Zhang Zhiqi, Chen Yugang, Zhou Liqi, Chen Chi, Han Zhen, Zhang Bingsen, Wu Qiang, Yang Lijun, Du Lingyu, Bu Yongfeng, Wang Peng, Wang Xizhang, Yang Hui, Hu Zheng
Key Laboratory of Mesoscopic Chemistry of MOE and Jiangsu Provincial Lab for Nanotechnology, School of Chemistry and Chemical Engineering, Nanjing University, 210023, Nanjing, China.
National Laboratory of Solid State Microstructures, College of Engineering and Applied Sciences, and Collaborative Innovation Center of Advanced Microstructures, Nanjing University, 210093, Nanjing, China.
Nat Commun. 2019 Apr 10;10(1):1657. doi: 10.1038/s41467-019-09596-x.
Single-site catalysts feature high catalytic activity but their facile construction and durable utilization are highly challenging. Herein, we report a simple impregnation-adsorption method to construct platinum single-site catalysts by synergic micropore trapping and nitrogen anchoring on hierarchical nitrogen-doped carbon nanocages. The optimal catalyst exhibits a record-high electrocatalytic hydrogen evolution performance with low overpotential, high mass activity and long stability, much superior to the platinum-based catalysts to date. Theoretical simulations and experiments reveal that the micropores with edge-nitrogen-dopants favor the formation of isolated platinum atoms by the micropore trapping and nitrogen anchoring of [PtCl], followed by the spontaneous dechlorination. The platinum-nitrogen bonds are more stable than the platinum-carbon ones in the presence of adsorbed hydrogen atoms, leading to the superior hydrogen evolution stability of platinum single-atoms on nitrogen-doped carbon. This method has been successfully applied to construct the single-site catalysts of other precious metals such as palladium, gold and iridium.
单原子位点催化剂具有高催化活性，但其简便构建和持久利用极具挑战性。在此，我们报道一种简单的浸渍吸附法，通过在分级氮掺杂碳纳米笼上协同微孔捕获和氮锚定来构建铂单原子位点催化剂。最优催化剂展现出创纪录的高电催化析氢性能，具有低过电位、高质量活性和长稳定性，远优于迄今的铂基催化剂。理论模拟和实验表明，带有边缘氮掺杂剂的微孔通过[PtCl]的微孔捕获和氮锚定有利于孤立铂原子的形成，随后自发脱氯。在存在吸附氢原子的情况下，铂 - 氮键比铂 - 碳键更稳定，导致铂单原子在氮掺杂碳上具有优异的析氢稳定性。该方法已成功应用于构建钯、金和铱等其他贵金属的单原子位点催化剂。
