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Structure of iridium oxide catalysts dictates performance differences for proton exchange membrane water electrolyzers
Proton exchange membrane water electrolyzers (PEMWEs) are promising zero-emission technologies. However, their high cost remains a barrier to widespread adoption. Iridium oxide is commonly used as an oxygen evolution reaction (OER) catalyst, and its cost and scarcity make it essential to reduce its loading while increasing its activity. Evaluation of iridium oxide activity should be carried out in the membrane electrode assembly (MEA) configuration to replicate realistic operating conditions. Herein, we present a comprehensive benchmarking framework to accurately evaluate the amorphous and crystalline iridium oxides at the MEA level. By systematically varying the catalyst loading, this study confirmed that each MEA was utilized uniformly, presenting intrinsic electrochemical properties independent of the loading. Through intrinsic charge density determined by voltammetry, we established two electrochemical descriptors to evaluate catalyst redox reactions. The mass activity was evaluated by correlating current vs. loading, and the slope provides loading-independent mass activity. The effect of the porous transport layer on OER activity was discussed, identifying a ‘background’ current at zero-loading. In conclusion, this study highlights potential pitfalls in MEA-level catalyst screening and underscores the importance of the loading study for reliable results.
Electronic Structure Calculations for Improving Catalyst Design for Use in the Hybrid Sulfur Cycle
The hybrid sulfur cycle is a promising means for efficient production of large quantities of hydrogen with a small carbon footprint. However, many challenges remain in designing catalysts that are stable at high temperatures and have high sulfur tolerance. Theoretical calculations can provide fundamental insights at the electronic scale to improve our understanding of reaction mechanisms and surface energetics, thereby facilitating improved catalyst design. Here, density functional theory was used to explore the reaction energetics of the hybrid sulfur cycle on Pt, Au, and Pt - Au surfaces. A database of information has been built that contains calculations from which adsorption energetics and density of states information can be extracted.
Replication Data for: Decoding reactive structures in dilute alloy catalysts
The data underlying this published work have been made publicly available in this repository as part of the IMASC Data Management Plan. This work was supported as part of the Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0012573.
Active Sites and Structural Transformation of NiFeOx Catalysts during Electrocatalytic Oxygen Evolution Reaction (OER): Effects of Catalyst Loading and Support
The 67th AVS International Symposium and Exhibition, Virtual, October 24-29, 2021.
Core-Shell Oxidative Aromatization Catalysts for Single Step Liquefaction of Distributed Shale Gas (Final Technical Report)
The objective of this project was to design and demonstrate a core-shell structured multifunctional catalyst to convert the light (dry) components of shale gas into liquid aromatic compounds (primarily benzene and toluene) in a single step. Operated in a modular oxidative aromatization system (OAS) under a cyclic redox scheme, the novel catalyst and process can significantly improve the value and transportability of distributed shale gas. Since the project started, each quarter addressed a different set of tasks related to the completion of the milestone detailed in the project award. The yearly summaries of these tasks are summarized below: Q1-Q4: • Conducted project planning and literature search. • Investigated a number of SHC redox catalysts using thermogravimetric analysis and fixed-bed reactor experiments. • Initiated process modeling towards generating two process models for the methane DHA base case and OAS process. • Developed DHA catalysts capable of producing >500 g/kg-cat-hr aromatics at 80% or greater aromatics selectivity at 700°C. Q5-Q8: • Developed alternative approaches with sequential bed configurations to enhance the aromatic yields based on OCM+DHA • Improved the zeolite synthesis efficiency by using the microwave-assisted technique and investigated the synthesis conditions on the zeolite yield, crystalline structure and morphology • Constructed a set of Aspen Plus process models with significant energy savings for OAS as compared to the base case non-oxidative DHA. • Adapted conventional hydrothermal method to be applicable to the microwave synthesizer unit for more efficient catalyst synthesis. • Studied the structure of the OCM catalyst and the dispersion of the carbonate in the redox reactions and in methane flow with Raman Spectroscopy. Q9-Q12: • Scaled up the catalyst synthesis with the microwave synthesis method. Based on its performance, procedural characterizations and catalytic performance testing were further conducted for the new microwave synthesized catalysts with the newly-developed product analysis procedure. • Developed the reaction system setup for the C2-DHA or OCM+DHA reaction product and achieved a better product collection-analysis method for the aromatic products with an improved carbon balance. The product from the OCM reaction exhibited complicated effects on the DHA catalyst. • Conducted additional OCM catalyst characterization using Near Ambient Pressure X-ray Photoelectron Spectroscopy and in situ Raman characterization • Validated the significant energy savings for OAS as compared to the base case non-oxidative DHA. Successfully set up the simulation model for the OCM+DHA+SHC reaction system based on the updated experimental results from NCSU. Q13-End of project: • Synthesized new zeolite catalysts by the microwave method, conducted characterizations (XRD, SEM, and TEM) and catalytic behavior testing. • Explored the “wet” C 2 H 6 and C 2 H 4 DHA reactions with using steam co-feed. A subsequent reduction as the regeneration step can regenerate the DHA catalyst and recover 99% activity of the fresh performance. • Achieved a 15.3% single-pass aromatic yield from methane by rationally combining the OCM and DHA at different temperatures. • Conducted a 105-hour stability test with an improved regeneration procedure, with an average aromatic yield of 13.8%. • Developed new catalyst and achieved a record-high 23.2% yield.
Atomically Dispersed Dual-Metal Site Catalysts for Enhanced CO[subscsript 2] Reduction: Mechanistic
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Size and Structure Effects of Carbon-Supported Ruthenium Nanoparticles on Waste Polypropylene Hydrogenolysis Activity, Selectivity, and Product Microstructure
Hydrogenolysis of plastic waste using Ru-based catalysts is promising for deconstructing polyolefins into lower molecular weight products. Yet, the effect of catalyst atomic structure and size on activity and product selectivity is poorly understood. Herein, we expose the effect of metal particle size and atomic structure on isotactic-polypropylene (i-PP) hydrogenolysis over Ru supported on carbon. Despite similar molecular weight distributions of solid and liquid products, their physical properties are distinct due to different chain regio-irregular CH3 sequences of steric pentads containing racemo configurations. We propose that i-PP hydrogenolysis entails an interplay of C–C bond scission and stereoisomerization. The active site’s local electronic environment and structure dictate the former, whereas polymer–catalyst surface interactions creating suitable polymer conformations control the latter. C–C scission and stereoisomerization are structure-sensitive. Small, disordered nanoclusters are effective in C–C bond scission, whereas larger metal nanoparticles promote stereoisomerization. Finally, we hypothesize that a heterogeneous distribution of metal active sites is essential for deconstruction and product (lubricant base oil) quality control.
Hollow-structured Ni-N-C catalysts for highly selective CO 2 electroreduction
Atomically dispersed single-atom catalysts have emerged as promising non-precious catalyst alternatives to expensive Ag and Au catalysts for electrochemical CO 2 reduction reaction (CO 2 RR). In particular, nickel-nitrogen-carbon (Ni-N-C) catalysts have demonstrated a high faradaic efficiency (FE) toward CO formation at low overpotentials. Nonetheless, the exact nature of Ni active sites under CO 2 RR remains elusive and conventional Ni-N-C catalysts are limited by microporosity and low density of Ni single atoms, hindering performance in CO 2 electrolyzers. Here, we report the synthesis of hollow-structured Ni-N-C ( hs -Ni-N-C) catalysts via a post-synthesis modification (PSM) strategy using partial ligand exchange of 2-methylimidazole with 3-amino-1,2,4-triazole. This approach enables the formation of a hollow structure, resulting in more than a twofold increase in Ni atom density compared to regular Ni-N-C (r-Ni-N-C). In a zero-gap CO 2 electrolyzer, the optimized hs -Ni-N-C allows for achieving an FE CO of 97% at a current density of > 100 mA cm⁻ 2 , while maintaining high CO selectivity with stable performance over 100 h at 2.5 V. hs-Ni-N-C shows a more than sevenfold increase in the CO partial current density relative to r-Ni-N-C resulting from the combined effects of a higher density of Ni single-atom sites, improved kinetics, and lower transport resistance under the operating conditions, as indicated by electrochemical impedance spectra and distribution of relaxation times analysis. Operando high energy-resolution X-ray absorption spectroscopy (XAS) reveals that atop-bonded CO on Ni single sites induces dynamic transformations of the Ni–N coordination environment, leading to a symmetric coordination structure of hs -Ni-N-C. Under CO 2 RR, the catalysts undergo a more pronounced structural change and form a minor fraction of Ni nanoparticles. Density functional theory calculations are consistent with the XAS results and provide molecular insights showing that the interplay between protonation and CO adsorption leads to adsorbate-induced restructuring of the Ni single atom. This work demonstrates the synergistic role of hollow structure and high-density Ni atoms in governing CO 2 RR selectivity and provides mechanistic insights into the structural dynamics of single-atom catalysts under operating conditions.
Prototype Atomically Dispersed Supported Metal Catalysts: Iridium and Platinum
Not provided.
Insights into the Structure–Activity Relationship in Aerobic Alcohol Oxidation over a Metal–Organic-Framework-Supported Molybdenum(VI) Catalyst
The understanding of structure–activity relationships at the atomic level has played a profound role in heterogeneous catalysis, providing valuable insights into designing suitable heterogeneous catalysts. However, uncovering the detailed roles of how such active species’ structures affect their catalytic performance remains a challenge owing to the lack of direct structural information on a specific active species. Herein, we deposited molybdenum(VI), an active species in oxidation reactions, on the Zr 6 node of a mesoporous zirconium-based metal–organic framework (MOF) NU-1200, using solvothermal deposition in MOFs (SIM). Due to the high crystallinity of the NU-1200 support, the precise structure of the resulting molybdenum catalyst, Mo-NU-1200, was characterized through single-crystal X-ray diffraction (SCXRD). Two distinct anchoring modes of the molybdenum species were observed: one mode (Mo1), displaying an octahedral geometry, coordinated to the node through one terminal oxygen atom and the other mode (Mo2) coordinated to two adjacent Zr 6 node oxygen atoms in a tetrahedral geometry. To investigate the role of base in the catalytic activity of these Mo centers, we assessed the activity of Mo-NU-1200 for the aerobic oxidation of 4-methoxybenzyl alcohol as a model reaction. The results revealed that Mo-NU-1200 exhibited remarkably higher catalytic reactivity under base-free conditions, while the presence of base inhibited the catalytic reactivity of this species. SCXRD studies revealed that the molybdenum binding motifs (structures of the supported metal on the Zr 6 node in the MOF) changed over the course of the reactions. Following the oxidation without base, both pristine coordination modes (Mo1 and Mo2) evolved into a new coordination mode (Mo3), in which the molybdenum atom coordinated to two adjacent oxygen atoms from the Zr 6 node in an octahedral geometry, while in the presence of base, the pristine Mo1 coordination mode evolved entirely into the pristine Mo2. Here, this study demonstrates the direct observation of an active species’ structural evolution from metal installation to subsequent catalytic reaction. As a result, these subtle structural changes in catalyst binding motifs led to distinct differences in catalytic activities, providing a compelling strategy for elucidating structure–activity relationships.
Physically Based Modeling of PEMFC Cathode Catalyst Layers: Effective Microstructure and Ionomer Structure–Property Relationship Impacts
Abstract This work presents a pseudo-two-dimensional proton exchange membrane fuel cell (PEMFC) model incorporating Nafion ionomer structure–property relationships in the cathode catalyst layer (CL) to capture and explain losses at low Pt loading. Structural data from neutron reflectometry and thin film Nafion conductivity measurements predict variations in the oxygen diffusion coefficient and ionic conductivity with changing CL ionomer thickness and Pt loading. By including these structure–property relationships, predicted polarization curves agree closely with previously published experimental data from cells with Pt loadings between 0.025 and 0.2 mg/cm2. Results demonstrate that structure–property relationships based on physically measurable ionomer and CL properties provide a feasible interpretation of PEMFC CL phenomena for a range of Pt loadings and help explain previously unaccounted-for losses at low Pt. Results also show that simulations must account for surface species coverage variations in order to properly capture the kinetic losses. Finally, results suggest that an increase in ionomer thickness surrounding the C/Pt surfaces may lead to improved cell performance due to improved ionic conductivity.
Hierarchical electrode design of highly efficient and stable unitized regenerative fuel cells (URFCs) for long-term energy storage
The unitized regenerative fuel cell (URFC) is a promising electrochemical device for intermittent renewable energy storage in chemical bonds. However, widespread application has been hindered due to low round-trip efficiencies (RTEs) and disappointing durability, in particular at high rates. In this study, we break through that barrier by demonstrating highly efficient, flexible, and stable URFCs via hierarchical design of the multiscale catalyst-layer structures. A more porous and less tortuous Pt and Ir catalyst layer is realized using a doctor blade fabrication method that significantly improves URFC performance. We demonstrate RTEs of 56% and 53% under constant-electrode and constant-gas mode, respectively, while operating at 1000 mA cm –2 , and significantly, a RTE of 45% at 2000 mA cm –2 , achievements that were previously viewed as unfeasible under the onerous demands of URFC operation. At the same time we demonstrate URFCs under both constant-electrode and constant-gas mode operated continuously for over 500 h with negligible degradation. These results demonstrate the viability of applying URFCs for long-term energy storage at previously unattainable efficiencies and cast new light on electrode design and optimization of URFCs.
Predicting Catalyst Surface Stability Under Reaction Conditions Using Deep Reinforcement Learning and Machine Learning Potentials
Catalysts are critical for most large-scale energy intensive chemical transformation processes, such as energy storage, liquid fuel production, and the formation of chemical building blocks. The catalyst composition, structure, and morphology impact the performance under reaction conditions and influences properties like activity and selectivity. Many industrial catalysts offer imperfect activity/selectivity, or contain expensive metals. Further, catalysts can deactivate over time as the morphology changes or harsh reactive environments alter the surface structure. Methods to automatically model and predict the kinetics of how catalyst surfaces will restructure would enable engineers to design around these challenges, improve performance, increase longevity. This project investigated a specific type of machine learning model, deep reinforcement learning, machine learning models to act as surrogates for the physical system, and compared the results of these approaches with a specialized high-throughput experimental synthesis and measurement platform.
An investigation of the physical and chemical changes of Pd nanoparticles on carbon supports in response to the release of hydrogen from aqueous formate solutions
Palladium nanoparticles on carbon supports (Pd/C) are effective for catalyzing hydrogen release from aqueous formate solutions but typically suffer from a gradual decrease of activity. This study finds two primary factors influencing activity: (i) the number of available surface Pd sites, and (ii) metal-support interactions which depend on the nature of the C support. We propose that the Pd/C catalyst is structure insensitive and undergoes Ostwald ripening to yield an active ‘conditioned’ catalyst with dispersion plateauing between ca. 15–20 %. Contrary to earlier studies, in-situ XANES experiments show that PdO is not an active catalyst for formate dehydrogenation. Calcination of Pd/C before dehydrogenation increases the catalytic activity which suggests a beneficial, albeit temporary, modification of the metal support interaction. N-containing supports minimize nanoparticle growth and also increase activity through a metal-support interaction. In conclusion, these findings advance our understanding of catalyst evolution and stability in formate dehydrogenation systems.
Active and Durable PGM-free Cathodic Electrocatalysts for Fuel Cell Application
Platinum Group Metal-free (PGM-free) Oxygen Reduction Reaction (ORR) electrocatalysts possess high intrinsic activity measured by a Rotating Disk Electrode (RDE) method. However, under fuel cell operating conditions, PGM-free ORR electrocatalysts have underperformed compared to platinum catalysts. PGM-free ORR electrocatalyst’s fuel cell performance can be improved by designing and optimizing the cathodic catalyst layer (CL) and Membrane Electrode Assembly (MEA) construction such that: 1) it efficiently provides oxygen access to ORR active sites (through catalyst morphology control); 2) it removes water from the CL (by tuning the hydrophobicity of the PGM-free catalysts and the catalyst layer structure); and 3) it increases proton conductivity (by homogeneous mixing of catalysts and ionomer). Studying the CL is complex due to the absence of well-established protocols of MEA activation, especially compared to platinum-containing catalysts. PGM-free fuel cell testing protocols would need to optimize potentiostatic vs galvanostatic measurements, scan rates, parameters of Electrochemical Impedance Spectroscopy (EIS) and Beginning of Experiment (BOE) criteria. To make the PGM-free catalyst’s fuel cell performance comparable to platinum, the synergistic effort of materials design, fine tuning of the catalyst layer and comprehensive electrochemical analysis is required.
Non-noble electrocatalysts for alkaline fuel cells
Carbons activated with macrocyclics have attracted increasing attention as alternative electrocatalysts for oxygen reduction. Initial activity of these catalysts is good, but performance declines rapidly. Pyrolyzing the macrocyclic on the carbon support leads to enhanced stability and the catalysts retain good activity. The approach described is designed to develop bulk doped catalysts with similar structures to pyrolyzed macrocyclic catalysts. The transition metal and coordinated ligands are dispersed throughout the bulk of the conductive carbon skeleton. Two approaches to realizing this concept are being pursued, both involving the doping of carbon precursors. In one approach, the precursor is a solid phase carbon-containing ion-exchange resin. The precursor is doped with a transition metal and/or nitrogen, and the resulting mixture is pyrolyzed. In the other approach, the precursor is a gas-phase hydrocarbon. This is introduced with a transition metal species and nitrogen species into a reactor and pyrolyzed. Several studies have been conducted to determine if there is a synergistic effect between the transition metal and nitrogen and the effect of different methods of introducing the metal-nitrogen (M-N) coordination on performance. One approach was to introduce the metal and nitrogen separately, for example, by sequentially doping FeCl3 and NH4OH into the resin. Catalysts were prepared from an undoped ion-exchange resin, a resin doped only with N, a resin doped only with Fe, and a resin doped with both Fe and N. Introduction of nitrogen alone has no beneficial effect on the performance of the catalysts. The introduction of the Fe alone significantly improves the performance in both the high and low current density regions. When both Fe and N are introduced, the performance at lower current densities (catalytic activity) is increased beyond that of the Fe-doped carbon, but the performance at higher current densities is similar to the carbon containing only Fe. Catalysts prepared from resins-Fe(bipy)3SO4 precursors have performance that is only slightly less then CoTMPP adsorbed and pyroloyzed on Vulcan XC-72. Their performance is much better than carbons which have had the N and Fe introduced separately.