Accelerated water activation and stabilized metal-organic framework via constructing triangular active-regions for ampere-level current density hydrogen production

Fanpeng Cheng; Xianyun Peng; Lingzi Hu; Bin Yang; Zhongjian Li; Chung-Li Dong; Jeng-Lung Chen; Liang-Ching Hsu; Lecheng Lei; Qiang Zheng; Ming Qiu; Liming Dai; Yang Hou

doi:10.1038/s41467-022-34278-6

Accelerated water activation and stabilized metal-organic framework via constructing triangular active-regions for ampere-level current density hydrogen production

Nat Commun. 2022 Oct 30;13(1):6486. doi: 10.1038/s41467-022-34278-6.

Authors

Fanpeng Cheng¹, Xianyun Peng², Lingzi Hu³, Bin Yang^{1

2}, Zhongjian Li^{1

2}, Chung-Li Dong⁴, Jeng-Lung Chen⁵, Liang-Ching Hsu⁵, Lecheng Lei^{1

2}, Qiang Zheng⁶, Ming Qiu⁷, Liming Dai⁸, Yang Hou^{9

10

11

12}

Affiliations

¹ Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, 310027, China.
² Institute of Zhejiang University - Quzhou, Quzhou, 324000, China.
³ Institute of Nanoscience and Nanotechnology, College of Physical Science and Technology, Central China Normal University, Wuhan, 430079, China.
⁴ Department of Physics, Tamkang University, Tamsui, 25137, Taiwan.
⁵ National Synchrotron Radiation Research Center, Hsinchu, 30076, Taiwan.
⁶ CAS Key Laboratory of Standardization and Measurement for Nanotechnology, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing, 100190, China.
⁷ Institute of Nanoscience and Nanotechnology, College of Physical Science and Technology, Central China Normal University, Wuhan, 430079, China. qium@mail.ccnu.edu.cn.
⁸ Australian Carbon Materials Centre (A-CMC), School of Chemical Engineering, University of New South Wales, Sydney, NSW, 2052, Australia. l.dai@unsw.edu.au.
⁹ Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, 310027, China. yhou@zju.edu.cn.
¹⁰ Institute of Zhejiang University - Quzhou, Quzhou, 324000, China. yhou@zju.edu.cn.
¹¹ School of Biological and Chemical Engineering, NingboTech University, Ningbo, 315100, China. yhou@zju.edu.cn.
¹² Donghai Laboratory, Zhoushan, China. yhou@zju.edu.cn.

Abstract

Two-dimensional metal-organic frameworks (MOFs) have been explored as effective electrocatalysts for hydrogen evolution reaction (HER). However, the sluggish water activation kinetics and structural instability under ultrahigh-current density hinder their large-scale industrial applications. Herein, we develop a universal ligand regulation strategy to build well-aligned Ni-benzenedicarboxylic acid (BDC)-based MOF nanosheet arrays with S introducing (S-NiBDC). Benefiting from the closer p-band center to the Fermi level with strong electron transferability, S-NiBDC array exhibits a low overpotential of 310 mV to attain 1.0 A cm^-2 with high stability in alkaline electrolyte. We speculate the newly-constructed triangular "Ni₂-S₁" motif as the improved HER active region based on detailed mechanism analysis and structural characterization, and the enhanced covalency of Ni-O bonds by S introducing stabilizes S-NiBDC structure. Experimental observations and theoretical calculations elucidate that such Ni sites in "Ni₂-S₁" center distinctly accelerate the water activation kinetics, while the S site readily captures the H atom as the optimal HER active site, boosting the whole HER activity.

Abstract

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