功函数差异自发诱导Ir/MoSe2内置电场催化高效PEM水电解

doi:10.1016/S1872-2067(25)64685-7

摘要/Abstract

摘要：

质子交换膜(PEM)电解水是实现可再生能源绿色制氢的核心技术, 传统电解槽需分别使用Ir基和Pt基催化剂用于析氧(OER)与析氢(HER)反应, 导致工艺复杂且成本高昂. 研发兼具高效双功能催化活性和稳定性的催化剂体系是简化电解槽设计、降低制氢成本的一个关键突破方向. 然而, 现有Ir基催化剂在酸性介质中面临金属溶解与团聚等问题, 难以在低贵金属载量下兼顾性能与寿命. 因此, 开发基于Ir基双功能催化剂并减少其用量成为研究重点.

本文基于功函数(WF)差异自发诱导内置电场的理论设计策略, 通过将Ir纳米颗粒负载在介孔碳球嵌入MoSe₂的载体上(Ir/MoSe₂@MCS)构建了一种高效的双功能催化剂, 旨在通过电荷再分布与界面电子调制突破双功能反应性能瓶颈, 在催化条件下实现催化活性重构, 为高性能PEM电解水催化剂的设计提供新思路. 通过对材料体系的理论筛选, 验证了MoSe₂ (WF = 5.25 eV)与Ir(WF = 5.12 eV)的WF差异可形成内置电场, 并通过密度泛函理论(DFT)揭示了其界面电荷自发从Ir向MoSe₂转移的机制(ΔՓ = 0.13 eV). 这种电荷非对称分布通过调控Ir活性中心的d带中心, 削弱了关键中间物的吸附强度, 优化了OER和HER的反应路径; OER决速步能垒降至1.65 eV, HER吉布斯自由能(ΔG_H*)趋近于零. 介孔碳嵌入MoSe₂复合结构提高了金属Ir催化剂的分散性、导电性与传质能力. Ir/MoSe₂@MCS在酸性OER和HER中分别仅需252和28 mV过电位即可获得10 mA cm^-2的动力学电流, 并且其质量活性(124.41 A g_Ir^-1@OER, 146.34 A g_Ir^-1@HER)相较于商用Ir/C提升了10多倍. 其双功能催化能力在PEM电解槽中得到了验证, 性能表现优异, 当Ir总负载量低至0.225 mg cm^-2时, 电解槽在25 °C下仅需1.68和1.89 V即可实现1和2 A cm^-2电流密度, 性能优于贵金属总负载量更高的商用Pt/C||IrO₂ (0.445 mg_Pt+Ir cm^-2). 该催化剂在1.65 V电压下连续运行30 h后, 其性能未见明显衰减, 优于商用催化电极. 通过X射线光电子能谱与高分辨透射电镜分析发现, MoSe₂载体的表面氧化对Ir活性中心起到“牺牲保护”作用, 抑制其过度氧化与迁移团聚, 而界面强金属-载体相互作用则通过电子耦合稳定了Ir的价态及结构, 多重协同机制确保了高效的双功能催化能力.

综上, 基于功函数差异自发诱导的内置电场设计双功能催化剂在电催化领域有重要的应用, 可延伸至其它金属体系. 通过界面电子结构的协同调控, 实现OER和HER反应的活性位点优化, 降低贵金属载量, 实现PEM电解水的高活性与稳定性. 未来工作可进一步探索该策略在多元催化剂体系的普适性, 为高效膜电极的研究提供新的平台.

关键词: 质子交换膜电解水, 内置电场, 功函数, 双功能电催化剂, Ir催化剂

Abstract:

Bifunctional Ir catalysts for proton exchange membrane (PEM) water electrolysis offer transformative potential by streamlining electrolyzer while achieving efficient performance remains challenging due to the distinct conditions required for oxygen and hydrogen evolution reaction (OER and HER). Herein, we propose a theory-directed design of Ir-based bifunctional catalysts, Ir nanoparticles supported on mesoporous carbon spheres embedded with MoSe₂ (Ir/MoSe₂@MCS), leveraging a work function (WF)-induced spontaneous built-in electric field to enhance catalytic performance. They demonstrate exceptional kinetics for both OER and HER, and potential application in the practical PEM electrolyzer, showcasing the effectiveness of this innovative approach. Low overpotentials of 252 mV for OER and 28 mV for HER to drive 10 mA cm^-2 were observed, and the PEM electrolyzer showed the current density of 2 A cm^-2 at 1.87 V and maintained stable activity at 1.65 V for over 30 h to deliver 1 A cm^-2. Density functional theory calculations reveal that the WF difference at Ir/MoSe₂ interface induces a spontaneous built-in electric field with asymmetric charge distributions, that modulate the electronic environment and d-band center of Ir promoting bifunctional active phase formation. This significantly lowers reaction barriers for water splitting by balancing intermediate adsorption, endowing the bifunctional activity.

Key words: Proton exchange membrane water electrolysis, Built-in electric field, Work function, Bifunctional electrocatalyst, Iridium catalyst

张冰洁, 王春燕, 杨甫林, 王书莉, 冯立纲. 功函数差异自发诱导Ir/MoSe₂内置电场催化高效PEM水电解[J]. 催化学报, 2025, 75: 95-104.

Zhang Bingjie, Wang Chunyan, Yang Fulin, Wang Shuli, Feng Ligang. Work function-induced spontaneous built-in electric field in Ir/MoSe₂ for efficient PEM water electrolysis[J]. Chinese Journal of Catalysis, 2025, 75: 95-104.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64685-7

https://www.cjcatal.com/CN/Y2025/V75/I8/95

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Fig. 1. (a) WF of Ir and MoSe2. (b) Electron transfer diagram. (c) Planar average potential along z direction at the Ir/MoSe2 interface. (d) The DOS diagram of bulk Ir, MoSe2 and Ir/MoSe2. (e) The DOS diagram of Ir and Ir in Ir/MoSe2. (f) COHP curves for O* intermediate adsorption on Ir active site for Ir and Ir/MoSe2.

Fig. 2. Fabrication procedure and structural characterization. (a) Schematic for MCS, MoSe2@MCS and Ir/MoSe2@MCS fabrication. (b-d) TEM images of the Ir/MoSe2@MCS. (e) SAED pattern. (f) HRTEM image. (g) STEM and corresponding elemental mapping images of the Ir/MoSe2@MHCS catalyst. (h) XRD patterns of MoSe2, MoSe2@MCS and Ir/MoSe2@MCS. XPS spectra of Ir 4f for Ir/MoSe2@MCS (i) and Mo 3d for MoSe2@MCS and Ir/MoSe2@MCS (j).

Fig. 3. Acidic OER and HER performance of Ir/MoSe2@MCS and other samples. (a) OER polarization curves (5 mV s-1). (b) Mass activity comparison. (c) Tafel slopes. (d) Nyquist plots. (e) HER polarization curves. (f) Mass activity comparison. (g) Tafel slopes. (h) Nyquist plots. (i) The Cdl values. (j) Polarization curves of the two-electrode electrolyzer. (k) CA curve for the Ir/MoSe2@MCS||Ir/MoSe2@MCS electrolyzer at 1.525 V and Pt/C||IrO2 electrolyzer at 1.623 V (inset: Schematic diagram of the device). (l)The collected H2 and O2 volumes as a function of operation time.

Fig. 4. Elemental mapping of Ir/MoSe2@MCS after 40 h of OER (a) and HER (b) stability test. The content change of Ir0 and Ir4+ (c) and Mo4+ and Mo6+ (d) after the stability test. (e) Schematic illustration of a PEMWE cell and components. (f) Performance curve of the PEM electrolyzer. (g) Chronoamperometric measurement of the PEMWE at 1.65 V using Ir/MoSe2@MCS as a bifunctional electrocatalyst (inset: photograph of the assembled cell). (g) PEMWE working at 1.65 V with Ir/MoSe2@MCS and Pt/C||IrO2 at 2.00 V for 30 h (inset: photograph of the assembled cell).

Fig. 5. (a) The PDOS diagram of IrO2/MoSe2 and IrO2. (b) Downshift of εd lowers the corresponding antibonding orbits. (c) The free energy diagrams for OER on the IrO2/MoSe2@MCS and IrO2 surface, showing the adsorption of oxygen intermediates (*O, *OH, and *OOH). (d) Gibbs free energy of the decision step of OER process. (e) HER on the Ir/MoSe2@MCS, Pt/C, Ir/C, and MoSe2 surface. (f) Schematic diagram of the Ir/MoSe2 adsorption/desorption intermediate process.

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功函数差异自发诱导Ir/MoSe₂内置电场催化高效PEM水电解

Work function-induced spontaneous built-in electric field in Ir/MoSe₂ for efficient PEM water electrolysis

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