Efficient Visible-Light-Driven CO₂ Reduction by a Cobalt Molecular Catalyst Covalently Linked to Mesoporous Carbon Nitride

Abstract

Achieving visible-light-driven carbon dioxide reduction with high selectivity control and durability while using only earth abundant elements requires new strategies. Hybrid catalytic material was prepared upon covalent grafting a Co−quaterpyridine molecular complex to semiconductive mesoporous graphitic carbon nitride (mpg-C 3 N 4) through an amide linkage. The molecular material was characterized by various spectroscopic techniques, including XPS, IR, and impedance spectroscopy. It proved to be a selective catalyst for CO production in acetonitrile using a solar simulator with a high 98% selectivity, while being remarkably robust since no degradation was observed after 4 days of irradiation (ca. 500 catalytic cycles). This unique combination of a selective molecular catalyst with a simple and robust semiconductive material opens new pathways for CO 2 catalytic light-driven reduction.

POM‐Incorporated CoO Nanowires for Enhanced Photocatalytic Syngas Production from CO2

“…Notably, we found that cobalt compounds demonstrate promising performance towards photocatalysis for its abundance and high performance . Quantities of Co‐based molecular catalysts have been applied to photocatalytic CO 2 reduction and hydrogen evolution . However, Co‐contained heterogeneous catalysts are seldom reported .…”

“…[19] Quantities of Co-based molecular catalysts have been applied to photocatalytic CO 2 reduction and hydrogen evolution. [20,21] However, Co-contained heterogeneous catalysts are seldom reported. [9,[22][23][24] Tang and co-workers synthesized Co 3 O 4 hexagonal platelets with enhanced photocatalytic CO 2 reduction performance.…”

Recent Progress on Carbon Nitride and Its Hybrid Photocatalysts for CO2 Reduction

“…Coordination complexes, montmorillonite (Mt), and MXene etc., have been, respectively, composited with g‐C 3 N 4 for promoting the photocatalytic CO 2 RR efficiency. [ 89,168–176 ] For instance, Kuriki et al prepared the Ru (I) complex/g‐C 3 N 4 composite which is a good heterogeneous photocatalyst for CO 2 RR under visible light. [ 169 ] The obtained optimized photocatalyst can converse CO 2 into HCOOH efficiently with high turnover numbers (>1000) and a relatively high apparent quantum efficiency (5.7% at 400 nm).…”

Atomic‐ and Molecular‐Level Functionalizations of Polymeric Carbon Nitride for Solar Fuel Production

“…Then the CO 2 molecule reacted with the Co(I)–porphyrin motif to be converted into CO. More recently, Robert and coworkers have covalently grafted a cobalt–quaterpyridine molecular complex (Coqpy‐Ph‐COOH) to semiconductive mesoporous PCN through an amide linkage. [ 147 ] As shown in Figure , under visible‐light irradiation, the CH 3 CN suspension of the Co‐complex‐functionalized PCN photocatalyst showed very high selectivity (97%) for CO evolution and a TON of 254 with long‐term durability over about 4 days. It also showed remarkably enhanced photocurrent responses with only a slight attenuation after ten cycles.…”