Molecular Engineering of Metal-Organic Frameworks as Efficient Electrochemical Catalysts for Water Oxidation

Yizhe Liu; Xintong Li; Shoufeng Zhang; Zilong Wang; Qi Wang; Yonghe He; Wei-Hsiang Huang; Qidi Sun; Xiaoyan Zhong; Jue Hu; Xuyun Guo; Qing Lin; Zhuo Li; Ye Zhu; Chu-Chen Chueh; Chi-Liang Chen; Zhengtao Xu; Zonglong Zhu

doi:10.1002/adma.202300945

Molecular Engineering of Metal-Organic Frameworks as Efficient Electrochemical Catalysts for Water Oxidation

Adv Mater. 2023 Jun;35(22):e2300945. doi: 10.1002/adma.202300945. Epub 2023 Apr 14.

Authors

Yizhe Liu¹, Xintong Li¹, Shoufeng Zhang¹, Zilong Wang², Qi Wang³, Yonghe He¹, Wei-Hsiang Huang^{4

5}, Qidi Sun¹, Xiaoyan Zhong³, Jue Hu⁶, Xuyun Guo⁷, Qing Lin⁸, Zhuo Li³, Ye Zhu⁷, Chu-Chen Chueh⁹, Chi-Liang Chen⁵, Zhengtao Xu¹⁰, Zonglong Zhu¹

Affiliations

¹ Department of Chemistry, City University of Hong Kong, Kowloon, 999077, Hong Kong.
² Siyuan Laboratory, Guangdong Provincial Engineering Technology Research Center of Vacuum Coating Technologies and New Energy Materials, Department of Physics, Jinan University, Guangzhou, Guangdong, 510632, P. R. China.
³ Department of Materials Science and Engineering, City University of Hong Kong, Kowloon, 999077, Hong Kong.
⁴ Graduate Institute of Applied Science and Technology, National Taiwan University of Science and Technology (NTUST), Taipei, 10607, Taiwan.
⁵ National Synchrotron Radiation Research Center, Hsinchu, 30076, Taiwan.
⁶ Faculty of Science, Kunming University of Science and Technology, Kunming, 650093, China.
⁷ Department of Applied Physics, The Hong Kong Polytechnic University, Hung Hom, 999077, Hong Kong.
⁸ ReadCrystal Biotech Co., Ltd., Suzhou, Jiangsu Province, 215505, P. R. China.
⁹ Department of Chemical Engineering, National Taiwan University, Taipei, 10617, Taiwan.
¹⁰ Institute of Materials Research and Engineering (IMRE), Agency of Science, Technology and Research (A*STAR), 2 Fusionopolis Way, Singapore, 138634, Singapore.

PMID: 36912205
DOI: 10.1002/adma.202300945

Abstract

Metal-organic framework (MOF) solids with their variable functionalities are relevant for energy conversion technologies. However, the development of electroactive and stable MOFs for electrocatalysis still faces challenges. Here, a molecularly engineered MOF system featuring a 2D coordination network based on mercaptan-metal links (e.g., nickel, as for Ni(DMBD)-MOF) is designed. The crystal structure is solved from microcrystals by a continuous-rotation electron diffraction (cRED) technique. Computational results indicate a metallic electronic structure of Ni(DMBD)-MOF due to the Ni-S coordination, highlighting the effective design of the thiol ligand for enhancing electroconductivity. Additionally, both experimental and theoretical studies indicate that (DMBD)-MOF offers advantages in the electrocatalytic oxygen evolution reaction (OER) over non-thiol (e.g., 1,4-benzene dicarboxylic acid) analog (BDC)-MOF, because it poses fewer energy barriers during the rate-limiting *O intermediate formation step. Iron-substituted NiFe(DMBD)-MOF achieves a current density of 100 mA cm^-2 at a small overpotential of 280 mV, indicating a new MOF platform for efficient OER catalysis.

Keywords: metal-organic frameworks; nickel-mercaptan links; oxygen evolution; thiol functionalization.

Abstract

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