M-O-Si键激活NiFe-LDH中的吸附质演化机制与晶格氧机制协同提升析氧反应

doi:10.1016/S1872-2067(25)64xxx-x

催化学报

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M-O-Si键激活NiFe-LDH中的吸附质演化机制与晶格氧机制协同提升析氧反应

谢静^a,b,1, 唐赢^a,c,1, 叶松波^b, 鲍文涛^a, 王天田^a, 赵云霞^a, 王世富^d, 郁洁^e, 李旭宁^c, 李昊^b,*, 于锋^a,*

^a石河子大学化学化工学院新疆兵团化工绿色过程重点实验室, 新疆石河子 832003, 中国;
^b东北大学材料科学高等研究所(WPI-AIMR), 仙台 980-8577, 日本;
^c新疆工业学院通识学院, 新疆战略性矿产资源绿色智能开发与高效利用兵团重点实验室, 新疆和田 848000, 中国;
^d中国科学院大连化学物理研究所, 催化基础国家重点实验室, 辽宁大连 116023, 中国;
^e天津大学化工学院, 天津 300350, 中国

收稿日期:2026-01-27 接受日期:2026-01-27
通讯作者: *电子信箱: yufeng05@mail.ipc.ac.cn (于锋), li.hao.b8@tohoku.ac.jp (李昊),.
作者简介:¹共同第一作者.
基金资助:
兵团科技计划项目(2025BC008, 2023AB033); 日本学术振兴会KAKENHI项目(JP25K01737); 日本科学技术振兴机构SPRING项目(JPMJSP2114).

Activating synergetic adsorbate evolution and lattice oxygen mechanisms in NiFe-LDH via M-O-Si bonding for improved oxygen evolution reaction

Xie Jing^a,b,1, Tang Ying^a,c,1, Ye Songbo^b, Bao Wentao^a, Wang Tiantian^a, Zhao Yunxia^a, Wang Shifu^d, Yu Jie^e, Li Xuning^c, Li Hao^b,*, Yu Feng^a,*

^aKey Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, School of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832003, Xinjiang, China;
^bAdvanced Institute for Materials Research (WPI-AIMR), Tohoku University, Sendai 980-8577, Japan;
^cXinjiang Production & Construction Corps Key Laboratory of Green and Intelligent Development and Efficient Utilization of Strategic Mineral Resources, College of General Education, Xinjiang University of Technology, Hotan 848000, Xinjiang, China;
^dState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
^eSchool of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China

Received:2026-01-27 Accepted:2026-01-27
Contact: *E-mail: yufeng05@mail.ipc.ac.cn (F. Yu), li.hao.b8@tohoku.ac.jp (H. Li).
About author:¹These authors contributed equally to this work.
Supported by:
Bingtuan Science and Technology Program (2025BC008, 2023AB033), JSPS KAKENHI (JP25K01737), and JST SPRING (JPMJSP2114).

摘要/Abstract

摘要： 析氧反应(OER)是电解水制氢的关键步骤, 其四电子转移过程容易导致高过电位, 降低电解水制氢的能量转换效率. 贵金属基催化剂(如IrO₂, RuO₂)具有优异的OER性能, 然而面临着资源稀缺、成本高昂等困境, 限制了其大规模应用. 因此, 开发高效、稳定、廉价的非贵金属OER催化剂具有重要意义. 镍铁层状双氢氧化物(NiFe-LDH)因其具有高比表面积和可调的电子结构, 是最具潜力的OER催化剂候选材料之一. 然而, NiFe-LDH还存在重构电位高、活性位点有限、晶格氧惰性等问题, 导致本征活性不足. 如何同时优化金属活性位点和促使晶格氧参与反应, 实现吸附质演化机制(AEM)和晶格氧机制(LOM)双路径协同, 是一个重要且具有挑战性的研究方向.
本文提出了一种构建M-O-Si (M = Ni, Fe)键的新策略, 成功降低了催化剂的相变电位, 优化了Ni位点上中间体的吸附能, 降低了AEM路径中电势决定步骤(PDS)的能垒. 同时, M-O-Si诱导O 2p带中心上移, 更多晶格氧参与了反应, 降低了LOM路径中PDS的能垒, 增强了Si-NiFe-LDH催化剂AEM与LOM的协同作用. 通过原位拉曼光谱分析, 发现Si-NiFe-LDH的Ni²⁺→Ni³⁺相变电位从1.50 V降至1.45 V, 说明M-O-Si键增强了电化学重构,促进了活性物种NiOOH的生成. 同时, ¹⁸O同位素标记的差分电化学质谱测试, 发现Si-NiFe-LDH在OER反应过程中的三种O₂信号显著增强, 说明Si掺杂不仅增强了AEM路径, 还促使更多晶格氧参与反应. 密度泛函理论计算表明, Si-NiFe-LDH催化剂在AEM反应路径中, Ni位点的PDS从*OH→*O转变为*OOH→O₂, 能垒从2.23降至1.60 eV. 微动力学火山图显示, Si-NiFe-LDH的Ni位点更接近理论最优吸附平衡区域. 在LOM反应路径中, PDS能垒从1.42降至1.15 eV. 通过投影态密度分析发现, O 2p带中心上移, 增强了晶格氧的释放能力. M-O-Si键通过协同调控Ni位点电子结构和晶格氧活性, 实现了AEM与LOM双反应路径的协同增强. 在1 M KOH电解液中, Si-NiFe-LDH在10和100 mA cm^-2电流密度下的OER过电位分别仅为174和250 mV, 相比NiFe-LDH分别降低了55和42 mV, 并在450 h测试中保持了优异的稳定性. 电化学活性面积(ECSA)归一化后, 其本征活性是NiFe-LDH的2.1倍, 表明Si掺杂对ECSA提升贡献有限, 性能提升主要源于M-O-Si键诱导的电子结构优化, 从而增强了本征反应活性. 此外, 该催化剂在析氢反应中也表现出112 mV的低过电位(@10 mA cm^-2). 在模拟太阳能驱动的全电解水测试中, 在1.55 V电压下即可实现水分解, 为绿电驱动电解水制氢提供了理论支撑.
综上, 本工作通过构建M-O-Si键, 优化了AEM与LOM双路径协同作用, 增强了反应活性, 显著降低了OER过电位. 该策略实现了高效的双机制协同催化, 为设计低成本、高性能的非贵金属OER催化剂提供了新思路.

关键词: 硅掺杂, M-O-Si键, 快速刻蚀, 析氧反应, 电解水

Abstract: High overpotential oxygen evolution reactions (OER) remain a strongly challenging factor for efficient hydrogen production via water electrolysis in energy harvesting devices. Here, we propose a new strategy for lowering overpotentials based on M-O-Si (M = Ni, Fe) covalent bond formation through a rapid 30-s chemical etching process to create a silicon-doped anemone-like NiFe layered double hydroxide (Si-NiFe-LDH/NF). Our strategy decreases the catalytic phase-transition potential and optimizes intermediate binding at Ni sites, reducing the adsorbate evolution mechanism barrier. Concurrently, it induces an upshift of the O 2p band center, which activates lattice oxygen and lowers the energy barrier along the lattice oxygen mechanism pathway. Our findings highlight the synergistic optimization of the dual mechanisms, demonstrating superior catalytic performance of Si-NiFe-LDH/NF in 1 M KOH relative to NiFe-LDH/NF, where OER overpotentials are reduced by 24% and 14.4% at current densities of 10 and 100 mA cm-2, respectively. In addition, a low hydrogen evolution reaction overpotential of 112 mV at 10 mA cm-2 is achieved. Finally, we demonstrate the strong potential of our strategy in industrial applications through the operation (at 1.55 V) of an assembled solar-powered total water electrolyzer.

Key words: Silicon doping, M-O-Si bond, Rapid etching, Oxygen evolution reaction, Water electrolysis

谢静, 唐赢, 叶松波, 鲍文涛, 王天田, 赵云霞, 王世富, 郁洁, 李旭宁, 李昊, 于锋. M-O-Si键激活NiFe-LDH中的吸附质演化机制与晶格氧机制协同提升析氧反应[J]. 催化学报, DOI: 10.1016/S1872-2067(25)64xxx-x.

Xie Jing, Tang Ying, Ye Songbo, Bao Wentao, Wang Tiantian, Zhao Yunxia, Wang Shifu, Yu Jie, Li Xuning, Li Hao, Yu Feng. Activating synergetic adsorbate evolution and lattice oxygen mechanisms in NiFe-LDH via M-O-Si bonding for improved oxygen evolution reaction[J]. Chinese Journal of Catalysis, DOI: 10.1016/S1872-2067(25)64xxx-x.

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M-O-Si键激活NiFe-LDH中的吸附质演化机制与晶格氧机制协同提升析氧反应

Activating synergetic adsorbate evolution and lattice oxygen mechanisms in NiFe-LDH via M-O-Si bonding for improved oxygen evolution reaction

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