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DOE OSTI2021

The Impact of 5-Hydroxymethylfurfural (HMF)-Metal Interactions on the Electrochemical Reduction Pathways of HMF on Various Metal Electrodes

5-Hydroxymethylfurfural (HMF), which can be derived from lignocellulosic biomass, is an important platform molecule that can be used to produce valuable biofuels and polymeric materials. Electrochemical reduction of HMF is of great interest as it uses water as the hydrogen source and achieves desired reduction reactions at room temperature and ambient pressure. Hydrogenation and hydrogenolysis are two important reactions for reductive HMF conversion. Therefore, elucidating key characteristics of electrocatalysts that govern the selectivity for hydrogenation and hydrogenolysis is critical in rationally developing efficient and selective electrocatalysts. Here in this study, combined experimental and computational investigations are used to demonstrate how the adsorption energy of HMF on metal surfaces and the resulting changes in the intramolecular bond lengths of adsorbed HMF directly impact the reduction pathways of HMF. These results make it possible to rationally understand a general trend in the behaviors observed when using various metal electrodes for HMF reduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Sustainable Synthesis of NiMo Alloy Nanoparticles for Hydrogen Evolution Catalysis Using a Recyclable Ionic Liquid Solvent

Advancing the sustainability of nanoparticle electrocatalyst synthesis requires reducing solvent waste without compromising catalytic performance. Here, we report a rapid, microwave‐assisted colloidal synthesis of NiMo alloy nanoparticles in the ionic liquid 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIM‐NTf 2 ), which serves as both reaction medium and recyclable solvent. NiMo nanoparticles with tunable compositions were obtained within 1 min at 230 °C, with Ni 0.86 Mo 0.14 giving the highest activity toward the hydrogen evolution reaction (HER), achieving an onset potential of −129 mV, an overpotential at 10 mA cm −2 of −290 mV versus RHE in acidic electrolyte, and >99% Faradaic efficiency. The ionic liquid was recovered and purified via aqueous NH 4 OH extraction, removing over 99% of residual Mo species, and reused for up to five successive syntheses. Nanoparticles prepared in recycled BMIM‐NTf 2 retained comparable crystallinity, morphology, and catalytic activity, with stable HER performance over 45 h of electrolysis. These results demonstrate that ionic liquid recycling can improve the sustainability of the preparation of NiMo nanoparticle electrocatalysts while preserving performance and material integrity.

bimetallic alloy↗

DOE OSTI2025

Optimizing Hybrid-Phase IrO2 Catalysts with Ti for Enhanced Oxygen Evolution Reaction for Proton Exchange Membrane Water Electrolysis

To realize a sustainable energy transition, water electrolysis-particularly proton exchange membrane water electrolysis (PEMWE)-holds significant promise. However, practical deployment is hindered by the cost and instability of the anode catalyst, IrO2. Recent studies indicate that tuning the Ir-O bond distance, via doping or composite formation, is key to enhancing the oxygen evolution reaction (OER) performance of IrO2-based electrocatalysts. Herein, a hybrid-phase Ti-incorporated IrO2 electrocatalyst is developed, exhibiting outstanding OER activity (298.8 mV at 100 mA cm-2) and stability over 25 h. This improvement originates from asymmetric interatomic interactions introduced by Ti, as revealed by combined experimental X-ray analyses and theoretical modeling. Ti incorporation induces tensile strain along the z-axis in IrO2 motifs, effectively reducing the average Ir-O bond distance and thereby enhancing OER activity. In situ X-ray absorption spectroscopy further confirms that at 1.5 V (vs. RHE), the elongated Ir-O bond facilitates -OOH* intermediate formation while suppressing Ir dissolution, contributing to superior stability. These findings underscore the critical role of Ir-O bond engineering in balancing activity and durability, offering strategic insights for the rational design of high-performance OER catalysts for renewable energy technologies.

08 HYDROGEN↗

DOE OSTI2024

Silica–Derived Nanostructured Electrode Materials for ORR, OER, HER, CO 2 RR Electrocatalysis, and Energy Storage Applications: A Review**

Silica-derived nanostructured catalysts (SDNCs) are a class of materials synthesized using nanocasting and templating techniques, which involve the sacrificial removal of a silica template to generate highly porous nanostructured materials. The surface of these nanostructures is functionalized with a variety of electrocatalytically active metal and non-metal atoms. SDNCs have attracted considerable attention due to their unique physicochemical properties, tunable electronic configuration, and microstructure. These properties make them highly efficient catalysts and promising electrode materials for next generation electrocatalysis, energy conversion, and energy storage technologies. The continued development of SDNCs is likely to lead to new and improved electrocatalysts and electrode materials. This review article provides a comprehensive overview of the recent advances in the development of SDNCs for electrocatalysis and energy storage applications. It analyzes 337,061 research articles published in the Web of Science (WoS) database up to December 2022 using the keywords “silica”, “electrocatalysts”, “ORR”, “OER”, “HER”, “HOR”, “CO 2 RR”, “batteries”, and “supercapacitors”. The review discusses the application of SDNCs for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO 2 RR), supercapacitors, lithium-ion batteries, and thermal energy storage applications. It concludes by discussing the advantages and limitations of SDNCs for energy applications.

25 ENERGY STORAGE↗

DOE OSTI2021

Mechanisms of water oxidation on heterogeneous catalyst surfaces

Water oxidation, an essential step in photosynthesis, has attracted intense research attention. Understanding the reaction pathways at the electrocatalyst/water interface is of great importance for the development of water oxidation catalysts. How the water is oxidized on the electrocatalyst surface by the positive charges is still an open question. This review summarizes current advances in studies on surface chemistry within the context of water oxidation, including the intermediates, reaction mechanisms, and their influences on the reaction kinetics. The Tafel analyses of some electrocatalysts and the rate-laws relative to charge consumption rates are also presented. Moreover, how the multiple charge transfer relies on the intermediate coverage and the accumulated charge numbers is outlined. Finally, the intermediates and rate-determining steps on some water oxidation catalysts are discussed based on density functional theories.

14 SOLAR ENERGY↗

DOE OSTI2022

Synthesis of amorphous Pd-based nanocatalysts for efficient alcoholysis of styrene oxide and electrochemical hydrogen evolution

Amorphous nanomaterials with long-range disordered structures could possess distinct properties and promising applications, especially in catalysis, as compared with their conventional crystalline counterparts. It is imperative to achieve the controlled preparation of amorphous noble metal-based nanomaterials for the exploration of their phase-dependent applications. Here, in this work, we report a facile wet-chemical reduction strategy to synthesize various amorphous multimetallic Pd-based nanomaterials, including PdRu, PdRh, and PdRuRh. The phase-dependent catalytic performances of distinct Pd-based nanomaterials towards diverse catalytic applications have been demonstrated. Specifically, the usage of PdRu nanocatalysts with amorphous and crystalline face-centered cubic (fcc) phases can efficiently switch the ring-opening route of styrene oxide to obtain different products with high selectivity through alcoholysis reaction and hydrogenation reaction, respectively. Moreover, when used as an electrocatalyst for hydrogen evolution reaction (HER), the synthesized amorphous PdRh nanocatalyst exhibits low overpotential and high turnover frequency values, outperforming its crystalline fcc counterpart and most of the reported Pd-based HER electrocatalysts.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Ruthenium-lead oxide for acidic oxygen evolution reaction in proton exchange membrane water electrolysis

Developing an active and stable anode catalyst for the proton exchange membrane water electrolyzer (PEM-WE) is a critical objective to enhance the economic viability of green hydrogen technology. However, the expensive iridium-based electrocatalyst remains the sole practical material with industrial-level stability for the acidic oxygen evolution reaction (OER) at the anode. Ruthenium-based catalysts have been proposed as more cost-effective alternatives with improved activity, though their stability requires enhancement. The current urgent goal is to reduce costs and noble metal loading of the OER catalyst while maintaining robust activity and stability. Here, in this study, we design a Ru-based OER catalyst incorporating Pb as a supporting element. This electrocatalyst exhibits an OER overpotential of 201 mV at 10 mA.cm -2 , simultaneously reducing Ru noble metal loading by similar to 40%. Normalization of the electrochemically active surface area unveils improved intrinsic activity compared to the pristine RuO 2 catalyst. During a practical stability test in a PEM-WE setup, our developed catalyst sustains stable performance over 300 h without notable degradation, underscoring its potential for future applications as a reliable anodic catalyst.

Electrocatalysis↗

DOE OSTI2022

Design of PGM-free cathodic catalyst layers for advanced PEM fuel cells

Here, the design of cathodic catalysts layer (CCL) consisted of Platinum Group Metal-free (PGM-free) electrocatalysts was done by catalyst coated membrane approach. Three different Fe-Mn-N-C compounds were synthesized with Fe:Mn ratio of 1:1, 2:1 and 2:1 with modified heat treatment profile. The catalysts were characterized by X-ray photoelectron spectroscopy, X-ray powder diffraction, pore and particle size distribution, zeta potential and transmission electron microscopy. Electrocatalysts were integrated into membrane electrode assembly and evaluated by electrochemical methods. Electrochemical impedance spectroscopy in combination with modeling were used for estimation of proton conductivity of CCL and its oxygen diffusivity. It was found that all CCLs possess extremely high proton conductivity, which was demonstrated for the first time for these types of PGM-free catalysts. The observed ORR mechanism was predominantly 4e- due to peroxide/radicals scavenging effect of Mn.

impedance↗

DOE OSTI2021

Parallels between enzyme catalysis, electrocatalysis, and photoelectrosynthesis

Catalysts are central to accelerating chemistry in biology and technology. In biochemistry, the relationship between the velocity of an enzymatic reaction and the concentration of chemical substrates is described via the Michaelis-Menten model. Additionally, the modeling and benchmarking of synthetic molecular electrocatalysts are also well developed. However, such efforts have not been as rigorously extended to photoelectrosynthetic reactions, where, in addition to chemical substrates and charge carriers, light is a required reagent. In this perspective, we draw parallels between concepts involving enzyme catalytic efficiency, the benchmarking of molecular electrocatalysts, and the performance of photoelectrosynthetic assemblies, while highlighting key differences, assumptions, and limitations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

The role of nonmetallic ion substitution in perovskite LaCoO 3 for improved oxygen evolution reaction activity

Transition metal perovskite (ABO 3 ) is an emerging type of oxygen evolution reaction (OER) electrocatalyst that shows reasonably good activity and moderate stability. Although efforts have been made to improve perovskite’ OER performance by various element substitution at A/B-site, the influence of ion, particularly non-metallic ion, substitutions on the OER mechanism are rarely studied. More and more evidence has shown that the metal-center theory has failed to explain lots of OER-related phenomena. Therefore, it is urgent to understand how the cation and anion sites in perovskite determine OER performance. In this work, we used a Fe and P co-doped LaCoO 3 as a model system to explore the influence of substitution in perovskite by combining operando/ex-situ X-ray characterization and density functional theory (DFT). We observed enhanced OER catalytic activities in co-doped materials, which are attributed to the stronger transition-metal-oxygen-bonding-covalency (TMOBC). The detailed analyses by O K-edge XAS, electrochemical performance, and DFT suggest that the hybridization between O 2p and transition metal 3d e g orbitals could be a more credible descriptor of perovskite for OER, which is the combination of e g orbital theory and TMOBC theory. The finding in our work provides insights into the OER catalysis mechanism on metal oxides, which could guide new design of cost-effective oxide electrocatalysts.

25 ENERGY STORAGE↗

DOE OSTI2024

Synthesis of rhenium coatings on 316 stainless steel and their electrochemical behavior towards water oxidation in saline environments

The production of electrolytic hydrogen or Green Hydrogen has attracted the attention of scientists as a potential enabler of sustainable energy production. The cleavage of the water molecule requires high energy, in order to produce hydrogen and oxygen through their corresponding half reactions, the hydrogen evolution and oxygen evolution reactions. Further, this latter reaction has been studied in more detail, since its slow kinetics make the water electrolysis less efficient, and, for instance, delay the formation of hydrogen in the counter compartment of the electrolytic cell. In this work, a study of the oxygen evolution reaction is presented. For this, a series of rhenium catalysts deposited onto stainless steel 316 are studied with the aim of analyzing the effect of the pure metal (Re) and the metal with heteroatoms (Re-C, Re-B, and Re-O). As one of the problems worldwide is the scarcity of freshwater, the study focuses on the performance of this series of catalysts in highly saline environments, representative of seawater. The synthesis and electrochemical performance is shown, giving high expectations that these electrocatalysts could be potential electrocatalysts in marine environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Identification of highly active surface iron sites on Ni(OOH) for the oxygen evolution reaction by atomic layer deposition

Atomic layer deposition (ALD) has become a versatile tool in catalysis, allowing for precise synthesis of catalysts useful for gaining fundamental understanding of complex systems. In this work, ALD was used to perform surface-directed modification of Ni(OH) 2 /Ni(OOH) electrocatalysts for the oxygen evolution reaction (OER) to elucidate the different roles of iron as a surface dopant and as iron distributed throughout the NiOOH structure. Electrochemical and material characterization of FeO x ALD-modified Ni(OH) 2 indicates that iron is deposited on the surface of Ni(OH) 2 sheets without modifying its bulk properties. Sub-monolayer amounts of iron were deposited on the surface of Ni(OH) 2 using low cycle numbers of ALD. This surface iron results in high OER activity, characteristic of Ni-Fe(OOH) catalysts. Ni(OH) 2 /Ni(OOH) catalysts modified to incorporate iron throughout the structure were prepared by depositing large cycle numbers of FeO x ALD, which results in the deposition of a Fe 2 O 3 overlayer. Corrosion of this Fe 2 O 3 overlayer during electrochemical cycling in alkaline electrolyte leads to the incorporation of iron throughout the structure of Ni(OH) 2 /Ni(OOH) while leaving some Fe at the surface. Incorporation of iron throughout the Ni(OH) 2 /Ni(OOH) structure was found to increase OER geometric activity for thick, high surface area Ni(OH) 2 /Ni(OOH) catalysts. Lastly, NiFeO x electrocatalysts synthesized fully by ALD were investigated for the OER; these catalysts demonstrated high OER activity and potential for photocatalysis applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

The role of coverage effects on the structure–sensitivity of formic acid electrooxidation on Pd surfaces

Direct formic acid (FA) fuel cells (DFAFCs) with Pd anode catalysts are promising for small portable applications. During the electrooxidation of formic acid (FAO), CO accumulates on the Pd electrocatalyst, thereby decreasing its performance. In this work, we use density functional theory (DFT; RPBE) to elucidate the significance of coverage effects on the structure–sensitivity of FAO over four low–index Pd surfaces: Pd(1 1 1), Pd(1 0 0), Pd(1 1 0), and Pd(2 1 1). We construct coverage–dependent Gibbs free energy diagrams and in agreement with experiment, predict that Pd(1 0 0) and Pd(2 1 1) are the most active surfaces. Additionally, we find that the presence of CO spectator species can alter the preferred electrooxidation pathway under different applied potentials. Furthermore, such pathway transitions appear to be critical for rationalizing experimental trends regarding electrocatalytic activity and are only captured when coverage effects are accounted for. Insights derived from this work may facilitate the design of improved FAO electrocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Investigation of oxygen evolution reaction with Ni foam and stainless-steel mesh electrodes in alkaline seawater electrolysis

We report alkaline seawater electrolysis is a promising method for hydrogen production; however, little progress has been made in investigating the substrates for oxygen evolution reaction (OER) electrocatalysts. Ni foam and stainless-steel mesh (SS mesh) were investigated systematically for OER in alkaline seawater electrolysis in this work. The overpotentials and Tafel slopes with SS meshes are smaller than Ni foams, and it also exhibits excellent stability. Interestingly, the performance of the SS mesh even outperforms various non-noble metal electrocatalysts and is comparable to commercial RuO2 and IrO2. The corrosion conditions of Ni foam and SS mesh electrodes were studied and revealed. Furthermore, the electrochemically active surface area (ECSA) of Ni foam is 12 times higher than SS mesh in the same geometric area, indicating the electrochemical activity of SS mesh is much superior to Ni foam. This work expands on promising substrates for alkaline seawater electrolysis, with cost and performance advantages.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Amino-tethering synthesis strategy toward highly accessible sub-3-nm L1 0 -PtM catalysts for high-power fuel cells

Because of the poor accessibility of embedded active sites, platinum (Pt)-based electrocatalysts suffer from insufficient Pt utilization and mass transport in membrane electrode assemblies (MEAs), limiting their performance in polymer electrolyte membrane fuel cells. Here, we report a simple and universal approach to depositing sub-3-nm L1 0 -PtM nanoparticles over external surfaces of carbon supports through pore-tailored amino (NH 2 )-modification, which enables not only excellent activity for the oxygen reduction reaction, but also enhanced Pt utilization and mass transport in MEAs. Using a low loading of 0.10 mg Pt ∙cm -2 , the MEA of PtCo/KB-NH 2 delivered an excellent mass activity of 0.691 A∙mgPt -1 , a record-high power density of 0.96 W∙cm -2 at 0.67 V, and only a 30-mV drop at 0.80 A∙cm -2 after 30,000 voltage cycles, which meets nearly all targets set by the Department of Energy. Finally, this work provides an efficient strategy for designing advanced Pt-based electrocatalysts and realizing high-power fuel cells.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2020

Durability evaluation of a Fe–N–C catalyst in polymer electrolyte fuel cell environment via accelerated stress tests

In this work, an “atomically-dispersed” iron-nitrogen-carbon (Fe–N–C) catalyst was used to provide a systematic comparison of platinum group metal (PGM)-free electrocatalyst degradation as a function of accelerated stress tests (ASTs) in an acidic polymer electrolyte fuel cell (PEFC). It was determined that the majority of catalyst degradation was caused by cell operation in presence of O 2 . In contrast, potential cycling of the Fe–N–C-containing cathode under inert atmosphere over typical PEFC cathode operation from 0.95 to 0.6 V had little to no effect. The increase in kinetic overpotential is shown to be the major source of the PEFC performance decrease during the ASTs. These results continue to showcase the need for development of robust PGM-free electrocatalysts in concert with improved electrochemical performance.

25 ENERGY STORAGE↗

DOE OSTI2023

Piezo-electrocatalytic oxidation of methanol with UV-ozone treated wurtzite zinc oxide nanostructures

Leveraging mechanically-induced piezoelectric polarization, piezocatalysis emerges as a viable mechanism for enhancing the efficiency of catalytic processes. Nanostructured, catalytically active, rationally designed piezoelectric semiconductors can achieve high-performance catalysts for various applications using cost-effective electrocatalytic pathways, such as mechanical stimuli. We design and demonstrate for the first time a cost-effective, high-performance piezo-electrocatalyst for anodic methanol oxidation, which is crucial for the practical application and deployment of direct methanol fuel cells in a variety of emerging clean energy technologies. We synthesized wurtzite ZnO nanorods and nanosheets treated with UV-O 3 to characterize and compare their efficacy for piezo-electrocatalytic methanol oxidation. The generation of piezoelectric polarization charges in nanostructured semiconducting ZnO catalysts significantly increased their electrocatalytic performance. By elucidating the charge transfer between mechanically-deformed ZnO nanostructures and methanol molecules, we identified the underlying mechanism for the piezo-electrocatalytic process for methanol oxidation. The facile synthesis of high-quality ZnO nanostructures enables low-cost, scalable manufacture and direct integration into electrocatalysts whose performance could be enhanced by harvesting mechanical energy that would otherwise be wasted in the working environment.

30 DIRECT ENERGY CONVERSION↗

DOE OSTI2021

Design Principles for Efficient and Stable Water Splitting Photoelectrocatalysts

Photoelectrochemical water splitting is a promising avenue for sustainable production of hydrogen used in the chemical industry and hydrogen fuel cells. The basic components of most photoelectrochemical water splitting systems are semiconductor light absorbers coupled to electrocatalysts, which perform the desired chemical reactions. A critical challenge for the design of these systems is the lack of stability for the majority of desired semiconductors under operating water splitting conditions. One strategy to address this issue is to protect the semiconductor by covering it with a stabilizing insulator layer, creating a metal–insulator–semiconductor (MIS) architecture, which has demonstrated improved stability. In addition to enhanced stability, the insulator layer may significantly affect the electron and hole transfer, which governs the recombination rates. Furthermore, the insertion of an insulator layer leads to the introduction of additional insulator/electrocatalyst and insulator/semiconductor interfaces. These interfaces can impact the system’s performance significantly, and they need to be carefully engineered to optimize the efficiencies of MIS systems. In this Account, we describe our recent progress in shedding light on the critical role of the insulator and the interfaces on the performance of MIS systems. We discuss our findings by focusing on the concrete example of planar n-type Si protected by a HfO 2 insulator layer and coupled to a Ni or Ir electrocatalyst that performs the oxygen evolution reaction, one of the water splitting half-reactions. To improve our fundamental understanding of the insulator layer, we precisely control the HfO 2 insulator thickness using atomic layer deposition (ALD), and we perform a series of rigorous electrochemical experiments coupled with theory and modeling. We demonstrate that by tuning the insulator thickness, we can control the flux and recombination of photogenerated electrons and holes to optimize the generated photovoltage. Despite optimizing the thickness, we find that the maximum generated photovoltage in MIS systems is often significantly lower than the upper performance limit, i.e., there are additional losses in the system that could not be addressed by optimizing the insulator thickness. We identify the sources of these losses and describe strategies to minimize them by a combination of improving the semiconductor light absorption, removing nonidealities associated with interfacial defects, and finding alternative insulators with improved charge carrier selectivity. Finally, we quantify the improvements that can be obtained by implementing these specific strategies. Our collective work outlines strategies to analyze MIS systems, identify the sources of efficiency losses, and optimize the design to approach the fundamental performance limits. Furthermore, these general approaches are broadly applicable to photoelectrochemical materials that utilize sunlight to produce value-added chemicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗