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

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

doi:10.1038/s41467-022-30670-4

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

Nat Commun. 2022 May 25;13(1):2916. doi: 10.1038/s41467-022-30670-4.

Authors

Shanlin Li^#^{1

2

3}, Ruguang Ma^#^{1

4}, Jingcong Hu³, Zichuang Li^{1

2}, Lijia Liu⁵, Xunlu Wang^{1

2}, Yue Lu³, George E Sterbinsky⁶, Shuhu Liu⁷, Lei Zheng⁷, Jie Liu¹, Danmin Liu³, Jiacheng Wang^{8

9

10}

Affiliations

¹ The State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, 200050, China.
² Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049, China.
³ Beijing Key Laboratory of Microstructure and Properties of Solids, Faculty of Materials and Manufacturing, Beijing University of Technology, Beijing, 100124, China.
⁴ School of Materials Science and Engineering, Suzhou University of Science and Technology, 99 Xuefu Road, Suzhou, 215011, China.
⁵ Department of Chemistry, Western University, 1151 Richmond Street, London, ON, N6A5B7, Canada.
⁶ Advanced Photon Source, Argonne National Laboratory, Argonne, IL, 60439, USA.
⁷ Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, 100049, China.
⁸ The State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, 200050, China. [email protected].
⁹ Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049, China. [email protected].
¹⁰ Hebei Provincial Key Laboratory Nonmetallic Materials, College of Materials Science and Engineering, North China University of Science and Technology, Tangshan, 063210, China. [email protected].

^# Contributed equally.

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 CH₃O* 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.

Grants and funding

52172058/National Natural Science Foundation of China (National Science Foundation of China)