steel fibers

Catalytic performances of isopropanol combustion and bed pressure drop in structured fixed bed reactor composed of cobalt oxides modified ZSM-5 zeolite membrane catalysts on paper-like stainless steel fibers (Co/ZSM-5/PSSF) and traditional granular ZSM-5 zeolites catalysts were investigated in this paper. Both of the catalyst samples were fabricated by wetness impregnation method and were characterized via X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectrometer (EDS) mapping and the N{sub 2} adsorption/desorption isotherm analyses. The result of EDS mapping revealed that cobalt oxides dispersed well on ZSM-5/PSSF. The Co/ZSM-5/PSSF catalyst display superior catalytic activity to granular Co/ZSM-5 catalyst, 50% and 90% isopropanol conversion temperatures over Co/ZSM-5/PSSF reduced 107 °C and 51 °C, respectively, compared with those over granular Co/ZSM-5 catalysts. The apparent activation energy for isopropanol combustion over Co/ZSM-5/PSSF (90 kJ/mol) was much lower than that over granular Co/ZSM-5 (134 kJ/mol). When the face velocity increased to 14.9 cm/s, the bed pressure drop of reactor filled with only Co/ZSM-5/PSSF catalysts was 9.5% of that of reactor filled with only granular Co/ZSM-5 catalysts. The ZSM-5 zeolite membrane on paper-like stainless steel fibers support provide good dispersion for cobalt oxides and Co/ZSM-5/PSSF show superior catalytic efficiency of isopropanol combustion and produced lower bed pressure drop in reactor compared with granular ZSM-5 zeolites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Heterometallic metal-organic framework-templated synthesis of porous Co{sub 3}O{sub 4}/ZnO nanocage catalysts for the carbonylation of glycerol

The efficient synthesis of glycerol carbonate (GLC) has recently received great attention due to its significance in reducing excess glycerol in biodiesel production as well as its promising applications in several industrial fields. However, the achievement of high conversion and high selectivity of GLC from glycerol in heterogeneous catalytic processes remains a challenge due to the absence of high-performance solid catalysts. Herein, highly porous nanocage catalysts composed of well-mixed Co{sub 3}O{sub 4} and ZnO nanocrystals were successfully fabricated via a facile heterometallic metal-organic framework (MOF)-templated synthetic route. Benefiting from a high porosity and the synergistic effect between Co{sub 3}O{sub 4} and ZnO, the as-prepared composite catalysts exhibited a significantly enhanced production efficiency of GLC in the carbonylation reaction of glycerol with urea compared to the single-component counterparts. The yield of GLC over the Co{sub 50}Zn{sub 50}-350 catalyst reached 85.2%, with 93.3% conversion and near 91% GLC selectivity, and this catalytic performance was superior to that over most heterogeneous catalysts. More importantly, the proposed templated synthetic strategy of heterometallic MOFs facilitates the regulation of catalyst composition and surface structure and can therefore be potentially extended in the tailoring of other metal oxide composite catalysts. - Graphical abstract: Highly porous Co{sub 3}O{sub 4}/ZnO nanocages were fabricated via a heterometallic MOF-templated route and exhibited a significantly enhanced photocatalytic performance in the production of glycerol carbonate. Display Omitted - Highlights: • Porous Co{sub 3}O{sub 4}/ZnO nanocages were synthesized by a facile thermolysis route of heterometallic MOFs. • The as-prepared nanocages possessed massive pores and Co{sub 3}O{sub 4}/ZnO heterojunctions. • The Co{sub 3}O{sub 4}/ZnO ratio in the composites was easily adjusted by tuning the Co/Zn ratio in the precursors. • The composite catalysts exhibited a significantly enhanced production efficiency of glycerol carbonate in the carbonylation reaction of glycerol with urea.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Biogas reforming over Ni catalysts dispersed in different mixed oxides containing Zn2+, Al3+ and Zr4+cations

Highlights: • The oxides mixture containing NiO, ZnO, Al{sub 2}O{sub 3}, NiAl{sub 2}O{sub 4} and ZnAl{sub 2}O{sub 4} was detected. • The results exhibited intermediate interactions between Ni0 and other phases. • Dry reforming of methane was applied to production of synthesis gas. • Deposition of the carbon filamentous on the catalysts surface was observed. - Abstract: The active phase plays an important role in the catalytic activity. However, its applicability is directly associated with other present phases in the mixture. In view of this, we report the performance of Ni catalysts dispersed on mixed oxides containing Zn{sup 2+}, Al{sup 3+} and Zr{sup 4+}cations in biogas reforming. For this purpose, the samples were characterized by X-ray powder diffraction, which showed the formation of a homogeneous mixture of binary (NiO, ZnO, ZrO{sub 2} and Al{sub 2}O{sub 3}) and ternary (NiAl{sub 2}O{sub 4} and ZnAl{sub 2}O{sub 4}) oxides. The temperature-programmed reduction (H{sub 2}-TPR) provided information on the catalyst reduction. The performance of the catalysts was evaluated using two reduction temperatures (650 °C and 750 °C). The reactions were carried out at 750 °C, where the Ni/ZnAlZr catalyst presented the highest CO{sub 2} conversion attributed to the basic sites, which favored the CO{sub 2} adsorption. Otherwise, the Ni/ZnZr catalyst (reduced at 650 °C) showed a high CH{sub 4} conversion. The catalysts were also reduced at 750 °C and a lower conversion of both reactants (CH{sub 4} and CO{sub 2}) was observed. We argued that the agglomeration process during the reduction condition deteriorates the performance of the catalysts reduced at 750 °C.

09 BIOMASS FUELS↗

DOE OSTI2026

Engineering acid-base active sites on an N-doped biochar catalyst for microwave-assisted biodiesel production from waste cooking oil

Acid-base bifunctional catalysts play a crucial role in converting high-free fatty acid (FFA) feedstocks into biodiesel by enabling the simultaneous esterification and transesterification of triglycerides in a single step, thereby minimizing saponification and streamlining the process. In this study, we report the design and development of a novel N-doped acid-base bifunctional biochar catalyst synthesized from renewable biomass precursors- glucose and chitosan. The catalyst’s acidic sites were introduced via surface functionalization with o-sulfobenzoic acid cyclic anhydride, grafting -SO₃H groups onto the carbon framework, while basic sites were generated from amine functionalities (-NH) derived from chitosan, yielding a robust and truly bifunctional surface. The catalyst was characterized and used for the microwave-assisted transesterification of waste cooking oil, and process optimization using response surface methodology (RSM-CCD) yielding a maximum biodiesel yield of 98.8 ± 0.4% under optimal conditions (methanol-to-oil molar ratio 20:1, catalyst loading 5.7 wt%, temperature 99 °C, and reaction time 46.6 min). The catalyst demonstrated good stability, maintaining a yield of 92.2 ± 0.4% after eight reuse cycles. A Life Cycle Assessment (LCA) conducted for 1 kg of biodiesel production revealed a global warming potential of 0.85 kg CO 2 eq and human toxicity potential of 1.59 kg 1,4-DB eq, with the largest environmental contributions arising from catalyst preparation and reuse. In conclusion, this work highlights a green and circular approach to biodiesel production, combining renewable catalyst design, waste feedstock utilization, and quantitative sustainability assessment to guide future developments in sustainable catalysis and biofuel engineering.

Bifunctional catalyst↗

DOE OSTI2018

Combustion behaviors and kinetics of sewage sludge blended with pulverized coal: With and without catalysts

Highlights: • High mass percentage of SS resulted in a great decrease in index S of the blends. • The combustion behaviors and kinetics of the blends with catalysts were studied. • All the catalysts improved the combustion performance of the blended fuel. • All the catalysts reduced the activation energy needed to combustion reaction. • Fe{sub 2}O{sub 3} was an optimal option for catalytic combustion among the tested catalysts. - Abstract: The combustion behaviors of sewage sludge (SS), pulverized coal (PC), and their blends were studied using a thermogravimetric analyzer. The effect of the mass ratio of SS to PC on the co-combustion characteristics was analyzed. The experiments showed that the ignition performance of the blends improved significantly as the mass percentage of SS increased, but its combustion intensity decreased. The burnout temperature (T{sub b}) and comprehensive combustibility index (S) of the blends were almost unchanged when the mass percentage of SS was less than 10%. However, a high mass percentage of SS (>10%) resulted in a great increase in T{sub b} and a notable decrease in S. Subsequently, the effects of different catalysts (CaO, CeO{sub 2}, MnO{sub 2}, and Fe{sub 2}O{sub 3}) on the combustion characteristics and activation energy of the SS/PC blend were investigated. The four catalysts promoted the release and combustion of volatile matters in the blended fuels and shifted their combustion profiles to a low temperature. In addition, their peak separating tendencies were obvious at 350–550 C, resulting in high peak widths. All the catalysts improved combustion activity of the blended fuel and accelerated fixed carbon combustion, which decreased the ignition temperature and burnout temperature of the fuels. CeO{sub 2} had the best catalytic effects in terms of the comprehensive combustion performance and activation energy, followed closely by Fe{sub 2}O{sub 3}. However, the rare-earth compounds are expensive to be applied in the catalytic combustion process of SS/PC blend at present. Based on both catalytic effects and economy, Fe{sub 2}O{sub 3} was potentially an optimal option for catalytic combustion among the tested catalysts.

09 BIOMASS FUELS↗

DOE OSTI2016

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

Overlayer Pt on Ni (Ni@Pt) or Co (Co@Pt) were synthesized and tested for H 2 generation from APR of lactose. H 2 chemisorption descriptor showed that Ni@Pt and Co@Pt overlayer catalysts had reduced H 2 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 H 2 binding strength decreasing the surface coverage of H 2 . 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, further providing evidence for overlayer formation. Lactose APR studies showed that lactose can be used as feedstock to produce H 2 and CO under desirable reaction conditions. The Pt active sites of Ni@Pt and Co@Pt overlayer catalysts showed significantly enhanced H 2 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 H 2 activity. Here, the results suggest that overlayer formation using directed deposition technique could modify the behavior of the surface metal and ultimately modify the APR activity.

09 BIOMASS FUELS↗

DOE OSTI2020

Reagent-Triggered Isomerization of Fluxional Cluster Catalyst via Dynamic Coupling

Metallic cluster catalysts have many thermodynamically accessible isomers with diverse active sites and low reaction barriers, and lately a strong hypothesis emerged that the many catalyst states collectively drive the catalysis. Furthermore, it remained a hypothesis that catalyst isomerization is actually kinetically feasible under the current reaction conditions. Using high-temperature dynamics simulations and sampling, a range of orientations, and vibrational energy distributions, we probe how thermal effects and molecular events affect cluster catalyst dynamics. We show that even such a delicate affair as the dissociation or scattering of a methane molecule on the heavy and thus slow Pt 13 cluster triggers substantial isomerization of the catalyst, far beyond thermal at 700 K. A kinetic coupling between the methane activity and cluster catalyst dynamics is observed. In return, the thermal dynamics of the cluster affects the methane reaction and scattering probabilities. Hence, molecular events at the surfaces of fluxional cluster catalysts should facilitate the population of an ensemble of catalyst states under the current reaction conditions, with implications for available active sites, reaction mechanisms, and apparent rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Impact of Catalyst Ink Dispersing Methodology on Fuel Cell Performance Using in-Situ X-ray Scattering

This work presents a study of the effects of ultrasonic dispersing methodology and time on catalyst agglomerate size in polymer electrolyte membrane fuel cell catalyst ink dispersions. Cathode catalyst inks were prepared and characterized to elucidate the influences of ultrasonic dispersing method and time on catalyst ink particle size and CCL electrochemical properties. In situ ultra-small-, small-, and wide-angle X-ray scattering analyses were used to study the impact of ultrasonication time and methodology on changes in the agglomerate, aggregate, and particle size and distribution during the dispersing process. Ex-situ transmission electron microscopy was also used to investigate the particle size of these inks. Fuel cell membrane electrode assemblies (MEAs) were prepared and tested to determine the influence of ink properties on CCL electrochemical properties, including the electrochemical active surface area, mass activity, H2/air polarization curves, and oxygen mass-transport resistances. It was found that a combination of brief tip sonication followed by bath sonication was most effective at breaking up agglomerates, leading to maximum catalyst activity and MEA performance. Extended tip sonication was found to be too aggressive and resulted in detachment of the platinum nanoparticles from the carbon black support, which decreased electrochemical surface area and MEA performance. Quantification of oxygen mass transport resistance showed that electrodes with large catalyst agglomerates due to insufficient sonication had a higher non-Fickian (pressure independent) than properly dispersed catalyst. Through correlation of the performance with catalyst particle size, the desired CCL structure was proposed, which will provide insight into dispersion strategies for lab-scale spray coating and other processing techniques, as well as for large-scale manufacturing.

30 DIRECT ENERGY CONVERSION↗

DOE OSTI2022

Deciphering the Mechanistic Role of Individual Oxide Phases and Their Combinations in Supported Mn–Na 2 WO 4 Catalysts for Oxidative Coupling of Methane

Oxidative coupling of methane (OCM) is an attractive direct route for upgrading methane to valuable chemicals. In this study, Temporal Analysis of Products (TAP) and steady state experiments are conducted to understand the role of individual oxide phases and their combinations in supported Mn-Na 2 WO 4 /SiO 2 catalysts for OCM. The results from TAP transient kinetic studies indicate that Mn plays an important role in promoting gas phase oxygen activation, while NaO x /SiO 2 and WO x /SiO 2 are relatively inert towards gas phase oxygen and methane activation. However, the supported catalyst combining Na and W in the form Na 2 WO 4 show enhanced gas phase oxygen activation exhibiting a much lower oxygen activation energy (148 kJ/mol) and enhanced activity toward methane activation as compared to the individual supported oxide catalysts. Addition of Mn to Na 2 WO 4 /SiO 2 further decreases the oxygen activation energy by 40 kJ/mol. Moreover, methane activation is also enhanced with CH 3 as the main intermediate but, with increasing Mn content, more CH 2 intermediates are observed. Different forms of oxygen (both dioxygen and atomic) are detected on the catalyst surface using isotopic pump/probe pulsing and their distribution is found to depend on the catalyst composition. An optimal Mn content in the Na 2 WO 4 /SiO 2 catalyst system is needed to enhance the amount of dioxide surface species (e.g., superoxide 16 O 2 - or peroxide 16 O 2 2- ) associated with the Na 2 WO 4 leading to high C 2 selectivity for OCM. When the Mn content is too high, the larger MnOx domains are shown to contribute to the formation of higher concertation of monoxide surface species that lead to nonselective OCM pathways. This insight from transient kinetic characterization using TAP combined with conventional steady state studies, provides a deeper understanding of the role of individual oxide phases and their combination on supported catalysts toward the formation of intermediate surface species and their impact on the OCM reaction mechanism. This knowledge is critical toward designing superior catalyst formulations for OCM.

10 SYNTHETIC FUELS↗

DOE OSTI2016

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

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

09 BIOMASS FUELS↗

DOE OSTI2017

Characterization of MoVTeNbO x catalysts during oxidation reactions using in situ/operando techniques: A review

The domestic fossil feedstock in recent years is shifting towards light hydrocarbons due to abundance of shale gas from hydraulic fracturing. This shift induces a need for greater flexibility in both new and existing processing plants to produce consumer products (polymers, paints, lubricants, etc.) from new feedstocks. The oxidative catalytic reactions operate at milder conditions than the processing of feedstocks through steam cracking. The conversion of light feedstocks (C3 and shorter hydrocarbons) to high value chemicals through highly selective catalysts in the presence of oxygen plays a crucial role in eliminating wastes, reducing greenhouse gas emissions and lowering market prices. Among all catalysts for light hydrocarbon processing through oxidation reactions, bulk mixed metal oxides such as MoVTe(Sb)NbO x catalysts are the most promising due to their performance under favorable reaction conditions (temperature, pressure, etc). Here, state-of-the-art in situ/operando techniques along with transient kinetics can revolutionize the development of catalysts by providing information about the nature of active sites, intermediates and kinetics under realistic industrial conditions. Only through detailed understanding of these catalyst behaviors can new synthesis methods be developed that will improve reactivity, selectivity and lifetimes of these catalysts. In this review, dynamic changes of this mixed oxide catalyst during the reaction (such as changes in surface composition, oxidation states, acidity, etc) are discussed mainly from knowledge and insights obtained from these in situ/operando approaches. The most common oxidation reactions driven by the MoVTeNbO x catalysts and studied under operando/in situ conditions to be discussed here are: (1) oxidative dehydrogenation of light alkanes (ethane and propane), (2) propane ammoxidation to acrylonitrile and (3) selective oxidation of propane to acrylic acid.

03 NATURAL GAS↗

DOE OSTI2018

In Situ UV-Visible Assessment of Iron-Based High-Temperature Water-Gas Shift Catalysts Promoted with Lanthana: An Extent of Reduction Study

Here, the extent of reduction of unsupported iron-based high-temperature water-gas shift catalysts with small (<5 wt %) lanthana contents was studied using UV-visible spectroscopy. Temperature- programmed reduction measurements showed that lanthana content higher than 0.5 wt % increased the extent of reduction to metallic Fe, while 0.5 wt % of lanthana facilitated the reduction to Fe 3 O 4 . In situ measurements on the iron oxide catalysts using mass and UV-visible spectroscopies permitted the quantification of the extent of reduction under temperature-programmed reduction and high-temperature water-gas shift conditions. The oxidation states were successfully calibrated against normalized absorbance spectra of visible light using the Kubelka-Munk theory. The normalized absorbance relative to the fully oxidized Fe 2 O 3 increased as the extent of reduction increased. XANES suggested that the average bulk iron oxidation state during the water-gas shift reaction was Fe +2.57 for the catalyst with no lanthana and Fe +2.54 for the catalysts with 1 wt % lanthana. However, the UV-vis spectra suggest that the surface oxidation state of iron would be Fe +2.31 for the catalyst with 1 wt % lanthana if the oxidation state of iron in the catalyst with 0 wt % lanthana were Fe +2.57 . The findings of this paper emphasize the importance of surface sensitive UV-visible spectroscopy for determining the extent of catalyst reduction during operation. Furthermore, the paper highlights the potential to use bench-scale UV-visible spectroscopy to study the surface chemistry of catalysts instead of less-available synchrotron X-ray radiation facilities.

36 MATERIALS SCIENCE↗

NASA NTRS2016

Relating FTS Catalyst Properties to Performance

During the reporting period June 23, 2011 to August 31, 2013, CAER researchers carried out research in two areas of fundamental importance to the topic of cobalt-based Fischer-Tropsch Synthesis (FTS): promoters and stability. The first area was research into possible substitute promoters that might be used to replace the expensive promoters (e.g., Pt, Re, and Ru) that are commonly used. To that end, three separate investigations were carried out. Due to the strong support interaction of γ-Al2O3 with cobalt, metal promoters are commonly added to commercial FTS catalysts to facilitate the reduction of cobalt oxides and thereby boost active surface cobalt metal sites. To date, the metal promoters examined have been those up to and including Group 11. Because two Group 11 promoters (i.e., Ag and Au) were identified to exhibit positive impacts on conversion, selectivity, or both, research was undertaken to explore metals in Groups 12 - 14. The three metals selected for this purpose were Cd, In, and Sn. At a higher loading of 25%Co on alumina, 1% addition of Cd, In, or Sn was found to-on average-facilitate reduction by promoting a heterogeneous distribution of cobalt consisting of larger lesser interacting cobalt clusters and smaller strongly interacting cobalt species. The lesser interacting species were identified in TPR profiles, where a sharp low temperature peak occurred for the reduction of larger, weakly interacting, CoO species. In XANES, the Cd, In, and Sn promoters were found to exist as oxides, whereas typical promoters (e.g., Re, Ru, Pt) were previously determined to exist in an metallic state in atomic coordination with cobalt. The larger cobalt clusters significantly decreased the active site density relative to the unpromoted 25%Co/Al2O3 catalyst. Decreasing the cobalt loading to 15%Co eliminated the large non-interacting species. The TPR peak for reduction of strongly interacting CoO in the Cd promoted catalyst occurred at a measurably lower temperature than in the unpromoted catalyst. Nevertheless, the Co clusters remained slightly larger, on average, in comparison with the unpromoted 15%Co/Al2O3 reference catalyst. None of the promoted catalysts (i.e., with Cd, In, or Sn) exhibited surface Co0 site densities higher than that of the unpromoted catalyst. In activity testing, the activities were even much lower than what was expected from the H2-TPD results. Two possible explanations were proposed: (1) the promoters may be located on the surfaces of cobalt particles, blocking surface Co0 but being able to desorb hydrogen or (2) the promoters may facilitate Co oxidation during FTS, as previously observed by Huffman and coworkers when K was added to cobalt catalysts.

Zirconia↗

DOE OSTI2020

Low‐PGM and PGM‐Free Catalysts for Proton Exchange Membrane Fuel Cells: Stability Challenges and Material Solutions

Abstract Fuel cells as an attractive clean energy technology have recently regained popularity in academia, government, and industry. In a mainstream proton exchange membrane (PEM) fuel cell, platinum‐group‐metal (PGM)‐based catalysts account for ≈50% of the projected total cost for large‐scale production. To lower the cost, two materials‐based strategies have been pursued: 1) to decrease PGM catalyst usage (so‐called low‐PGM catalysts), and 2) to develop alternative PGM‐free catalysts. Grand stability challenges exist when PGM catalyst loading is decreased in a membrane electrode assembly (MEA)—the power generation unit of a PEM fuel cell—or when PGM‐free catalysts are integrated into an MEA. More importantly, there is a significant knowledge gap between materials innovation and device integration. For example, high‐performance electrocatalysts usually demonstrate undesired quick degradation in MEAs. This issue significantly limits the development of PEM fuel cells. Herein, recent progress in understanding the degradation of low‐PGM and PGM‐free catalysts in fuel cell MEAs and materials‐based solutions to address these issues are reviewed. The key factors that degrade the MEA performance are highlighted. Innovative, emerging material concepts and development of low‐PGM and PGM‐free catalysts are discussed.

Du, Lei↗

DOE OSTI2019

Surface Engineering of 3D Gas Diffusion Electrodes for High‐Performance H 2 Production with Nonprecious Metal Catalysts

Abstract In this work, a methodology is demonstrated to engineer gas diffusion electrodes for nonprecious metal catalysts. Highly active transition metal phosphides are prepared on carbon‐based gas diffusion electrodes with low catalyst loadings by modifying the O/C ratio at the surface of the electrode. These nonprecious metal catalysts yield extraordinary performance as measured by low overpotentials (51 mV at −10 mA cm −2 ), unprecedented mass activities (>800 A g −1 at 100 mV overpotential), high turnover frequencies (6.96 H 2 s −1 at 100 mV overpotential), and high durability for a precious metal‐free catalyst in acidic media. It is found that a high O/C ratio induces a more hydrophilic surface directly impacting the morphology of the CoP catalyst. The improved hydrophilicity, stemming from introduced oxyl groups on the carbon electrode, creates an electrode surface that yields a well‐distributed growth of cobalt electrodeposits and thus a well‐dispersed catalyst layer with high surface area upon phosphidation. This report demonstrates the high‐performance achievable by CoP at low loadings which facilitates further cost reduction, an important part of enabling the large‐scale commercialization of non‐platinum group metal catalysts. The fabrication strategies described herein offer a pathway to lower catalyst loading while achieving high efficiency and promising stability on a 3D electrode.

Sanchez, Joel↗