Structure-activity relationship of small organic molecule functionalized Bi-based heterogeneous catalysts for electrocatalytic reduction of CO2 to formate

Kun Liu; Junping Niu; Yijia Bai; Jianlei Qi; Limin Han; Ning Zhu; Ligang Yan

doi:10.1016/j.jcis.2024.12.246

Structure-activity relationship of small organic molecule functionalized Bi-based heterogeneous catalysts for electrocatalytic reduction of CO₂ to formate

J Colloid Interface Sci. 2025 Jan 3;683(Pt 2):1030-1040. doi: 10.1016/j.jcis.2024.12.246. Online ahead of print.

Authors

Kun Liu¹, Junping Niu¹, Yijia Bai¹, Jianlei Qi¹, Limin Han², Ning Zhu³, Ligang Yan⁴

Affiliations

¹ Chemical Engineering College, Inner Mongolia University of Technology, Aimin street 49 Xincheng District, Hohhot 010051 PR China; Inner Mongolia Engineering Research Center for CO2 Capture and Utilization, Aimin street 49, Xincheng District, Hohhot 010051 PR China; Key Laboratory of CO2 Resource Utilization at Universities of Inner Mongolia Autonomous Region, Aimin street 49 Xincheng District, Hohhot 010051 PR China.
² Chemical Engineering College, Inner Mongolia University of Technology, Aimin street 49 Xincheng District, Hohhot 010051 PR China; Inner Mongolia Engineering Research Center for CO2 Capture and Utilization, Aimin street 49, Xincheng District, Hohhot 010051 PR China; Key Laboratory of CO2 Resource Utilization at Universities of Inner Mongolia Autonomous Region, Aimin street 49 Xincheng District, Hohhot 010051 PR China; Inner Mongolia Vocational College of Chemical Engineering, Vocational Park, Saihan District, Hohhot 010051 PR China.
³ Chemical Engineering College, Inner Mongolia University of Technology, Aimin street 49 Xincheng District, Hohhot 010051 PR China; Inner Mongolia Engineering Research Center for CO2 Capture and Utilization, Aimin street 49, Xincheng District, Hohhot 010051 PR China; Key Laboratory of CO2 Resource Utilization at Universities of Inner Mongolia Autonomous Region, Aimin street 49 Xincheng District, Hohhot 010051 PR China. Electronic address: [email protected].
⁴ Chemical Engineering College, Inner Mongolia University of Technology, Aimin street 49 Xincheng District, Hohhot 010051 PR China; Inner Mongolia Engineering Research Center for CO2 Capture and Utilization, Aimin street 49, Xincheng District, Hohhot 010051 PR China; Key Laboratory of CO2 Resource Utilization at Universities of Inner Mongolia Autonomous Region, Aimin street 49 Xincheng District, Hohhot 010051 PR China. Electronic address: [email protected].

PMID: 39764986
DOI: 10.1016/j.jcis.2024.12.246

Abstract

Ligand engineering has proven to be an effective strategy for tuning and controlling the microenvironment of coordinated metal centers, highlighting the critical bridge between the activity and structural features of catalysts during electrocatalytic CO₂ reduction reactions (eCO₂RR). However, the limited availability of diverse organic ligands has hindered the development of novel high-performing electrocatalysts. In contrast, small organic molecules have been widely used in the fabrication of metal complexes due to their well-defined functionalities, low cost, and easy accessibility. Herein, functionalized small organic molecules were employed to prepare a new type of Bi-based heterogeneous molecular catalyst. These molecular catalysts enhance both electrical conductivity and catalytic activity for converting CO₂ to formate in the eCO₂RR. The relationship between the structure and electrochemical performance of organic-functionalized Bi-based heterogeneous catalysts was thoroughly investigated. Comprehensive characterization and kinetic studies demonstrated that the functional groups of the organic molecules construct bond pathways for electron transfer and promote the transformation of the active phase from Bi to Bi₂O₂CO₃. In-situ Raman spectroscopy reveal that the organic molecules remain intact during the structural reorganization, which is beneficial for the sustained generation of Bi₂O₂CO₃ active site during the eCO₂RR process. Consequently, the organic functionalized Bi-based catalysts achieved a high formate Faradaic efficiency (FE_HCOO^-) of 89.8 % and a high current density (j_HCOO^-) of 40.0 mA cm^-2 at a potential of -0.95 V vs. RHE in an H-type cell. This work establishes a novel strategy for creating active heterogeneous catalysts using small organic molecules, opening new avenues for the development of efficient electrocatalysts for CO₂ reduction.

Keywords: Bond pathways of electron transfer; Organo-functionalized; Structural reorganization; Structure-activity relationship.