Coordination environment tuning of nickel sites by oxyanions to optimize methanol electro-oxidation activity

作者：Shanlin Li, Ruguang Ma, Jingcong Hu, Zichuang Li, Lijia Liu, Xunlu Wang, Yue Lu, George E. Sterbinsky, Shuhu Liu, Lei Zheng, Jie Liu, Danmin Liu, Jiacheng Wang · 发表于：Nature Communications · 年份：2022 · DOI：10.1038/s41467-022-30670-4 · 被引用次数：333 · 研究领域：Electrocatalysts for Energy Conversion、Advanced battery technologies research、Supercapacitor Materials and Fabrication

Abstract To achieve zero-carbon economy, advanced anode catalysts are desirable for hydrogen production and biomass upgrading powered by renewable energy. Ni-based non-precious electrocatalysts are considered as potential candidates because of intrinsic redox attributes, but in-depth understanding and rational design of Ni site coordination still remain challenging. Here, we perform anodic electrochemical oxidation of Ni-metalloids (NiP x , NiS x , and NiSe x ) to in-situ construct different oxyanion-coordinated amorphous nickel oxyhydroxides (NiOOH-TO x ), among which NiOOH-PO x shows optimal local coordination environment and boosts electrocatalytic activity of Ni sites towards selective oxidation of methanol to formate. Experiments and theoretical results demonstrate that NiOOH-PO x possesses improved adsorption of OH* and methanol, and favors the formation of CH 3 O* intermediates. The coordinated phosphate oxyanions effectively tailor the d band center of Ni sites and increases Ni-O covalency, promoting the catalytic activity. This study provides additional insights into modulation of active-center coordination environment via oxyanions for organic molecules transformation.