在硫化钼基面上调控原子级协同活性中心用于碱氢演化反应

doi:10.1016/S1872-2067(24)60034-3

催化学报 ›› 2024, Vol. 61: 281-290.DOI: 10.1016/S1872-2067(24)60034-3

在硫化钼基面上调控原子级协同活性中心用于碱氢演化反应

罗旭宇^a^,^b^,¹, 王颖^a^,¹, 杨光^b, 刘璐^a, 郭诗颖^a, 崔义^b^,^*(), 许小勇^a^,^*()

^a扬州大学物理科学与技术学院, 江苏扬州 225002
^b中国科学院苏州纳米技术与纳米仿生研究所, 真空互联纳米技术工作站, 江苏苏州 215123

收稿日期:2024-01-27 接受日期:2024-04-08 出版日期:2024-06-18 发布日期:2024-06-20
通讯作者: * 电子信箱: xxy@yzu.edu.cn (许小勇),ycui2015@sinano.ac.cn (崔义).
作者简介:
¹共同第一作者.
基金资助:
国家自然科学基金(11974303);国家自然科学基金(12074332);江苏省青蓝工程(137050317);扬州大学高端人才计划(137080051);化学重点学科交叉研究基金(yzuxk202014)

Atomically tailoring synergistic active centers on molybdenum sulfide basal planes for alkaline hydrogen generation

Xuyu Luo^a^,^b^,¹, Ying Wang^a^,¹, Guang Yang^b, Lu Liu^a, Shiying Guo^a, Yi Cui^b^,^*(), Xiaoyong Xu^a^,^*()

^aSchool of Physics Science & Technology, Yangzhou University, Yangzhou 225002, Jiangsu, China
^bi-Lab, Vacuum Interconnected Nanotech Workstation, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou 215123, Jiangsu, China

Received:2024-01-27 Accepted:2024-04-08 Online:2024-06-18 Published:2024-06-20
Contact: * E-mail: xxy@yzu.edu.cn (X. Xu), ycui2015@sinano.ac.cn (Y. Cui).
About author:
¹Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(11974303);National Natural Science Foundation of China(12074332);Qinglan Project of Jiangsu Province(137050317);High-End Talent Program of Yangzhou University(137080051);Interdisciplinary Research Foundation for Chemistry Discipline(yzuxk202014)

摘要/Abstract

摘要：

电解水技术是一种生产高纯氢燃料的方法, 能够增强可再生能源发电系统的消纳能力. 相较于质子交换膜(PEM)电解槽, 碱性(ALK)电解槽可以使用非贵金属基催化电极, 拥有更高的经济效益和市场占有率. 然而, 由于ALK电解槽处于质子稀缺环境, 阴极氢气演化反应(HER)动力学变得更加复杂, 需要快速解离水分子提供动态质子微环境. 硫化钼(MoS₂)纳米片边缘具有合适的质子吸附和演化的活性位点, 是制备HER催化剂的潜力材料. 但其二维基面原子由于配位饱和, 显示出较弱的质子吸附能力. 如何调控MoS₂基面以实现水解动力与质子吸附演化动力的集成, 提升MoS₂纳米片的碱性HER活性, 具有重要的科学和应用意义.
本文提出了一种Co/O双原子植入策略, 精准调控双活性位点及其电子结构, 实现了水解离动力和质子吸附演化动力的高效耦联. 首先, 利用刻蚀和电沉积的两步实验法, 在MoS₂基面上成功引入O和Co原子; 随后, 结合高分辨透射电镜、高角环形暗场-扫描透射电子显微镜、同步辐射X射线吸收精细结构谱等表征分析技术, 精准识别了掺杂Co/O原子的位置和配位情况: O原子替换部分S原子, Co原子占据Mo原子的上方, 构建出立体凸起的“O-Co-S₂”配位构型. 催化在线的原位表征分析结果表明: 该独特的“O-Co-S₂”原子基序发挥着水解离与氢演化反应协同催化效应. 密度泛函理论计算结果也证实了该协同机制, 其中Co位点促进水的解离反应, 而S位点则有助于质子的转化生成氢气. 因此, Co/O掺杂MoS₂催化剂(Co-O@MoS₂)表现出较好的碱性HER活性: 仅需81 mV的过电位, 即可达到100 mA cm^‒2的电流密度, Tafel斜率低至42 mV dec^‒1, 在600 mA cm^‒2的高电流密度测试中运行300 h活性无衰减. 上述碱性HER性能不仅远高于原始的MoS₂纳米片, 而且也领先于部分已报道结果.
综上所述, 本文在MoS₂基面上构筑了原子级协同催化活性中心, 显著促进了碱性HER反应性能, 为原子活化工程开发先进催化剂提供参考, 在原子级基序构造、表征和功能分析方面提供借鉴.

关键词: 碱水电解, 氢气演化反应, 硫化钼, 原子尺度活化, 协同活性位点

Abstract:

Alkaline water electrolysis allows the adoption of non-precious metal catalysts, but increases the challenge of cathodic hydrogen evolution reaction (HER) with the proton-deficient environment. Here we report an “all-in-one” design by atomic-level tailoring on molybdenum sulfide (MoS₂) basal planes with synergistic active centers to trigger water dissociation for proton supply and meanwhile improve proton adsorption for hydrogen evolution. The resultant Co/O-codoped MoS₂ (Co-O@MoS₂) catalyst shows superb alkaline HER activity with a small Tafel slope of 42 mV dec^-1 and an overpotential as low as 81 mV at 100 mA cm^-2, and considerable stability over 300 h even at industrial-grade high current density of 600 mA cm^-2, which are among the best records for precious-metal-free HER catalysts in alkaline media. The markedly enhanced alkaline HER performance is attributed to the synergistic effect from atomically constructed O-Co-S₂ motifs with local electronic interactions, in which Co sites promote the premier water dissociation, and S sites facilitate proton transition to generate hydrogen, respectively. This work presents an atomic-scale structural modification to create synergistic active sites for alkaline HER and provides insights into the atomic activation engineering towards advanced catalysts.

Key words: Alkaline water electrolysis, Hydrogen evolution reaction, Molybdenum sulfide, Atomic-scale activation, Synergistic active center

罗旭宇, 王颖, 杨光, 刘璐, 郭诗颖, 崔义, 许小勇. 在硫化钼基面上调控原子级协同活性中心用于碱氢演化反应[J]. 催化学报, 2024, 61: 281-290.

Xuyu Luo, Ying Wang, Guang Yang, Lu Liu, Shiying Guo, Yi Cui, Xiaoyong Xu. Atomically tailoring synergistic active centers on molybdenum sulfide basal planes for alkaline hydrogen generation[J]. Chinese Journal of Catalysis, 2024, 61: 281-290.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60034-3

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图/表 5

Fig. 1. Schematic diagram of atomic-level synergistic active ‘O-Co-S2’ motifs onto MoS2 basal planes with protrudent Co sites serving for favorable WD and OH* transition to provide proton supply and planar S sites serving for nearly optimal H* transition to evolve H2.

Fig. 2. Structure characterizations of Co-O@MoS2. (A) SEM image of Co-O@MoS2 nanosheets grown on CFC. (B) TEM image of Co-O@MoS2. Inset: the SAED pattern. (C) HRTEM image of Co-O@MoS2. Inset: the magnified lattice fringe in plane region. (D) HAADF-STEM image of Co-O@MoS2. (E) Aberration-corrected HAADF-STEM image with simulated hexagonal units of Co-O@MoS2. (F) Atomic intensity profiles along the three different colored lines labeled in (E). (G) EDX elemental mapping images of Co-O@MoS2.

Fig. 3. Coordination characterizations of atomic Co site. (A) High-resolution XPS spectrum of Co 2p in Co-O@MoS2. (B) Normalized Co K-edge XANES spectra and (C) Fourier-transformed k2-weighted Co K-edge EXAFS spectra of Co-O@MoS2, CoO, Co2O3, and Co foil. (D) Co K-edge EXAFS (points) and fit curve (line) for Co-O@MoS2. Inset: a configuration model of O-Co-S2 center. (E) Wavelet transform for the k2-weighted EXAFS spectra of Co-O@MoS2, Co2O3, and Co foil.

Fig. 4. HER performance of Co-O@MoS2 catalyst. LSV curves of MoS2, O@MoS2, Co-O@MoS2 and Pt/C catalysts on CFC substrates measured in 1.0 mol L-1 KOH at 5 mV s-1 scan rate (A), and the corresponding Tafel slopes (B). (C) In situ Raman spectra of Co-O@MoS2 with applied potentials in control. EIS Nyquist plots (D), Cdl (E), and TOF curves (F) of MoS2, O@MoS2, and Co-O@MoS2. (G) Stability test of Co-O@MoS2 for 300 h in CA model at -242 mV vs. RHE, with arrow marks for electrolyte adding.

Fig. 5. DFT Calculations on HER mechanism. (A) Charge density difference of MoS2 and Co-O@MoS2. The brown and green contours indicate electron accumulation and depletion, respectively. (B,C) PDOS for MoS2 and Co-O@MoS2. The insets show the unoccupied orbital distributions (purple contour) near Fermi level. (D) Gipps free energy for H* absorption at different sites. The inset shows the markers of different S sites on Co-O@MoS2. (E) Relative energy diagram along alkaline HER route on MoS2 and Co-O@MoS2. The inset shows the schematic of catalytic mechanism of alkaline HER with the absorption configurations of various intermediates.

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在硫化钼基面上调控原子级协同活性中心用于碱氢演化反应

Atomically tailoring synergistic active centers on molybdenum sulfide basal planes for alkaline hydrogen generation

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