Tailoring Coordination Microenvironment of Cu(I) in Metal–Organic Frameworks for Enhancing Electroreduction of CO2to CH4

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Abstract
The coordination microenvironment of metal active sites in metal–organic frameworks (MOFs) plays a crucial role in its performance for electrochemical CO2reduction reaction (CO2RR). However, it remains a challenge to clarify the structure–performance relationship for CO2RR catalyzed by MOFs. Herein, a series of MOFs with different coordination microenvironments of Cu(I) sites (CuCl, CuBr, and CuI) to evaluate their performances for CO2RR is synthesized. With the increasing radius of halogen atom, the CO2adsorption capacity increases and d‐band center of Cu positively shifts to the Fermi level, leading to enhance the selectivity of CO2to CH4conversion. CuI gives the highest total Faradaic efficiency (FE) of 83.2%, with a FE of CH4up to 57.2% and CH4partial current density of 60.7 mA cm−2at −1.08 V versus reversible hydrogen electrode. Theoretical calculations reveal that the shifted d‐band center of Cu site contributes to reduced formation energies of *CH2O and *CH3O intermediates, which is the potential‐determining step of CO2RR and thus facilitates the electrocatalytic CO2reduction to CH4. This study opens a new avenue for studying the relationship between the coordination microenvironment of active site and electroreduction reaction performance of MOFs.
Funding Information
  • National Natural Science Foundation of China (22171131, 52076045)
  • National Basic Research Program of China (2017YFA0303504, 2019YFC1906700)

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