An official website of the United States government
High-efficiency and low-cost catalysts for the oxygen evolution reaction (OER) in acidic electrolytes are critical for electrochemical water splitting in proton exchange membrane (PEM) electrolyzers to produce green hydrogen, a clean fuel for sustainable energy conversion and storage. Among OER catalysts, solid-state synthesized SrCo1−xIrxO3 has demonstrated superior activity compared to commercial standards, such as IrO2 and RuO2. However, the solid-state synthesis process is economically inefficient for industrial use due to the potential for impurities and low yield of the final product. In addition, the requirement for electrochemical cycling to activate the catalyst introduces contaminations and uncertainties for industrial applications. In this study, a modified solution-based sol–gel method was employed to produce SrCo0.5Ir0.5O3 (SCIO) with high purity and yield. Subsequent ball milling and acid leaching treatments were applied, resulting in a catalyst with higher efficiency than those activated solely by electrochemical cycling. The electrochemical analysis and physical characterizations of our SCIO catalyst after ex-situ post-synthesis treatments show a similar active phase in composition and structure to those obtained through in situ electrochemical cycling and activation. Our approach simplifies the preparation process, making the catalyst ready for direct use in PEM electrolyzers without further treatment, offering a promising solution for producing high-performance, industrial-scale OER catalysts.
more »
« less
This content will become publicly available on December 19, 2026
Engineering CoO x -Based Self-Supported Anodes for Pure-Water-Fed Anion-Exchange-Membrane Electrolysis
Commercial membrane electrolyzers rely on acidic fluorocarbon membranes and ionomers, requiring the use of expensive IrOx-based oxygen-evolution catalysts. Anion-exchange-membrane water electrolyzers (AEMWEs) operate in an alkaline environment, enabling the use of non-precious-metal catalysts. Here, we study and engineer CoOx-based catalyst-coated anodes deposited via hydrothermal synthesis directly onto porous transport layers both with and without thermal annealing. Self-supported, nanoneedle-structured Co3O4 anode, formed by annealing the as-synthesized cobalt carbonate hydroxide, Co(CO3)x(OH)y, outperforms the baseline Co3O4 nanoparticle ink-based anode in pure-water-fed AEMWE, due to improved catalyst layer continuity and thus number of electroactive Co species. The as-synthesized and unannealed Co(CO3)x(OH)y), however, appears to undergo substantial conversion to a more-active CoOx(OH)y phase predominantly at the surface, with nominally Co3+ present and higher electrical conductivity, lowering the cell voltage ~200 mV at 1.0 A∙cm-2 in pure-water-fed AEMWE compared to the conventional Co3O4 nanoparticle anodes. We analyze the differences in electrode electrochemical response between pure-water and KOH feed modes finding distinct activation and degradation modes. The Co(CO3)x(OH)y anode shows significant activation and slower degradation linked to the conversion to oxyhydroxide. We propose catalyst layer designs that promote both hydroxide and electron transport, alongside interfacial engineering strategies to obtain high performance while mitigating anode degradation.
more »
« less
- Award ID(s):
- 2400195
- PAR ID:
- 10685056
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- ACS Catalysis
- Volume:
- 16
- Issue:
- 1
- ISSN:
- 2155-5435
- Page Range / eLocation ID:
- 311 to 322
- Subject(s) / Keyword(s):
- anion-exchange-membrane water electrolysis, self-supported catalyst, catalyst-ionomer interface, non-precious-group-metal catalyst, oxygen evolution reaction
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
null (Ed.)Acidic oxygen evolution reaction (OER) electrocatalysts that have high activity, extended durability, and lower costs are needed to further the development and wide-scale adoption of proton-exchange membrane electrolyzers. In this work, we report hydrous cobalt–iridium oxide two-dimensional (2D) nanoframes exhibit higher oxygen evolution activity and similar stability compared with commercial IrO 2 ; however, the bimetallic Co–Ir catalyst undergoes a significantly different degradation process compared with the monometallic IrO 2 catalyst. The bimetallic Co–Ir 2D nanoframes consist of interconnected Co–Ir alloy domains within an unsupported, carbon-free, porous nanostructure that allows three-dimensional molecular access to the catalytically active surface sites. After electrochemical conditioning within the OER potential range, the predominately bimetallic alloy surface transforms to an oxide/hydroxide surface. Oxygen evolution activities determined using a rotating disk electrode configuration show that the hydrous Co–Ir oxide nanoframes provide 17 times higher OER mass activity and 18 times higher specific activity compared to commercial IrO 2 . The higher OER activities of the hydrous Co–Ir nanoframes are attributed to the presence of highly active surface iridium hydroxide groups. The accelerated durability testing of IrO 2 resulted in lowering of the specific activity and partial dissolution of Ir. In contrast, the durability testing of hydrous Co–Ir oxide nanoframes resulted in the combination of a higher Ir dissolution rate, an increase in the relative contribution of surface iridium hydroxide groups and an increase in specific activity. The understanding of the differences in degradation processes between bimetallic and monometallic catalysts furthers our ability to design high activity and stability acidic OER electrocatalysts.more » « less
-
Alkaline anion exchange membranes (AAEMs) are an important component of alkaline exchange membrane fuel cells (AEMFCs), which facilitate the efficient conversion of fuels to electricity using nonplatinum electrode catalysts. However, low hydroxide conductivity and poor long-term alkaline stability of AAEMs are the major limitations for the widespread application of AEMFCs. In this paper, we report the synthesis of highly conductive and chemically stable AAEMs from the living polymerization of trans -cyclooctenes. A trans -cyclooctene–fused imidazolium monomer was designed and synthesized on gram scale. Using these highly ring-strained monomers, we produced a range of block and random copolymers. Surprisingly, AAEMs made from the random copolymer exhibited much higher conductivities than their block copolymer analogs. Investigation by transmission electron microscopy showed that the block copolymers had a disordered microphase segregation which likely impeded ion conduction. A cross-linked random copolymer demonstrated a high level of hydroxide conductivity (134 mS/cm at 80 °C). More importantly, the membranes exhibited excellent chemical stability due to the incorporation of highly alkaline-stable multisubstituted imidazolium cations. No chemical degradation was detected by 1 H NMR spectroscopy when the polymers were treated with 2 M KOH in CD 3 OH at 80 °C for 30 d.more » « less
-
null (Ed.)A new transmetallation approach is described for the synthesis of metal oxide nanocrystals (NCs). Typically, the synthesis of metal oxide NCs in oleyl alcohol is driven by metal-based esterification catalysis with oleic acid to produce oleyl oleate ester and M-OH monomers, which then condense to form M x O y solids. Here we show that the synthesis of Cu 2 O NCs by this method is limited by the catalytic ability of copper to drive esterification and thus produce Cu + -OH monomers. However, inclusion of 1–15 mol% of a group 13 cation (Al 3+ , Ga 3+ , or In 3+ ) results in efficient synthesis of Cu 2 O NCs and exhibits size/morphology control based on the nature of M 3+ . Using a continuous-injection procedure where the copper precursor (Cu 2+ -oleate) and catalyst (M 3+ -oleate) are injected into oleyl alcohol at a controlled rate, we are able to monitor the reactivity of the precursor and M 3+ catalyst using UV-visible and FTIR absorbance spectroscopies. These time-dependent measurements clearly show that M 3+ catalysts drive esterification to produce M 3+ -OH species, which then undergo transmetallation of hydroxide ligands to generate Cu + -OH monomers required for Cu 2 O condensation. Ga 3+ is found to be the “goldilocks” catalyst, producing NCs with the smallest size and a distinct cubic morphology not observed for any other group 13 metal. This is believed to be due to rapid transmetallation kinetics between Ga 3+ -OH and Cu + -oleate. These studies introduce a new mechanism for the synthesis of metal oxides where inherent catalysis by the parent metal ( i.e. copper) can be circumvented with the use of a secondary catalyst to generate hydroxide ligands.more » « less
-
null (Ed.)Oxygen evolution reaction (OER) catalysts are critical components of photoanodes for photoelectrochemical (PEC) water oxidation. Herein, nanostructured metal boride MB (M = Co, Fe) electrocatalysts, which have been synthesized by a Sn/SnCl 2 redox assisted solid-state method, were integrated with WO 3 thin films to build heterojunction photoanodes. As-obtained MB modified WO 3 photoanodes exhibit enhanced charge carrier transport, amended separation of photogenerated electrons and holes, prolonged hole lifetime and increased charge carrier density. Surface modification of CoB and FeB significantly enhances the photocurrent density of WO 3 photoanodes from 0.53 to 0.83 and 0.85 mA cm −2 , respectively, in transient chronoamperometry (CA) at 1.23 V vs. RHE (V RHE ) under interrupted illumination in 0.1 M Na 2 SO 4 electrolyte (pH 7), corresponding to an increase of 1.6 relative to pristine WO 3 . In contrast, the pristine MB thin film electrodes do not produce noticeable photocurrent during water oxidation. The metal boride catalysts transform in situ to a core–shell structure with a metal boride core and a metal oxide (MO, M = Co, Fe) surface layer. When coupled to WO 3 thin films, the CoB@CoO x nanostructures exhibit a higher catalytic enhancement than corresponding pure cobalt borate (Co-B i ) and cobalt hydroxide (Co(OH) x ) electrocatalysts. Our results emphasize the role of the semiconductor–electrocatalyst interface for photoelectrodes and their high dependency on materials combination.more » « less
