Song Qianqian, Li Junqi, Wang Shaolan, Liu Junli, Liu Xiaoxu, Pang Lingyan, Li Hu, Liu Hui
School of Materials Science and Engineering, Shaanxi Key Laboratory of Green Preparation and Functionalization for Inorganic Materials, Shaanxi University of Science and Technology, Xi'an, 710021, P. R. China.
Small. 2019 Oct;15(44):e1903395. doi: 10.1002/smll.201903395. Epub 2019 Sep 10.
Extending available body space loading active species and controllably tailoring the d-band center to Fermi level of catalysts are of paramount importance but extremely challenging for the enhancement of electrocatalytic performance. Herein, a melamine-bridged self-construction strategy is proposed to in situ embed Co-based bimetallic nanoparticles in the body of N-doped porous carbon spheres (CoM-e-PNC), and achieve the controllable tailoring of the d-band center position by alloying of Co and another transition metal M (M = Ni, Fe, Mn, and Cu). The enrichment and exposure of the active sites in the body interior of porous carbon spheres, and the best balance between the adsorption of OH species and the desorption of O induced by optimizing the d-band center position, collectively enhance the oxygen evolution reaction (OER) performance. Meanwhile, the relationship of d-band center position and OER activity is found to exhibit the volcano curve rule, where the CoNi-e-PNC catalyst shows optimal OER performance with an overpotential of 0.24 V at 10 mA cm in alkaline media, outperforming those of the ever-reported CoNi-based catalysts. Besides, CoNi-e-PNC catalyst also demonstrates high OER stability with slight current decrease after 100 h.
扩展可用的体相空间负载活性物种以及可控地调整催化剂的d带中心至费米能级对于提高电催化性能至关重要,但极具挑战性。在此,提出了一种三聚氰胺桥连的自构建策略,以原位将钴基金属双原子纳米颗粒嵌入氮掺杂多孔碳球(CoM-e-PNC)的体相中,并通过钴与另一种过渡金属M(M = Ni、Fe、Mn和Cu)合金化实现d带中心位置的可控调整。多孔碳球内部活性位点的富集和暴露,以及通过优化d带中心位置在OH物种吸附和O脱附之间实现的最佳平衡,共同提高了析氧反应(OER)性能。同时,发现d带中心位置与OER活性的关系呈现火山曲线规律,其中CoNi-e-PNC催化剂在碱性介质中10 mA cm时过电位为0.24 V,表现出最佳的OER性能,优于以往报道的钴镍基催化剂。此外,CoNi-e-PNC催化剂还表现出高OER稳定性,在100 h后电流略有下降。