Coordination environment tuning of nickel sites by oxyanions to optimize methanol electro-oxidation activity.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 35614111.
- Also identified by DOI 10.1038/s41467-022-30670-4 and PMC identifier 9133001.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
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<sub>x</sub>, NiS<sub>x</sub>, and NiSe<sub>x</sub>) to in-situ construct different oxyanion-coordinated amorphous nickel oxyhydroxides (NiOOH-TO<sub>x</sub>), among which NiOOH-PO<sub>x</sub> 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<sub>x</sub> possesses improved adsorption of OH* and methanol, and favors the formation of CH<sub>3</sub>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.