Uncoordinated amino groups of MIL-101 anchoring cobalt porphyrins for highly selective CO2 electroreduction

A Bohan; Xixiong Jin; Min Wang; Xia Ma; Yang Wang; Lingxia Zhang

doi:10.1016/j.jcis.2023.10.089

Uncoordinated amino groups of MIL-101 anchoring cobalt porphyrins for highly selective CO₂ electroreduction

J Colloid Interface Sci. 2024 Jan 15;654(Pt B):830-839. doi: 10.1016/j.jcis.2023.10.089. Epub 2023 Oct 21.

Authors

A Bohan¹, Xixiong Jin¹, Min Wang¹, Xia Ma¹, Yang Wang¹, Lingxia Zhang²

Affiliations

¹ Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding-xi Road, Shanghai 200050, PR China; Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, No. 19A Yuquan Road, Beijing 100049, PR China.
² Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding-xi Road, Shanghai 200050, PR China; Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, No. 19A Yuquan Road, Beijing 100049, PR China; School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, 1 Sub-lane Xiangshan, Hangzhou 310024, PR China. Electronic address: zhlingxia@mail.sic.ac.cn.

PMID: 37898067
DOI: 10.1016/j.jcis.2023.10.089

Abstract

Electrocatalytic carbon dioxide reduction reaction (CO₂RR) presents a sustainable route to address energy crisis and environmental issues, where the rational design of catalysts remains crucial. Metal-organic frameworks (MOFs) with high CO₂ capture capacities have immense potential as CO₂RR electrocatalysts but suffer from poor activity. Herein we report a redox-active cobalt protoporphyrin grafted MIL-101(Cr)-NH₂ for CO₂ electroreduction. Material characterizations reveal that porphyrin molecules are covalently attached to uncoordinated amino groups of the parent MOF without compromising its well-defined porous structure. Furthermore, in situ spectroscopic techniques suggest inherited CO₂ concentrate ability and more abundant adsorbed carbonate species on the modified MOF. As a result, a maximum CO Faradaic efficiency (FE_CO) up to 97.1% and a turnover frequency of 0.63 s^-1 are achieved, together with FE_CO above 90% within a wide potential window of 300 mV. This work sheds new light on the coupling of MOFs with molecular catalysts to enhance catalytic performances.

Keywords: CO(2) reduction; Covalent grafting; Electrocatalysis; Metal–organic frameworks; Porphyrin.