Issue 5, 2022

Host–guest molecular interaction promoted urea electrosynthesis over a precisely designed conductive metal–organic framework

Abstract

The highly selective electrocatalytic activation of N2 and CO2 to synthesize value-added urea via a C–N coupling reaction is an extremely challenging reaction that is largely inhibited by the poor chemisorption and coupling abilities of the reactant molecules. Herein, the novel conductive MOF Co–PMDA–2-mbIM (PMDA = pyromellitic dianhydride; 2-mbIM = 2-methyl benzimidazole) is designed, attaining a record-high urea yield rate of 14.47 mmol h−1 g−1 with a FE of 48.97% at −0.5 V vs. RHE. The host–guest interactions involved not only generate desirable local electrophilic and nucleophilic regions but they also allow evolution from high-spin state Co3+ (HS: t42ge2g) to intermediate-spin state Co4+ (IS: t42ge1g) in CoO6 octahedrons. Thus, N2 and CO2 can be adsorbed in a targeted fashion and activated to produce the desired *N[double bond, length as m-dash]N* and *CO intermediates. Subsequently, the low eg orbital occupied Co4+ (t42ge1g) easily accepts electrons from σ orbital of *N[double bond, length as m-dash]N* and effectively triggers the C–N coupling reaction to emerge *NCON* urea precursor.

Graphical abstract: Host–guest molecular interaction promoted urea electrosynthesis over a precisely designed conductive metal–organic framework

Supplementary files

Article information

Article type
Paper
Submitted
18 Dec 2021
Accepted
29 Mar 2022
First published
30 Mar 2022

Energy Environ. Sci., 2022,15, 2084-2095

Host–guest molecular interaction promoted urea electrosynthesis over a precisely designed conductive metal–organic framework

M. Yuan, J. Chen, H. Zhang, Q. Li, L. Zhou, C. Yang, R. Liu, Z. Liu, S. Zhang and G. Zhang, Energy Environ. Sci., 2022, 15, 2084 DOI: 10.1039/D1EE03918K

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