Constructing Highly Porous Low Iridium Anode Catalysts Via Dealloying for Proton Exchange Membrane Water Electrolyzers

Liang, Jiashun; Fu, Cehuang; Hwang, Sooyeon; Dun, Chaochao; Luo, Liuxuan; Shadike, Zulipiya; Shen, Shuiyun; Zhang, Junliang; Xu, Hui; Wu, Gang

doi:10.1002/adma.202409386

Constructing Highly Porous Low Iridium Anode Catalysts Via Dealloying for Proton Exchange Membrane Water Electrolyzers

Journal Article · Thu Dec 05 00:00:00 EST 2024 · Advanced Materials

DOI:https://doi.org/10.1002/adma.202409386· OSTI ID:2503923

Liang, Jiashun ^[1]; Fu, Cehuang ^[2]; Hwang, Sooyeon ^[3]; Dun, Chaochao ^[4]; Luo, Liuxuan ^[5]; Shadike, Zulipiya ^[5]; Shen, Shuiyun ^[5]; Zhang, Junliang ^[5]; Xu, Hui ^[6]; ^[1]

Washington Univ., St. Louis, MO (United States)
State Univ. of New York at Buffalo, NY (United States); Shanghai Jiao Tong Univ. (China)
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry
Shanghai Jiao Tong Univ. (China)
Envision Energy USA, Burlington, MA (United States)

Iridium (Ir) is the most active and durable anode catalyst for the oxygen evolution reaction (OER) for proton exchange membrane water electrolyzers (PEMWEs). However, their large-scale applications are hindered by high costs and scarcity of Ir. Lowering Ir loadings below 1.0 mgcm^-2 causes significantly reduced PEMWE performance and durability. Therefore, developing efficient low Ir-based catalysts is critical to widely commercializing PEMWEs. Herein, an approach is presented for designing porous Ir metal aerogel (MA) catalysts via chemically dealloying IrCu alloys. In this study, the unique hierarchical pore structures and multiple channels of the Ir MA catalyst significantly increase electrochemical surface area (ECSA) and enhance OER activity compared to conventional Ir black catalysts, providing an effective solution to design low-Ir catalysts with improved Ir utilization and enhanced stability. An optimized membrane electrode assembly (MEA) with an Ir loading of 0.5 mg_Ir cm^-2 generated 2.0 A cm^-2 at 1.79 V, higher than the Ir black at a loading of 2.0 mg_Ir cm^-2 (1.63 A cm^-2). The low-Ir MEA demonstrated an acceptable decay rate of ≈40 µV h^-1 during durability tests at 0.5 (>1200 h) and 2.0 A cm^-2 (400 h), outperforming the commercial Ir-based MEA (175 µV h^-1 at 2.0 mg_Ir cm^-2).

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: US Department of Energy; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division (SC-22.3 ); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; SC0012704

OSTI ID:: 2503923

Alternate ID(s):: OSTI ID: 2479984
OSTI ID: 2572886

Report Number(s):: BNL--226484-2025-JAAM; https://escholarship.org/uc/item/8kn5663c; ark:/13030/qt8kn5663c

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Journal Issue: 4 Vol. 37; ISSN 0935-9648; ISSN 1521-4095

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (57)

On the Durability of Iridium‐Based Electrocatalysts toward the Oxygen Evolution Reaction under Acid Environment She, Liaona; Zhao, Guoqiang; Ma, Tianyi Advanced Functional Materials https://doi.org/10.1002/adfm.202108465	journal	October 2021
One-Pot Synthesis of Highly Anisotropic Five-Fold-Twinned PtCu Nanoframes Used as a Bifunctional Electrocatalyst for Oxygen Reduction and Methanol Oxidation Zhang, Zhicheng; Luo, Zhimin; Chen, Bo Advanced Materials, Vol. 28, Issue 39 https://doi.org/10.1002/adma.201603075	journal	August 2016
Recent Progress in Advanced Electrocatalyst Design for Acidic Oxygen Evolution Reaction Li, Leigang; Wang, Pengtang; Shao, Qi Advanced Materials, Vol. 33, Issue 50 https://doi.org/10.1002/adma.202004243	journal	March 2021
Recent Development of Oxygen Evolution Electrocatalysts in Acidic Environment An, Li; Wei, Chao; Lu, Min Advanced Materials, Vol. 33, Issue 20 https://doi.org/10.1002/adma.202006328	journal	March 2021
Tailored Electronic Structure of Ir in High Entropy Alloy for Highly Active and Durable Bifunctional Electrocatalyst for Water Splitting under an Acidic Environment Kwon, Jiseok; Sun, Seho; Choi, Seunggun Advanced Materials, Vol. 35, Issue 26 https://doi.org/10.1002/adma.202300091	journal	May 2023
KIr₄O₈ Nanowires with Rich Hydroxyl Promote Oxygen Evolution Reaction in Proton Exchange Membrane Water Electrolyzer Li, Zhenyu; Li, Xiang; Wang, Mengna Advanced Materials, Vol. 36, Issue 30 https://doi.org/10.1002/adma.202402643	journal	May 2024
Recent Progress in Electrocatalysts for Acidic Water Oxidation Lei, Zhanwu; Wang, Tanyuan; Zhao, Bote Advanced Energy Materials, Vol. 10, Issue 23 https://doi.org/10.1002/aenm.202000478	journal	April 2020
Essentials of High Performance Water Electrolyzers – From Catalyst Layer Materials to Electrode Engineering Pham, Chuyen Van; Escalera‐López, Daniel; Mayrhofer, Karl Advanced Energy Materials, Vol. 11, Issue 44 https://doi.org/10.1002/aenm.202101998	journal	October 2021
Synergistic Co─Ir/Ru Composite Electrocatalysts Impart Efficient and Durable Oxygen Evolution Catalysis in Acid Chong, Lina; Wen, Jianguo; Song, Erhong Advanced Energy Materials, Vol. 13, Issue 37 https://doi.org/10.1002/aenm.202302306	journal	August 2023
Hybrid 3D‐Ordered Membrane Electrode Assembly (MEA) with Highly Stable Structure, Enlarged Interface, and Ultralow Ir Loading by Doping Nano TiO₂ Nanoparticles for Water Electrolyzer Liu, Yiyang; Tian, Bin; Ning, Fandi Advanced Energy Materials, Vol. 14, Issue 10 https://doi.org/10.1002/aenm.202303353	journal	December 2023
Boron‐Induced Interstitial Effects Drive Water Oxidation on Ordered Ir−B Compounds Chen, Ding; Yu, Ruohan; Zhao, Hongyu Angewandte Chemie, Vol. 136, Issue 35 https://doi.org/10.1002/ange.202407577	journal	June 2024
The Common Intermediates of Oxygen Evolution and Dissolution Reactions during Water Electrolysis on Iridium Kasian, Olga; Grote, Jan-Philipp; Geiger, Simon Angewandte Chemie International Edition, Vol. 57, Issue 9 https://doi.org/10.1002/anie.201709652	journal	February 2018
Efficient Electrochemical Reduction of CO ₂ to HCOOH over Sub-2 nm SnO ₂ Quantum Wires with Exposed Grain Boundaries Liu, Subiao; Xiao, Jing; Lu, Xue Feng Angewandte Chemie International Edition, Vol. 58, Issue 25 https://doi.org/10.1002/anie.201903613	journal	May 2019
The electronic structure of iridium and its oxides: The electronic structure of iridium and its oxides Pfeifer, Verena; Jones, Travis E.; Velasco Vélez, Juan J. Surface and Interface Analysis, Vol. 48, Issue 5 https://doi.org/10.1002/sia.5895	journal	December 2015
Nanoporous Al‐Ni‐Co‐Ir‐Mo High‐Entropy Alloy for Record‐High Water Splitting Activity in Acidic Environments Jin, Zeyu; Lv, Juan; Jia, Henglei Small, Vol. 15, Issue 47 https://doi.org/10.1002/smll.201904180	journal	October 2019
Constructing Nanoporous Ir/Ta₂O₅ Interfaces on Metallic Glass for Durable Acidic Water Oxidation Qiao, Yijing; Luo, Min; Cai, Lebin Small, Vol. 20, Issue 2 https://doi.org/10.1002/smll.202305479	journal	September 2023
“Inner” and “outer” active surface of RuO2 electrodes Ardizzone, S.; Fregonara, G.; Trasatti, S. Electrochimica Acta, Vol. 35, Issue 1 https://doi.org/10.1016/0013-4686(90)85068-X	journal	January 1990
Cyclic voltammetry as a technique for determining the surface area of RuO2 electrodes Burke, Laurence D.; Murphy, Oliver J. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 96, Issue 1 https://doi.org/10.1016/S0022-0728(79)80299-5	journal	February 1979
Oxygen and hydrogen evolution reactions on Ru, RuO 2 , Ir, and IrO 2 thin film electrodes in acidic and alkaline electrolytes: A comparative study on activity and stability Cherevko, Serhiy; Geiger, Simon; Kasian, Olga Catalysis Today, Vol. 262 https://doi.org/10.1016/j.cattod.2015.08.014	journal	March 2016
pH dependence of OER activity of oxides: Current and future perspectives Giordano, Livia; Han, Binghong; Risch, Marcel Catalysis Today, Vol. 262 https://doi.org/10.1016/j.cattod.2015.10.006	journal	March 2016
Bridging gaps between lab- and fab-oriented anode design for proton exchange membrane water electrolyzers Xu, Jun; Yang, Yuting; Jin, Huanyu Chem https://doi.org/10.1016/j.chempr.2024.09.004	journal	October 2024
Metallic-Ir-based anode catalysts in PEM water electrolyzers: Achievements, challenges, and perspectives Fu, Cehuang; O'Carroll, Thomas; Shen, Shuiyun Current Opinion in Electrochemistry, Vol. 38 https://doi.org/10.1016/j.coelec.2023.101227	journal	April 2023
Stability and deactivation of OER electrocatalysts: A review Zeng, Feng; Mebrahtu, Chalachew; Liao, Longfei Journal of Energy Chemistry, Vol. 69 https://doi.org/10.1016/j.jechem.2022.01.025	journal	June 2022
Oxygen evolution activity and stability of iridium in acidic media. Part 1. – Metallic iridium Cherevko, Serhiy; Geiger, Simon; Kasian, Olga Journal of Electroanalytical Chemistry, Vol. 773 https://doi.org/10.1016/j.jelechem.2016.04.033	journal	July 2016
Oxygen evolution activity and stability of iridium in acidic media. Part 2. – Electrochemically grown hydrous iridium oxide Cherevko, Serhiy; Geiger, Simon; Kasian, Olga Journal of Electroanalytical Chemistry, Vol. 774 https://doi.org/10.1016/j.jelechem.2016.05.015	journal	August 2016
Stability challenges of electrocatalytic oxygen evolution reaction: From mechanistic understanding to reactor design Chen, Feng-Yang; Wu, Zhen-Yu; Adler, Zachary Joule, Vol. 5, Issue 7 https://doi.org/10.1016/j.joule.2021.05.005	journal	July 2021
Extraordinary acidic oxygen evolution on new phase 3R-iridium oxide Fan, Zhenglong; Ji, Yujin; Shao, Qi Joule, Vol. 5, Issue 12 https://doi.org/10.1016/j.joule.2021.10.002	journal	December 2021
Mass-efficient catalyst layer of hierarchical sub-nanosheets on nanowire for practical proton exchange membrane electrolyzer Tao, Lu; Lv, Fan; Wang, Dawei Joule, Vol. 8, Issue 2 https://doi.org/10.1016/j.joule.2024.01.002	journal	February 2024
Review on mechanisms and recovery procedures for reversible performance losses in polymer electrolyte membrane fuel cells Mitzel, Jens; Zhang, Qian; Gazdzicki, Pawel Journal of Power Sources, Vol. 488 https://doi.org/10.1016/j.jpowsour.2020.229375	journal	March 2021
3D nanoporous iridium-based alloy microwires for efficient oxygen evolution in acidic media Zhao, Yang; Luo, Min; Chu, Shufen Nano Energy, Vol. 59 https://doi.org/10.1016/j.nanoen.2019.02.020	journal	May 2019
IrCuNi Deeply Concave Nanocubes as Highly Active Oxygen Evolution Reaction Electrocatalyst in Acid Electrolyte Liu, Di; Lv, Qingqing; Lu, Siqi Nano Letters, Vol. 21, Issue 7 https://doi.org/10.1021/acs.nanolett.0c04878	journal	March 2021
Glassy Carbon Substrate Oxidation Effects on Electrode Stability for Oxygen Evolution Reaction Catalysis Stability Benchmarking Edgington, Jane; Deberghes, Adrien; Seitz, Linsey C. ACS Applied Energy Materials, Vol. 5, Issue 10 https://doi.org/10.1021/acsaem.2c01690	journal	September 2022
Low-Loading and Highly Stable Membrane Electrode Based on an Ir@WO _x NR Ordered Array for PEM Water Electrolysis Jiang, Guang; Yu, Hongmei; Li, Yonghuan ACS Applied Materials & Interfaces, Vol. 13, Issue 13 https://doi.org/10.1021/acsami.0c20791	journal	March 2021
Promoting Oxygen Evolution Reaction Induced by Synergetic Geometric and Electronic Effects of IrCo Thin-Film Electrocatalysts Kim, Kyu-Su; Park, Shin-Ae; Jung, Hyun Dong ACS Catalysis, Vol. 12, Issue 11 https://doi.org/10.1021/acscatal.2c00856	journal	May 2022
Standardizing OER Electrocatalyst Benchmarking in Aqueous Electrolytes: Comprehensive Guidelines for Accelerated Stress Tests and Backing Electrodes Zlatar, Matej; Escalera-López, Daniel; Rodríguez, Miquel Gamón ACS Catalysis, Vol. 13, Issue 23 https://doi.org/10.1021/acscatal.3c03880	journal	November 2023
Iridium-Based Nanowires as Highly Active, Oxygen Evolution Reaction Electrocatalysts Alia, Shaun M.; Shulda, Sarah; Ngo, Chilan ACS Catalysis, Vol. 8, Issue 3 https://doi.org/10.1021/acscatal.7b03787	journal	January 2018
Electrocatalytic Oxygen Evolution Reaction (OER) on Ru, Ir, and Pt Catalysts: A Comparative Study of Nanoparticles and Bulk Materials Reier, Tobias; Oezaslan, Mehtap; Strasser, Peter ACS Catalysis, Vol. 2, Issue 8 https://doi.org/10.1021/cs3003098	journal	July 2012
Grain-Boundary-Dependent CO ₂ Electroreduction Activity Feng, Xiaofeng; Jiang, Kaili; Fan, Shoushan Journal of the American Chemical Society, Vol. 137, Issue 14 https://doi.org/10.1021/ja5130513	journal	April 2015
Highly Crystalline Iridium–Nickel Nanocages with Subnanopores for Acidic Bifunctional Water Splitting Electrolysis Ding, Hui; Su, Caijie; Wu, Jiabao Journal of the American Chemical Society, Vol. 146, Issue 11 https://doi.org/10.1021/jacs.4c01379	journal	March 2024
Mesoporous Metallic Iridium Nanosheets Jiang, Bo; Guo, Yanna; Kim, Jeonghun Journal of the American Chemical Society, Vol. 140, Issue 39 https://doi.org/10.1021/jacs.8b05206	journal	August 2018
Activity–Stability Trends for the Oxygen Evolution Reaction on Monometallic Oxides in Acidic Environments Danilovic, Nemanja; Subbaraman, Ramachandran; Chang, Kee-Chul The Journal of Physical Chemistry Letters, Vol. 5, Issue 14 https://doi.org/10.1021/jz501061n	journal	July 2014
Iridium single atoms incorporated in Co3O4 efficiently catalyze the oxygen evolution in acidic conditions Zhu, Yiming; Wang, Jiaao; Koketsu, Toshinari Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-35426-8	journal	December 2022
Iridium oxide nanoribbons with metastable monoclinic phase for highly efficient electrocatalytic oxygen evolution Liao, Fan; Yin, Kui; Ji, Yujin Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-36833-1	journal	March 2023
Nano-metal diborides-supported anode catalyst with strongly coupled TaOx/IrO2 catalytic layer for low-iridium-loading proton exchange membrane electrolyzer Wang, Yuannan; Zhang, Mingcheng; Kang, Zhenye Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-40912-8	journal	August 2023
Considerations for the scaling-up of water splitting catalysts Kibsgaard, Jakob; Chorkendorff, Ib Nature Energy, Vol. 4, Issue 6 https://doi.org/10.1038/s41560-019-0407-1	journal	May 2019
Water electrolysers with closed and open electrochemical systems Lagadec, Marie Francine; Grimaud, Alexis Nature Materials, Vol. 19, Issue 11 https://doi.org/10.1038/s41563-020-0788-3	journal	October 2020
The gap between academic research on proton exchange membrane water electrolysers and industrial demands Tao, Hua Bing; Liu, Han; Lao, Kejie Nature Nanotechnology, Vol. 19, Issue 8 https://doi.org/10.1038/s41565-024-01699-x	journal	July 2024
The stability number as a metric for electrocatalyst stability benchmarking Geiger, Simon; Kasian, Olga; Ledendecker, Marc Nature Catalysis, Vol. 1, Issue 7 https://doi.org/10.1038/s41929-018-0085-6	journal	June 2018
Acid-stable manganese oxides for proton exchange membrane water electrolysis Kong, Shuang; Li, Ailong; Long, Jun Nature Catalysis, Vol. 7, Issue 3 https://doi.org/10.1038/s41929-023-01091-3	journal	January 2024
Ultrathin Ir nanowires as high-performance electrocatalysts for efficient water splitting in acidic media Fu, Luhong; Yang, Fulin; Cheng, Gongzhen Nanoscale, Vol. 10, Issue 4 https://doi.org/10.1039/C7NR09377B	journal	January 2018
A review on fundamentals for designing oxygen evolution electrocatalysts Song, Jiajia; Wei, Chao; Huang, Zhen-Feng Chemical Society Reviews, Vol. 49, Issue 7 https://doi.org/10.1039/C9CS00607A	journal	January 2020
Ultrathin perovskite derived Ir-based nanosheets for high-performance electrocatalytic water splitting Liu, Shangheng; Zhang, Yingtian; Mao, Xinnan Energy & Environmental Science, Vol. 15, Issue 4 https://doi.org/10.1039/D1EE03687D	journal	January 2022
PEM Fuel cell and electrolysis cell technologies and hydrogen infrastructure development – a review Wang, Yun; Pang, Yiheng; Xu, Hui Energy & Environmental Science, Vol. 15, Issue 6 https://doi.org/10.1039/D2EE00790H	journal	January 2022
IrO _x · n H ₂ O with lattice water–assisted oxygen exchange for high-performance proton exchange membrane water electrolyzers Xu, Jun; Jin, Huanyu; Lu, Teng Science Advances, Vol. 9, Issue 25 https://doi.org/10.1126/sciadv.adh1718	journal	June 2023
Ir-Sn pair-site triggers key oxygen radical intermediate for efficient acidic water oxidation Zheng, Xiaobo; Yang, Jiarui; Li, Peng Science Advances, Vol. 9, Issue 42 https://doi.org/10.1126/sciadv.adi8025	journal	October 2023
Deciphering the Poisoning Effect of Sulfate on a Perovskite-Derived IrO_xH_y Catalyst for Water Oxidation in Acid Seow, Justin Zhu Yeow; Chen, Yubo; Ge, Jingjie Journal of The Electrochemical Society, Vol. 170, Issue 4 https://doi.org/10.1149/1945-7111/accb70	journal	April 2023
OER Catalyst Stability Investigation Using RDE Technique: A Stability Measure or an Artifact? El-Sayed, Hany A.; Weiß, Alexandra; Olbrich, Lorenz F. Journal of The Electrochemical Society, Vol. 166, Issue 8 https://doi.org/10.1149/2.0301908jes	journal	January 2019

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