南京大学胡征团队报道了碳基纳米笼上单点铂的杂原子配位与析氢的关系。相关研究成果于2024年3月11日发表于国际一流学术期刊《德国应用化学》。

单中心催化剂的电催化性能与金属原子的电子结构密切相关。

该文中，研究人员在未掺杂和杂原子掺杂的多级碳纳米笼上构建了一系列Pt SSCs，其沿着S-、P-、C-和N-配位的Pt SSCs表现出增加的析氢反应（HER）活性。理论模拟表明，由于低配位，Pt-SCSs上存在多H原子吸附过程，并计算出一个新的描述符，即ΔGH（4）（第4H的吸附能）来评估HER活性。

相对于C配位的Pt，由于N到Pt的电子转移，N配位的Pt具有更高的反应性，这丰富了费米能级附近Pt 5d轨道的态密度，并促进了质子的捕获，这与P配位和S配位的情况正好相反。稳定的N配位Pt来源于整个多氢原子吸附过程的动力学稳定性。

该研究的实验进展和理论理解为深入了解杂原子配位与析氢的相关性提供了依据，这对碳基载体上先进Pt-SCSs的合理设计具有重要意义。

附：英文原文

Title: Correlation between Heteroatom Coordination and Hydrogen Evolution for Single-site Pt on Carbon-based Nanocages

Author: Xueyi Cheng, Chenghui Mao, Jingyi Tian, Minqi Xia, Lijun Yang, Xizhang Wang, Qiang Wu, Zheng Hu

Issue&Volume: 2024-03-11

Abstract: The electrocatalytic performance of single-site catalysts (SSCs) is closely correlated with the electronic structure of metal atoms. Herein we construct a series of Pt SSCs on undoped and heteroatom-doped hierarchical carbon nanocages, which exhibit increasing hydrogen evolution reaction (HER) activities along S-, P-, C- and N-coordinated Pt SSCs. Theoretical simulation indicates a multi-H-atom adsorption process on Pt SSCs due to the low coordination, and a new descriptor, i.e., ΔGH(4) (the adsorption energy of the 4th H), is figured out to evaluate the HER activities. Relative to C- coordinated Pt, N-coordinated Pt has higher reactivity due to the electron transfer of N-to-Pt, which enriches the density of states of Pt 5d orbital near the Fermi level and facilitates the capturing of protons, just the opposite to the situations for P- and S-coordinated ones. The stable N-coordinated Pt originates from the kinetic stability throughout the multi-H-atom adsorption process. The experimental progress and theoretical understanding in this study provides a deep insight into the correlation of heteroatom coordination and hydrogen evolution, which is significant for the rational design of advanced Pt SSCs on carbon-based supports.

DOI: 10.1002/anie.202401304

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202401304