Developing stable and efficient electrocatalysts is vital for boosting oxygen evolution reaction (OER) rates in sustainable hydrogen production. High-entropy oxides (HEOs) consist of five or more metal cations, providing opportunities to tune their catalytic properties toward high OER efficiency. This work combines theoretical and experimental studies to scrutinize the OER activity and stability for spinel-type HEOs. Density functional theory confirms that randomly mixed metal sites show thermodynamic stability, with intermediate adsorption energies displaying wider distributions due to mixing-induced equatorial strain in active metal-oxygen bonds. The rapid sol-flame method is employed to synthesize HEO, comprising five 3d-transition metal cations, which exhibits superior OER activity and durability under alkaline conditions, outperforming lower-entropy oxides, even with partial surface oxidations. The study highlights that the enhanced activity of HEO is primarily attributed to the mixing of multiple elements, leading to strain effects near the active site, as well as surface composition and coverage.
This content will become publicly available on February 13, 2025
- Award ID(s):
- 2026193
- PAR ID:
- 10525090
- Author(s) / Creator(s):
- ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; more »
- Publisher / Repository:
- Royal Society of Chemistry
- Date Published:
- Journal Name:
- Journal of Materials Chemistry A
- Volume:
- 12
- Issue:
- 7
- ISSN:
- 2050-7488
- Page Range / eLocation ID:
- 3910 to 3922
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
Synergistic effects of mixing and strain in high entropy spinel oxides for oxygen evolution reactionmore » « less
Abstract -
null (Ed.)The emergence of high-entropy materials (HEMs) with their excellent mechanical properties, stability at high temperatures, and high chemical stability is poised to yield new advancement in the performance of energy storage and conversion technologies. This review covers the recent developments in catalysis, water splitting, fuel cells, batteries, supercapacitors, and hydrogen storage enabled by HEMs covering metallic, oxide, and non-oxide alloys. Here, first, the primary rules for the proper selection of the elements and the formation of a favorable single solid solution phase in HEMs are defined. Furthermore, recent developments in different fields of energy conversion and storage achieved by HEMs are discussed. Higher electrocatalytic and catalytic activities with longer cycling stability and durability compared to conventional noble metal-based catalysts are reported for high-entropy materials. In electrochemical energy storage systems, high-entropy oxides and alloys have shown superior performance as anode and cathode materials with long cycling stability and high capacity retention. Also, when used as metal hydrides for hydrogen storage, remarkably high hydrogen storage capacity and structural stability are observed for HEMs. In the end, future directions and new energy-related technologies that can be enabled by the application of HEMs are outlined.more » « less
-
more » « less
Abstract A high‐throughput computational framework to identify novel multinary perovskite redox mediators is presented, and this framework is applied to discover the Gd‐containing perovskite oxide compositions Gd2BB′O6,GdA′B2O6, and GdA′BB′O6that split water. The computational scheme uses a sequence of empirical approaches to evaluate the stabilities, electronic properties, and oxygen vacancy thermodynamics of these materials, including contributions to the enthalpies and entropies of reduction, Δ
H TRand ΔS TR. This scheme uses the machine‐learned descriptor τ to identify compositions that are likely stable as perovskites, the bond valence method to estimate the magnitude and phase of BO6octahedral tilting and provide accurate initial estimates of perovskite geometries, and density functional theory including magnetic‐ and defect‐sampling to predict STCH‐relevant properties. Eighty‐three promising STCH candidate perovskite oxides down‐selected from 4392 Gd‐containing compositions are reported, three of which are referred to experimental collaborators for characterization and exhibit STCH activity. The results demonstrate that the high‐throughput computational scheme described herein—which is used to evaluate Gd‐containing compositions but can be applied to any multinary perovskite oxide compositional space(s) of interest—accelerates the discovery of novel STCH active redox mediators with reasonable computational expense. -
more » « less
A unique approach was used to synthesize the high entropy alloy MoNbTaVW via reduction of metal-oxide precursors in a microwave plasma. The metal-oxides underwent ball milling and consolidation before plasma annealing at 1800 °C for 1 h with hydrogen as feedgas. X-ray diffraction, scanning electron microscopy/energy dispersive x-ray analysis, and Vickers hardness testing reveal characteristics of the high-entropy alloy. This includes a predominantly single-phase body-centered cubic structure, homogeneous distribution of all five metals, and 6.8 ± 0.9 GPa hardness, comparable with other reports for the same five-metal high entropy alloy configuration. Localized microwave plasma particle sintering is evident from the microstructure. These results highlight the promising potential of microwave plasma as a fast, economical, and flexible processing tool for high entropy alloys.
-
more » « less
Abstract Chemical looping air separation (CLAS) is a promising technology for oxygen generation with high efficiency. The key challenge for CLAS is to design robust oxygen sorbents with suitable redox properties and fast redox kinetics. In this work, perovskite-structured Sr1-xCaxFe1-yCoyO3oxygen sorbents were investigated and demonstrated for oxygen production with tunable redox properties, high redox rate, and excellent thermal/steam stability. Cobalt doping at B site was found to be highly effective, 33% improvement in oxygen productivity was observed at 500 °C. Moreover, it stabilizes the perovskite structure and prevents phase segregation under pressure swing conditions in the presence of steam. Scalable synthesis of Sr0.8Ca0.2Fe0.4Co0.6O3oxygen sorbents was carried out through solid state reaction, co-precipitation, and sol-gel methods. Both co-precipitation and sol-gel methods are capable of producing Sr0.8Ca0.2Fe0.4Co0.6O3sorbents with satisfactory phase purity, high oxygen capacity, and fast redox kinetics. Large scale evaluation of Sr0.8Ca0.2Fe0.4Co0.6O3, using an automated CLAS testbed with over 300 g sorbent loading, further demonstrated the effectiveness of the oxygen sorbent to produce 95% pure O2with a satisfactory productivity of 0.04 gO2gsorbent−1h−1at 600 °C.
