Fu Hui, Zhang Nan, Lai Feili, Zhang Longsheng, Wu Zhenzhong, Li Hanjun, Zhu Haiyan, Liu Tianxi
The Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, International Joint Research Laboratory for Nano Energy Composites, Jiangnan University, Wuxi, 214122, China.
Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Leuven, 3001, Belgium.
Small. 2022 Sep;18(38):e2203510. doi: 10.1002/smll.202203510. Epub 2022 Aug 19.
Surface strains are necessary to optimize the oxygen adsorption energy during the oxygen reduction reaction (ORR) in the four-electron process, but the surface strains regulation for ORR in the two-electron process to produce hydrogen peroxide (H O ) is rarely studied. Herein, it is reported that the tensile strained B-doped Ni nanoparticles on carbon support (Ni-B@BNC) could enhance the adsorption of O , stabilize OO bond, and boost the electrocatalytic ORR to H O . Moreover, the Ni-B@BNC catalysts exhibit volcano-type activity for electrocatalytic ORR to H O as a function of the strain intensity, which is controlled by B content. Among them, Ni -B @BNC exhibits the highest H O selectivity of over 86%, H O yield of 128.5 mmol h g , and Faraday efficiency of 94.9% at 0.6 V vs reversible hydrogen electrode as well as durable stability after successive cycling, being one of the state-of-the-art electrocatalysts for two-electron ORR. The density functional theory calculations reveal that tensile strain introduced by doping B into Ni nanoparticles could decrease the state density of Ni-3d orbital and optimize the binding energy of OOH* during ORR. A new direction is provided here for the design of highly active and stable catalysts for potential H O production and beyond.
表面应变对于在四电子过程的氧还原反应（ORR）中优化氧吸附能是必要的，但对于两电子过程中ORR生成过氧化氢（H₂O₂）的表面应变调控研究较少。在此，据报道，碳载体上的拉伸应变B掺杂Ni纳米颗粒（Ni-B@BNC）可增强O₂的吸附，稳定OO键，并促进电催化ORR生成H₂O₂。此外，Ni-B@BNC催化剂对电催化ORR生成H₂O₂表现出火山型活性，其作为应变强度的函数，由B含量控制。其中，Ni₀.₉₅B₀.₀₅@BNC在相对于可逆氢电极0.6 V时表现出超过86%的最高H₂O₂选择性、128.5 mmol h⁻¹ g⁻¹的H₂O₂产率和94.9%的法拉第效率，以及连续循环后的持久稳定性，是两电子ORR的最先进电催化剂之一。密度泛函理论计算表明，通过向Ni纳米颗粒中掺杂B引入的拉伸应变可降低Ni-3d轨道的态密度，并优化ORR过程中OOH*的结合能。本文为设计用于潜在H₂O₂生产及其他方面的高活性和稳定催化剂提供了一个新方向。
