Issue 21, 2021

Rational incorporation of defects within metal–organic frameworks generates highly active electrocatalytic sites

Abstract

The allure of metal–organic frameworks (MOFs) in heterogeneous electrocatalysis is that catalytically active sites may be designed a priori with an unparalleled degree of control. An emerging strategy to generate coordinatively-unsaturated active sites is through the use of organic linkers that lack a functional group that would usually bind with the metal nodes. To execute this strategy, we synthesize a model MOF, Ni-MOF-74 and incorporate a fraction of 2-hydroxyterephthalic acid in place of 2,5-dihydroxyterephthalic acid. The defective MOF, Ni-MOF-74D, is evaluated vs. the nominally defect-free Ni-MOF-74 with a host of ex situ and in situ spectroscopic and electroanalytical techniques, using the oxidation of hydroxymethylfurtural (HMF) as a model reaction. The data indicates that Ni-MOF-74D features a set of 4-coordinate Ni–O4 sites that exhibit unique vibrational signatures, redox potentials, binding motifs to HMF, and consequently superior electrocatalytic activity relative to the original Ni-MOF-74 MOF, being able to convert HMF to the desired 2,5-furandicarboxylic acid at 95% yield and 80% faradaic efficiency. Furthermore, having such rationally well-defined catalytic sites coupled with in situ Raman and infrared spectroelectrochemical measurements enabled the deduction of the reaction mechanism in which co-adsorbed *OH functions as a proton acceptor in the alcohol oxidation step and carries implications for catalyst design for heterogeneous electrosynthetic reactions en route to the electrification of the chemical industry.

Graphical abstract: Rational incorporation of defects within metal–organic frameworks generates highly active electrocatalytic sites

Supplementary files

Article information

Article type
Edge Article
Submitted
29 jan 2021
Accepted
23 apr 2021
First published
29 apr 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2021,12, 7324-7333

Rational incorporation of defects within metal–organic frameworks generates highly active electrocatalytic sites

N. Heidary, D. Chartrand, A. Guiet and N. Kornienko, Chem. Sci., 2021, 12, 7324 DOI: 10.1039/D1SC00573A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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