Bioinspired iron porphyrins with appended poly-pyridine/amine units for boosted electrocatalytic CO2 reduction reaction
Jinxiu Han,
Ni Wang,
Xialiang Li,
Haitao Lei,
Yabo Wang,
Hongbo Guo,
Xiaotong Jin,
Qingxin Zhang,
Xinyang Peng,
Xue-Peng Zhang,
Wei Zhang,
Ulf-Peter Apfel,
Rui Cao
Affiliations
Jinxiu Han
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, China
Ni Wang
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, China
Xialiang Li
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, China
Haitao Lei
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, China
Yabo Wang
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, China
Hongbo Guo
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, China
Xiaotong Jin
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, China
Qingxin Zhang
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, China
Xinyang Peng
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, China
Xue-Peng Zhang
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, China; Corresponding authors.
Wei Zhang
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, China
Ulf-Peter Apfel
Ruhr-Universität Bochum, Fakultät für Chemie und Biochemie, Anorganische Chemie I Universitätsstrasse 150, 44801, Bochum, Germany; Fraunhofer UMSICHT, Department for Electrosynthesis, 46047, Oberhausen, Germany
Rui Cao
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, China; Corresponding authors.
Developing highly efficient electrocatalysts for the CO2 reduction reaction (CO2RR) has attracted increasing interest in the past decade. Herein, we report on the design and synthesis of Fe porphyrin 1 with an appended N,N-di(2-picolyl)ethylenediamine (DPEN) unit that boosts electrocatalytic activity for CO2-to-CO conversion in acetonitrile with water as the proton source. By mimicking carbon monoxide dehydrogenase (CODH), 1 has poly-pyridine/amine units located at the active site to form hydrogen-bonded water-containing networks that enable fast proton transfer. The protonated and positively charged DPEN unit can also stabilize CO2 reduction intermediates through electrostatic and hydrogen-bonding interactions. These factors make 1 a highly active electrocatalyst for the CO2RR by achieving a TOFmax of 5.0 × 104 s−1 with water providing the protons. These critical roles of the DPEN unit in the CO2RR are further supported by theoretical studies. This work is significant to highlight the benefits of using molecular catalysts to elucidate structural effects.
