Cu2+-based materials are a promising class of catalysts for the production of high value-added chemicals in electrocatalytic carbon dioxide reduction (CO2RR), but the inevitable and uncontrollable recombination process often occurs during the reaction, resulting in the inactivation of the catalyst or the formation of new active sites, which brings great challenges to the exploration of its structure-property relationship. Based on this,Academician Han Buxing of the Institute of Chemistry of the Chinese Academy of Sciences and Professor Wu Haihong of East China Normal UniversityA simple strategy for constructing the coordination of Cu2+ and 3, 4-ethylenedioxythiophene (EDOT) to stabilize Cu2+ ions and prepare a novel layered coordination polymer (Cupedot) was reported. The cupedot can be used in a flow cell with a current density of 354 mA cm2 at 62A Faraday efficiency (Fe) of 7% selectively reduced CO2 to CH4 with a catalyst stability of at least 15 h.
VASP Interpretation
Density functional theory (DFT) calculations show that the enhancement of CH4 product activity on the Cupedot electrocatalyst may be attributed to *CO2 to *COoh(-1.).04 ev) and *co to *cho (-0..)51 ev). The calculated value of the free energy of *co to produce co(g) is 077 EV, indicating that there is a thermodynamic difficulty in CO desorption, which inhibits CO formation. At the same time, the δG value of *cho was more negative than that of *co-cho, indicating that the protonation of *CO on the cupedot was more energetically favorable, thus promoting the generation of CH4.
In addition, the authors calculated the ED energy level of Cupedot to -249 EV, which is higher than Cu, Cuo and CuS, indicating that the Ed energy level of Cu2+ is closer to the Fermi level after coordination with EDOT. The results showed that the electronic interaction between CupEDOT and CO2 was stronger, and it was easier to form deep reduction products (CH4). The fourth-harmonic components of FTACV were obtained on the Cupedot, Cuo, Cus, and Cu electrodes in the flow cell, and the CUPEDOT showed narrower and stronger peaks at the corrected potential, indicating that the kinetics of the protonation process were enhanced.
highly stable layered coordination polymer electrocatalyst towards efficient co2-to-ch4 conversion. adv. mater.,, doi: ht-tps: