Tunable metal hydroxide-organic frameworks for catalysing oxygen evolution

Shuai Yuan; Jiayu Peng; Bin Cai; Zhehao Huang; Angel T Garcia-Esparza; Dimosthenis Sokaras; Yirui Zhang; Livia Giordano; Karthik Akkiraju; Yun Guang Zhu; René Hübner; Xiaodong Zou; Yuriy Román-Leshkov; Yang Shao-Horn

doi:10.1038/s41563-022-01199-0

Tunable metal hydroxide-organic frameworks for catalysing oxygen evolution

Nat Mater. 2022 Jun;21(6):673-680. doi: 10.1038/s41563-022-01199-0. Epub 2022 Feb 24.

Authors

Shuai Yuan^#^{1

2

3}, Jiayu Peng^#⁴, Bin Cai^#^{1

2

5}, Zhehao Huang⁶, Angel T Garcia-Esparza⁷, Dimosthenis Sokaras⁷, Yirui Zhang⁸, Livia Giordano¹, Karthik Akkiraju⁴, Yun Guang Zhu^{1

8}, René Hübner⁹, Xiaodong Zou⁶, Yuriy Román-Leshkov¹⁰, Yang Shao-Horn^{11

12

13}

Affiliations

¹ Research Laboratory of Electronics, Massachusetts Institute of Technology, Cambridge, MA, USA.
² Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA.
³ State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China.
⁴ Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA.
⁵ School of Chemistry and Chemical Engineering, Shandong University, Jinan, China.
⁶ Department of Materials and Environmental Chemistry, Stockholm University, Stockholm, Sweden.
⁷ Stanford Synchrotron Radiation Light Source, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
⁸ Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA.
⁹ Institute of Ion Beam Physics and Materials Research, Helmholtz-Zentrum Dresden-Rossendorf, Dresden, Germany.
¹⁰ Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA. yroman@mit.edu.
¹¹ Research Laboratory of Electronics, Massachusetts Institute of Technology, Cambridge, MA, USA. shaohorn@mit.edu.
¹² Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA. shaohorn@mit.edu.
¹³ Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA. shaohorn@mit.edu.

^# Contributed equally.

PMID: 35210585
DOI: 10.1038/s41563-022-01199-0

Abstract

The oxygen evolution reaction is central to making chemicals and energy carriers using electrons. Combining the great tunability of enzymatic systems with known oxide-based catalysts can create breakthrough opportunities to achieve both high activity and stability. Here we report a series of metal hydroxide-organic frameworks (MHOFs) synthesized by transforming layered hydroxides into two-dimensional sheets crosslinked using aromatic carboxylate linkers. MHOFs act as a tunable catalytic platform for the oxygen evolution reaction, where the π-π interactions between adjacent stacked linkers dictate stability, while the nature of transition metals in the hydroxides modulates catalytic activity. Substituting Ni-based MHOFs with acidic cations or electron-withdrawing linkers enhances oxygen evolution reaction activity by over three orders of magnitude per metal site, with Fe substitution achieving a mass activity of 80 A [Formula: see text] at 0.3 V overpotential for 20 h. Density functional theory calculations correlate the enhanced oxygen evolution reaction activity with the MHOF-based modulation of Ni redox and the optimized binding of oxygenated intermediates.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

Catalysis
Hydroxides
Metal-Organic Frameworks*
Oxygen*

Substances

Hydroxides
Metal-Organic Frameworks
hydroxide ion
Oxygen