Liu Zonglin, Li Baoqiang, Feng Yujie, Jia Dechang, Li Caicai, Zhou Yu
Institute for Advanced Ceramics, State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin, 150001, China.
MIIT Key Laboratory of Advanced Structural-Functional Integration Materials & Green Manufacturing Technology, Harbin Institute of Technology, Harbin, 150001, China.
Small Methods. 2022 Oct;6(10):e2200637. doi: 10.1002/smtd.202200637. Epub 2022 Jul 27.
The structure and properties of the carrier significantly affect the catalytic activity of the active centers for supported electrocatalysts. Therefore, elaborate design and regulation of the physicochemical properties of carbon carriers are essential to improve the activity and stability of the carbon-supported ruthenium-based catalysts. Herein, enlightened by the unique characteristics of coexisting sp and sp carbon nuclei in N-doped carbon dots (NCDs), a hybrid structure of N-doped carbon substrates featuring N-doped sp /sp carbon interfaces loaded with Ru nanoparticles (Ru/NCDs) is obtained. Spectroscopic analysis and density functional theory calculations illustrate that the interaction between Ru and NCDs effectively modulates the electronic structure of the active center Ru, and the formed N-doped sp /sp carbon interface lowers the energy barrier of the intermediates in hydrogen evolution reaction (HER) and balances the hydrogen adsorption and desorption and, thereby, greatly improves the activity of Ru/NCDs. Remarkably, Ru/NCDs exhibit excellent HER activity and stability in comparison to Pt/C, which merely requires overpotentials as low as 37 and 14 mV at 10 mA cm in alkaline and acidic electrolytes, respectively. This finding will provide more thoughts about the influence of substrate properties on the catalytic activity and rational design of carbon-loaded electrocatalysts.
载体的结构和性质对负载型电催化剂活性中心的催化活性有显著影响。因此，精心设计和调控碳载体的物理化学性质对于提高碳负载钌基催化剂的活性和稳定性至关重要。在此，受氮掺杂碳点（NCDs）中同时存在的sp和sp碳核独特特性的启发，获得了一种具有负载钌纳米颗粒（Ru/NCDs）的氮掺杂sp/sp碳界面的氮掺杂碳基底杂化结构。光谱分析和密度泛函理论计算表明，Ru与NCDs之间的相互作用有效地调节了活性中心Ru的电子结构，并且形成的氮掺杂sp/sp碳界面降低了析氢反应（HER）中中间体的能垒，平衡了氢吸附和解吸，从而极大地提高了Ru/NCDs的活性。值得注意的是，与Pt/C相比，Ru/NCDs在碱性和酸性电解质中分别在10 mA cm下仅需要低至37和14 mV的过电位，就表现出优异的HER活性和稳定性。这一发现将为底物性质对催化活性的影响以及碳负载电催化剂的合理设计提供更多思路。
