Details

Autor(en) / Beteiligte

• Peng, Xinyang
• Zhang, Mengchun
• Qin, Haonan
• Han, Jinxiu
• Xu, Yuhan
• Li, Wenzi
• Zhang, Xue‐Peng
• Zhang, Wei
• Apfel, Ulf‐Peter
• Cao, Rui

Titel

Switching Electrocatalytic Hydrogen Evolution Pathways through Electronic Tuning of Copper Porphyrins

Ist Teil von

• Angewandte Chemie International Edition, 2024-03, Vol.63 (13), p.e202401074-n/a

Auflage

International ed. in English

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2024

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• The electronic structure of metal complexes plays key roles in determining their catalytic features. However, controlling electronic structures to regulate reaction mechanisms is of fundamental interest but has been rarely presented. Herein, we report electronic tuning of Cu porphyrins to switch pathways of the hydrogen evolution reaction (HER). Through controllable and regioselective β‐oxidation of Cu porphyrin 1, we synthesized analogues 2–4 with one or two β‐lactone groups in either a cis or trans configuration. Complexes 1–4 have the same Cu‐N4 core site but different electronic structures. Although β‐oxidation led to large anodic shifts of reductions, 1–4 displayed similar HER activities in terms of close overpotentials. With electrochemical, chemical and theoretical results, we show that the catalytically active species switches from a CuI species for 1 to a Cu0 species for 4. This work is thus significant to present mechanism‐controllable HER via electronic tuning of catalysts. A series of Cu porphyrins with fine‐tuned electronic structures are synthesized and examined as electrocatalysts for hydrogen evolution. Mechanism studies reveal that the catalytically active species switches from a formal CuI species to a formal Cu0 species upon decreasing the electron density of these Cu porphyrins. This work presents an unparalleled example of regulating hydrogen evolution reaction mechanism via electronic tuning of catalysts.