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Tuning d-Band Structure of CuII in Coordinated Polymer via d-π Conjugation for Improving CO2 Electroreduction
Fengtao Zhang1,2, Peng Wang3, Runyao Zhao1,2
1Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, No.2 north 1st street, 100190, Beijing, P. R. China.
Abstract:
Copper-coordinated catalysts are reported to be effective for electrocatalytic CO2 reduction reaction (CO2 RR) to C2 products but suffer from low selectivity. Herein a strategy was developed to tune the d-band structure of CuII via coordinating with aromatic ligands to form Cu-based conjugated polymers for CO2 RR to C2 chemicals. The catalysts derived from copper chloride coordinating with tetraminobenzoquinone (TABQ) and with 1,2,4,5-benzenetetramine possessed high-density and compact Cu single-atom sites and displayed high activity for CO2 RR to C2 products. Especially, Cu-TABQ exhibited a maximum C2 faradaic efficiency of 63.2 % with a current density of 423 mA cm-2 at -1.17 V (vs. reversible hydrogen electrode). Density functional theory calculations indicated that the TABQ linker possessing C=O groups significantly widened the d-band of coordinated CuII , which facilitated binding of *CO intermediate on the catalyst and thus enhanced C-C coupling. This work provides mechanistic insight into the CuII -coordinated polymers for CO2 RR with high selectivity toward C2 products.
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