Electrochemical evolution of a metal oxyhydroxide surface on two‐dimensional layered metal phosphorus trisulfides enables the oxidation of amine to nitrile
Binglan Wu,
Karim Harrath,
Marshet Getaye Sendeku,
Tofik Ahmed Shifa,
Yuxin Huang,
Jing Tai,
Fekadu Tsegaye Dajan,
Kassa Belay Ibrahim,
Xueying Zhan,
Zhenxing Wang,
Elisa Moretti,
Ying Yang,
Fengmei Wang,
Alberto Vomiero
Affiliations
Binglan Wu
State Key Laboratory of Chemical Resource Engineering, College of Chemistry Beijing University of Chemical Technology Beijing China
Karim Harrath
Fundamental Science Center of Rare Earths, Ganjiang Innovation Academy, Chinese Academy of Science Ganzhou China
Marshet Getaye Sendeku
CAS Key Laboratory of Nanosystem and Hierarchical Fabrication National Center for Nanoscience and Technology (NCNST) Beijing China
Tofik Ahmed Shifa
Department of Molecular Sciences and Nanosystems Ca' Foscari University of Venice Venezia Mestre Italy
Yuxin Huang
State Key Laboratory of Chemical Resource Engineering, College of Chemistry Beijing University of Chemical Technology Beijing China
Jing Tai
Testing and Analysis Center, Institute of Chemistry Chinese Academy of Sciences Beijing China
Fekadu Tsegaye Dajan
CAS Key Laboratory of Nanosystem and Hierarchical Fabrication National Center for Nanoscience and Technology (NCNST) Beijing China
Kassa Belay Ibrahim
Department of Molecular Sciences and Nanosystems Ca' Foscari University of Venice Venezia Mestre Italy
Xueying Zhan
CAS Key Laboratory of Nanosystem and Hierarchical Fabrication National Center for Nanoscience and Technology (NCNST) Beijing China
Zhenxing Wang
CAS Key Laboratory of Nanosystem and Hierarchical Fabrication National Center for Nanoscience and Technology (NCNST) Beijing China
Elisa Moretti
Department of Molecular Sciences and Nanosystems Ca' Foscari University of Venice Venezia Mestre Italy
Ying Yang
Shaanxi Provincial Key Laboratory of Electroanalytical Chemistry, Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, College of Chemistry & Materials Science Northwest University Xi'an China
Fengmei Wang
State Key Laboratory of Chemical Resource Engineering, College of Chemistry Beijing University of Chemical Technology Beijing China
Alberto Vomiero
Department of Molecular Sciences and Nanosystems Ca' Foscari University of Venice Venezia Mestre Italy
Abstract Selective oxidation of amines to imines through electrocatalysis is an attractive and efficient way for the chemical industry to produce nitrile compounds, but it is limited by the difficulty of designing efficient catalysts and lack of understanding the mechanism of catalysis. Herein, we demonstrate a novel strategy by generation of oxyhydroxide layers on two‐dimensional iron‐doped layered nickel phosphorus trisulfides (Ni1−xFexPS3) during the oxidation of benzylamine (BA). In‐depth structural and surface chemical characterizations during the electrocatalytic process combined with theoretical calculations reveal that Ni(1−x)FexPS3 undergoes surface reconstruction under alkaline conditions to form the metal oxyhydroxide/phosphorus trichalcogenide (NiFeOOH/Ni1−xFexPS3) heterostructure. Interestingly, the generated heterointerface facilitates BA oxidation with a low onset potential of 1.39 V and Faradaic efficiency of 53% for benzonitrile (BN) synthesis. Theoretical calculations further indicate that the as‐formed NiFeOOH/Ni1−xFexPS3 heterostructure could offer optimum free energy for BA adsorption and BN desorption, resulting in promising BN synthesis.
