单原子钌诱导界面水结构调控实现高效的碱性氢氧化反应

doi:10.1016/S1872-2067(24)60283-4

摘要/Abstract

摘要：

合理设计催化剂的几何与电子结构以提高催化位点的本征活性是电催化领域的关键之一. 具有单位点分散结构的单原子催化剂表现出较高的原子利用率及催化效率, 特别是与金属团簇/纳米颗粒耦合时, 其可为涉及不同反应中间体的复杂过程提供多元活性位点, 从而显著提升各种电催化过程的反应性能. 然而, 目前对于单原子与金属团簇/纳米颗粒协同效应的探究仍局限于催化剂电子结构及反应中间体热力学吸附能的调控上, 而忽视了优化电化学界面, 特别是改善双电层环境中的界面水结构及氢键相互作用对于电催化反应动力学的重要影响.

因此为了深入探究单原子位点的催化作用, 本文利用多孔氮掺杂碳的限域锚定效应, 以及简易的浸渍煅烧还原法制备了氮碳负载的钌单原子及纳米颗粒耦合催化剂(记为Ru_1,_n/NC), 并选择碱性氢氧化反应(HOR)作为研究模型以阐明两者间的协同效应. 透射电子显微镜及高角环形暗场-扫描透射显微镜表征表明, 平均粒径约为1.8 nm的Ru纳米颗粒均匀分散在氮碳载体上, 并且其周围可观测到明显的Ru单原子, 证明耦合催化剂Ru_1,_n/NC的成功制备. X射线光电子能谱及吸收谱表征表明高价态Ru单原子的存在及由Ru向氮碳基底的电荷转移过程, 同时扩展X射线吸收精细结构表明, Ru_1,_n/NC中主要存在Ru-Ru及Ru-N配位环境. 电化学测试表明, Ru_1,_n/NC在0.1 mol L^-1 KOH溶液中的HOR性能显著超越单一的Ru纳米颗粒对照样品, 并且与目前最为先进的商业铂碳催化剂相当, 其面积及质量比活性分别达到0.43 mA cm_PGM^-2及1.15 mA μg_PGM^-1, 与Ru纳米颗粒相比提升了两倍之多. 密度泛函理论计算结果发现, Ru单原子及纳米颗粒耦合结构的设计调控了Ru的d带中心位置及其吸附水后的反键轨道填充度, 从而优化了其氢及水结合能. 并且Ru_1,_n/NC表面吸附的水分子可利用氢键作用促进OH^-向电极表面的转移, 以便其与相邻的吸附氢中间体结合完成HOR过程. 随后利用表面增强原位红外光谱探究了界面水结构在HOR电势下的动态演变过程. Ru_1,_n/NC得益于带正电荷Ru单原子的存在, 可以稳定强氢键水分子中带有负电荷的氧端, 因而在任意电势下均具有最高的强氢键水占比, 表明氢键网络联通性最为优异, 可以加速碱性HOR中的质子耦合电子转移动力学, 从而促进溶液中OH^-物种通过Grotthuss机制向电极表面的传输速率, 最终显著提升了Ru基材料的碱性氢电催化能力.

综上所述, 本文成功制备了具有高本征活性及原子利用率的钌单原子及纳米颗粒耦合催化剂, 并揭示了钌单原子对于界面双电层中的水分子及氢键网络结构的调控作用, 最终揭示了其碱性HOR性能提升的本质原因, 为单原子催化剂的合理设计拓宽思路.

关键词: 双电层环境, 氢氧化反应, 界面水结构, 物质传输过程, 单原子位点

Abstract:

The employment of single atom catalysts (SACs) remarkably increases atomic utilization and catalytic efficiency in various electrochemical processes, especially when coupled with metal clusters/nanoparticles. However, the synergistic effects mainly focus on the energetics of key intermediates during the electrocatalysis, while the properties of electrode surface and electric-double-layer (EDL) structure are largely overlooked. Herein, we report the synthesis of Ru nanoparticles integrated with neighboring Ru single atoms on nitrogen doped carbon (Ru_1,_n/NC) as efficient catalysts toward hydrogen oxidation reaction (HOR) under alkaline electrolytes. Electrochemical data, in situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy, and density functional theory calculations reveal that the positively charged Ru single atoms could lead to the dynamically regulated proportion of strongly hydrogen-bonded interfacial water structure with O-down conformation and optimized connectivity of the hydrogen-bond network in the EDL region, which contribute to the accelerated diffusion of hydroxide ions to the electrified interfaces. Consequently, the obtained Ru_1,_n/NC catalyst displays remarkable HOR performance with the mass activity of 1.15 mA μg_PGM^-1under alkaline electrolyte. This work demonstrates the promise of single atoms for interfacial water environment adjustment and mass transfer process modulation, providing new insights into rational design of highly-effective SAC-based electrocatalysts.

Key words: Electric double layer, Hydrogen oxidation reaction, Interfacial water structure, Mass transfer process, Single atoms

靳一鸣, 成文静, 罗威. 单原子钌诱导界面水结构调控实现高效的碱性氢氧化反应[J]. 催化学报, 2025, 74: 240-249.

Yiming Jin, Wenjing Cheng, Wei Luo. Ru single atoms-induced interfacial water structure regulation for efficient alkaline hydrogen oxidation reaction[J]. Chinese Journal of Catalysis, 2025, 74: 240-249.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60283-4

https://www.cjcatal.com/CN/Y2025/V74/I7/240

图/表 5

Fig. 1. (a) XRD patterns of Ru1,n/NC, Ru/C and Ru1/NC. (b-d) TEM and HAADF-STEM images of Ru1,n/NC (Ru single atoms are highlighted by red circles). (e) EDS-elemental mappings of Ru1,n/NC.

Fig. 2. High-resolution XPS spectra of N 1s in Ru1,n/NC (a) and Ru 3p in Ru1,n/NC and Ru/C (b). Ru K-edge XANES (c), oxidation states analysis (d) and EXAFS spectra (e) of Ru foil, Ru1,n/NC and RuO2. (f) Ru K-edge EXAFS (point) and curvefit (line) shown in R-space of Ru1,n/NC. Wavelet transformation of Ru K-edge EXAFS data for Ru foil (g), Ru1,n/NC (h) and RuO2 (i).

Fig. 3. (a) HOR polarization curves in H2-saturated 0.1 mol L-1 KOH with a scan rate of 10 mV s-1 at a rotation rate of 1600 rpm. (b) Linear fitting curves in the micro-polarization region. (c) Tafel plots with the Butler-Volmer fitting lines. (d) Comparison of the mass-normalized kinetic current density (jk,m) and the ECSA-normalized exchange current density (j0,s). (e) Accelerated durability test for HOR of Ru1,n/NC in Ar-saturated 0.1 mol L-1 KOH solution. The inset histogram exhibits the j0 decline after 1000 cycle CVs test. (f) Comparison of jk,m with several previously reported noble metal-based electrocatalysts.

Fig. 4. (a,b) In situ SEIRAS spectra recorded at potentials from 0 to 0.2 VRHE for Ru1,n/NC, and Ru/C catalysts in H2-saturated 0.1 mol L-1 KOH solution. (c,d) Deconvolution of the OH stretching vibration peaks (around 3000 to 3600 cm-1) from 0 to 0.2 VRHE. (e) Changes in the proportion of strongly hydrogen-bonded water with applied potential (from 0 to 0.2 VRHE) for Ru1,n/NC and Ru/C. (f) Schematic illustration of interfacial water structures of Ru1,n/NC and the promoted OH- transfer assisted by strongly hydrogen-bonded water with O-down conformation.

Fig. 5. (a) Differential charge density of Ru1/NC, Ru1,n/NC and Ru/C (The yellow region represents for charge accumulation and the blue region for charge depletion). Free energy diagram of adsorbed hydrogen (b) and water binding energy (c) of Ru1/NC, Ru1,n/NC and Ru/C. (d) Local density of states of Ru d-orbitals in hydrogen adsorption sites for Ru1,n/NC and Ru/C. (e) COHP analysis of Ru ds-O 2p valence-electron-orbital interaction for Ru1,n/NC and Ru/C. (f) The adsorption energy of OH- with and without the assistance of adsorbed water of Ru1,n/NC (the left panel) and Ru/C (the right panel).

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