Citation: Xiaoqian Wei, Hanyu Gao, Tiantian Wang, Zijian Li, Yanru Geng, Guiping Zheng, Min Gyu Kim, Haeseong Jang, Xien Liu, Qing Qin. Neodymium-doped hollow Ir/IrO2 nanospheres with low geometric iridium density enable excellent acidic water oxidation performance[J]. Chinese Journal of Structural Chemistry, ;2025, 44(7): 100600. doi: 10.1016/j.cjsc.2025.100600 shu

Neodymium-doped hollow Ir/IrO2 nanospheres with low geometric iridium density enable excellent acidic water oxidation performance

Reducing the Ir loading while preserving catalytic performance and mechanical robustness in anodic catalyst layers remains a critical challenge for the large-scale implementation of proton exchange membrane water electrolysis (PEMWE). Herein, we present a structural engineering strategy involving neodymium-doped Ir/IrO2 (Nd–Ir/IrO2) hollow nanospheres with precisely adjustable shell thickness and cavity dimensions. The optimized catalyst demonstrates excellent oxygen evolution reaction (OER) performance in acidic media, achieving a remarkably low overpotential of 259 mV at a benchmark current density of 10 mA cm−2 while exhibiting substantially enhanced durability compared to commercial IrO2 and Ir/IrO2 counterparts. Notably, the Nd–Ir/IrO2 catalyst delivers a mass activity of 541.6 A gIr−1 at 1.50 V vs. RHE, representing a 74.5-fold enhancement over conventional IrO2. Comprehensive electrochemical analysis and advanced characterization techniques reveal that the hierarchical hollow architecture simultaneously addresses multiple critical requirements: (i) abundant exposed active sites enabled by an enhanced electrochemical surface area, (ii) optimized mass transport pathways through engineered porosity, and (iii) preserved structural integrity via a continuous conductive framework, collectively enabling significant Ir loading reduction without compromising catalytic layer performance. Fundamental mechanistic investigations further disclose that Nd doping induces critical interfacial Nd–O–Ir configurations that stabilize lattice oxygen, together with intensified electron effect among mixed valent Ir that inhibits the overoxidation of Ir active sites during the OER process, synergistically ensuring enhanced catalytic durability. Our work establishes a dual-modulation paradigm integrating nanoscale architectural engineering with atomic-level heteroatom doping, providing a viable pathway toward high-performance PEMWE systems with drastically reduced noble metal requirements.
- Oxygen evolution catalyst,
- Low iridium geometric density,
- Electronic effect,
- Nanoscale architectural engineering,
- Anodic catalyst layer
1. [1]
  Heng Gao , Zhaocong Cheng , Guangshui Tu , Zonglin Qiu , Xieyi Xiao , Haotian Zhou , Handou Zheng , Haiyang Gao . Thermally robust bis(imino)pyridyl iron catalysts for ethylene polymerization: Synergy effects of weak π-π interaction, steric bulk, and electronic tuning. Chinese Chemical Letters, 2025, 36(5): 110762-. doi: 10.1016/j.cclet.2024.110762
2. [2]
  Zhili Yang , Liqun Liu , Xuebi Rao , Zeyu Jin , Jialin Sun , Yongkang Zhu , Shiming Zhang . Deprotonation effect doubles active site density in Fe-N₄-C catalyst for oxygen reduction electrocatalysis. Chinese Chemical Letters, 2025, 36(11): 111440-. doi: 10.1016/j.cclet.2025.111440
3. [3]
  Shengxia Yang , Yukang Pan , Tianyu Kong , Chaoran Jia , Yueyang Cui , Xuehua Li , Yannan Zhou , Haijun Liu , Xinyu Zhang , Bin Dong , Qunwei Tang . Ru and S co-modification-induced synergistic morphology and electronic engineering of nickel-iron hydroxide with efficient oxygen evolution. Chinese Chemical Letters, 2025, 36(12): 111540-. doi: 10.1016/j.cclet.2025.111540
4. [4]
  Zhongjie Song , Nannan Zhang , Jun Yu , Huiyu Sun , Zhengying Wu , Yukou Du . Growth of Ce-doped NiCo-LDHs on tin dioxide-modified nickel foam as oxygen evolution reaction catalyst electrode. Chinese Chemical Letters, 2026, 37(1): 111804-. doi: 10.1016/j.cclet.2025.111804
5. [5]
  Hong Yin , Zhipeng Yu . Hexavalent iridium catalyst enhances efficiency of hydrogen production. Chinese Journal of Structural Chemistry, 2025, 44(1): 100382-100382. doi: 10.1016/j.cjsc.2024.100382
6. [6]
  Yaqin Zheng , Lian Zhuo , Meng Li , Chunying Rong . Enhancing Understanding of the Electronic Effect of Substituents on Benzene Rings Using Quantum Chemistry Calculations. University Chemistry, 2025, 40(3): 193-198. doi: 10.12461/PKU.DXHX202406119
7. [7]
  Xudong Liu , Huili Fan , Junping Xiao , Min Yang , Yan Li . Teaching Approaches to the A_E + A_N Mechanism of Electrophilic Addition Reactions between Olefins and Inorganic Acids in Organic Chemistry. University Chemistry, 2025, 40(7): 367-372. doi: 10.12461/PKU.DXHX202409041
8. [8]
  Doudou Liu , Weiwei Guo , Guoliang Mei , Youpeng Dan , Rong Yang , Chao Huang , Yanling Zhai , Xiaoquan Lu . Application of catalyst Cu-t-ZrO₂ based on the electronic metal-support interaction in electrocatalytic nitrate reduction. Chinese Chemical Letters, 2025, 36(8): 110578-. doi: 10.1016/j.cclet.2024.110578
9. [9]
  Yizhe Chen , Yuzhou Jiao , Liangyu Sun , Cheng Yuan , Qian Shen , Peng Li , Shiming Zhang , Jiujun Zhang . Nonmetallic phosphorus alloying to regulate the oxygen reduction mechanisms of platinum catalyst. Chinese Chemical Letters, 2025, 36(4): 110789-. doi: 10.1016/j.cclet.2024.110789
10. [10]
  Kun Wang , Tianxue Gong , Yaohuang Huang , Boyang Han , Hanxiao Yang , Pavlo O. Dral , Weiwei Fang . Bornylimidazo[1,5–a]pyridin-3-ylidene allylic Pd catalyst with optimal electronic and steric properties for synthesis of 3,3′-disubstituted oxindoles. Chinese Chemical Letters, 2025, 36(7): 110539-. doi: 10.1016/j.cclet.2024.110539
11. [11]
  Bingke Zhang , Dongbo Wang , Jiamu Cao , Wen He , Gang Liu , Donghao Liu , Chenchen Zhao , Jingwen Pan , Sihang Liu , Weifeng Zhang , Xuan Fang , Liancheng Zhao , Jinzhong Wang . Tuning Stark effect by defect engineering on black titanium dioxide mesoporous spheres for enhanced hydrogen evolution. Chinese Chemical Letters, 2024, 35(11): 110254-. doi: 10.1016/j.cclet.2024.110254
12. [12]
  Xuyun Lu , Yanan Chang , Shasha Wang , Xiaoxuan Li , Jianchun Bao , Ying Liu . Hydrogen peroxide electrosynthesis via two-electron oxygen reduction: From pH effect to device engineering. Chinese Chemical Letters, 2025, 36(5): 110277-. doi: 10.1016/j.cclet.2024.110277
13. [13]
  Xue Zhao , Rui Zhao , Qian Liu , Henghui Chen , Jing Wang , Yongfeng Hu , Yan Li , Qiuming Peng , John S Tse . A p-d block synergistic effect enables robust electrocatalytic oxygen evolution. Chinese Chemical Letters, 2024, 35(11): 109496-. doi: 10.1016/j.cclet.2024.109496
14. [14]
  Yongsheng Xu , Lisha Yao , Jian Li , Yanzhao Dong , Dongyang Xie , Miaomiao Zhang , Feng Li , Yunsheng Dai , Jinli Zhang , Haiyang Zhang . Dual-ligand engineering over Au-based catalyst for efficient acetylene hydrochlorination. Chinese Chemical Letters, 2025, 36(3): 110318-. doi: 10.1016/j.cclet.2024.110318
15. [15]
  Jiawei Ge , Xian Wang , Heyuan Tian , Hao Wan , Wei Ma , Jiangying Qu , Junjie Ge . Iridium-based catalysts for oxygen evolution reaction in proton exchange membrane water electrolysis. Chinese Chemical Letters, 2025, 36(5): 109906-. doi: 10.1016/j.cclet.2024.109906
16. [16]
  Zhengkun QIN , Zicong PAN , Hui TIAN , Wanyi ZHANG , Mingxing SONG . A series of iridium(Ⅲ) complexes with fluorophenyl isoquinoline ligand and low-efficiency roll-off properties: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1235-1244. doi: 10.11862/CJIC.20240429
17. [17]
  Peng Wang , Daijie Deng , Suqin Wu , Li Xu . Cobalt-based deep eutectic solvent modified nitrogen-doped carbon catalyst for boosting oxygen reduction reaction in zinc-air batteries. Chinese Journal of Structural Chemistry, 2024, 43(1): 100199-100199. doi: 10.1016/j.cjsc.2023.100199
18. [18]
  Guanjun Chen , Jiayi Yang , Zheming Huang , Long Chen , Wenyuan Duan , Tong Wang , Xingang Kong , Haibo Yang . Engineering the interlayer sodium density in layered sodium cobalt oxide for boosted chlorine evolution reaction. Chinese Chemical Letters, 2025, 36(12): 111662-. doi: 10.1016/j.cclet.2025.111662
19. [19]
  Tengjia Ni , Xianbiao Hou , Huanlei Wang , Lei Chu , Shuixing Dai , Minghua Huang . Controllable defect engineering based on cobalt metal-organic framework for boosting oxygen evolution reaction. Chinese Journal of Structural Chemistry, 2024, 43(1): 100210-100210. doi: 10.1016/j.cjsc.2023.100210
20. [20]
  Yuanhua Xiao , Jinhui Shou , Shiwei Zhang , Ya Shen , Junwei Liu , Dangcheng Su , Yang Kong , Xiaodong Jia , Qingxiang Yang , Shaoming Fang , Xuezhao Wang . Synergistic interlayer confinement and built-in electric field construct reconstruction-inhibited cobalt selenide for robust oxygen evolution at high current density. Chinese Chemical Letters, 2025, 36(11): 111441-. doi: 10.1016/j.cclet.2025.111441

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(120)
HTML views(0)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142