Journal Article

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

Hu, Jingcong, Li, Zichuang, Li, Shanlin, Wang, Xunlu, Zheng, Lei, Ma, Ruguang, Liu, Lijia, Lu, Yue, Liu, Jie, Sterbinsky, George E., Wang, Jiacheng, Liu, Danmin, Liu, Shuhu

2022

Overview

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. Coordination environments around metal sites are important in electrocatalysis. Here, Ni metalloid oxidation produces oxyanion doped amorphous Ni-oxyhydroxides where substitution with phosphorus is found to boost methanol electrooxidation activity.

• Publisher: Nature Publishing Group UK,Nature Publishing Group,Nature Portfolio
• Subject: 140/133 / 140/146 / 147/135 / 147/143 / 639/301/299/886 / 639/638/161/886 / 639/638/224 / 639/638/911 / Anodizing / Catalysts / Catalytic activity / Coordination / Electrocatalysts / Electrochemical oxidation / Electrochemistry / Humanities and Social Sciences / Hydrogen production / INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY / Intermediates / Metalloids / Methanol / multidisciplinary / Nickel / Optimization / Organic chemistry / Oxidation / Phosphorus / Renewable energy / Science / Science (multidisciplinary)