Dual‐Synergistic S‐Scheme Heterojunction for Targeting Dibenzylamine via Cascade Photoredox Catalysis of Benzylamine
Abstract
Abstract Photocatalysis integrates oxidation and reduction processes, offering significant potential for driving synthetic transformations under mild conditions. However, the development of light‐driven redox cascade reactions—essential for expanding reaction diversity—remains challenging and unexplored. In this study, a semiconductor cluster‐based S‐scheme heterojunction, T4‐CdCu/ZIS , is designed for the photocatalytic redox cascade conversion of benzylamine (BA) to dibenzylamine (DBA) under a CO 2 atmosphere. The heterojunction operates via a dual internal‐external synergy. Internally, Fermi level‐engineered synergy enhances charge transfer kinetics, enabling rapid carrier separation and suppressed recombination while preserving favorable redox potentials. Externally, this internal synergy drives the tandem oxidation of BA to N ‐benzylbenzaldimine (BBAD) and its subsequent reduction to DBA, facilitated by a tight interface and highly exposed clusters. Consequently, exceptional photocatalytic BA conversion is achieved, yielding a record production rate of 8.31 mmol·g −1 ·h −1 with complete DBA selectivity. Mechanistic investigations suggest that BA undergoes dehydrocoupling on oxidative ZIS to form the BBAD intermediate, which then migrates to T4‐CdCu for reduction to DBA via adsorbed H species. As proof‐of‐concept, a drug, Cinacalcet , exemplifies the synthesis potential of secondary amines. This work provides a sustainable route for synthesizing secondary amines and inspires the design of advanced heterojunction catalysts for efficient redox cascade reactions.
Article Details
Authors (10)
Chao‐Li Chen
State Key Laboratory of Bioactive Molecules and Druggability Assessment Guangdong Basic Research Center of Excellence for Natural Bioactive Molecules and Discovery of Innovative Drugs College of Chemistry and Materials Science and Guangdong Provincial Key Laboratory of Supramolecular Coordination Chemistry Jinan University Guangzhou 510632 China
Jia‐Xing Liu
State Key Laboratory of Bioactive Molecules and Druggability Assessment Guangdong Basic Research Center of Excellence for Natural Bioactive Molecules and Discovery of Innovative Drugs College of Chemistry and Materials Science and Guangdong Provincial Key Laboratory of Supramolecular Coordination Chemistry Jinan University Guangzhou 510632 China
Xu‐Hang Zhong
State Key Laboratory of Bioactive Molecules and Druggability Assessment Guangdong Basic Research Center of Excellence for Natural Bioactive Molecules and Discovery of Innovative Drugs College of Chemistry and Materials Science and Guangdong Provincial Key Laboratory of Supramolecular Coordination Chemistry Jinan University Guangzhou China
Pei‐Lin Ou
State Key Laboratory of Bioactive Molecules and Druggability Assessment Guangdong Basic Research Center of Excellence for Natural Bioactive Molecules and Discovery of Innovative Drugs College of Chemistry and Materials Science and Guangdong Provincial Key Laboratory of Supramolecular Coordination Chemistry Jinan University Guangzhou 510632 China
Jia‐Xin Liu
State Key Laboratory of Bioactive Molecules and Druggability Assessment Guangdong Basic Research Center of Excellence for Natural Bioactive Molecules and Discovery of Innovative Drugs College of Chemistry and Materials Science and Guangdong Provincial Key Laboratory of Supramolecular Coordination Chemistry Jinan University Guangzhou 510632 China
Zhong‐Yu Liang
State Key Laboratory of Bioactive Molecules and Druggability Assessment Guangdong Basic Research Center of Excellence for Natural Bioactive Molecules and Discovery of Innovative Drugs College of Chemistry and Materials Science and Guangdong Provincial Key Laboratory of Supramolecular Coordination Chemistry Jinan University Guangzhou 510632 China
Shang‐Fu Yuan
State Key Laboratory of Bioactive Molecules and Druggability Assessment Guangdong Basic Research Center of Excellence for Natural Bioactive Molecules and Discovery of Innovative Drugs College of Chemistry and Materials Science and Guangdong Provincial Key Laboratory of Supramolecular Coordination Chemistry Jinan University Guangzhou China
Bingzhe Wang
Jinan University , , , ,
Dong‐Sheng Li
College of Materials and Chemical Engineering Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials China Three Gorges University Yichang China
Tao Wu