Matthew Jouny1, Jing-Jing Lv1,2, Tao Cheng3,4,5, Byung Hee Ko1, Jun-Jie Zhu2, William A Goddard6,7, Feng Jiao8. 1. Center for Catalytic Science and Technology, Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE, USA. 2. State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China. 3. Joint Center for Artificial Photosynthesis, California Institute of Technology, Pasadena, CA, USA. 4. Materials and Process Simulation Center, California Institute of Technology, Pasadena, CA, USA. 5. Institute of Functional Nano & Soft Materials, Jiangsu Key Laboratory for Carbon-based Functional Materials & Devices, Joint International Research Laboratory of Carbon-based Functional Materials and Devices, Soochow University, Suzhou, Jiangsu, China. 6. Joint Center for Artificial Photosynthesis, California Institute of Technology, Pasadena, CA, USA. wag@caltech.edu. 7. Materials and Process Simulation Center, California Institute of Technology, Pasadena, CA, USA. wag@caltech.edu. 8. Center for Catalytic Science and Technology, Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE, USA. jiao@udel.edu.
Abstract
The electroreduction of CO2 is a promising technology for carbon utilization. Although electrolysis of CO2 or CO2-derived CO can generate important industrial multicarbon feedstocks such as ethylene, ethanol, n-propanol and acetate, most efforts have been devoted to promoting C-C bond formation. Here, we demonstrate that C-N bonds can be formed through co-electrolysis of CO and NH3 with acetamide selectivity of nearly 40% at industrially relevant reaction rates. Full-solvent quantum mechanical calculations show that acetamide forms through nucleophilic addition of NH3 to a surface-bound ketene intermediate, a step that is in competition with OH- addition, which leads to acetate. The C-N formation mechanism was successfully extended to a series of amide products through amine nucleophilic attack on the ketene intermediate. This strategy enables us to form carbon-heteroatom bonds through the electroreduction of CO, expanding the scope of products available from CO2 reduction.
The electroreduction of CO2 is a promising technology for n class="Chemical">carbon utilization. Although electrolysis of CO2 or CO2-derived CO can generate important industrial multicarbon feedstocks such as ethylene, ethanol, n-propanol and acetate, most efforts have been devoted to promoting C-C bond formation. Here, we demonstrate that C-N bonds can be formed through co-electrolysis of CO and NH3 with acetamide selectivity of nearly 40% at industrially relevant reaction rates. Full-solvent quantum mechanical calculations show that acetamide forms through nucleophilic addition of NH3 to a surface-bound ketene intermediate, a step that is in competition with OH- addition, which leads to acetate. The C-N formation mechanism was successfully extended to a series of amide products through amine nucleophilic attack on the ketene intermediate. This strategy enables us to form carbon-heteroatom bonds through the electroreduction of CO, expanding the scope of products available from CO2 reduction.
Authors: Mahinder Ramdin; Bert De Mot; Andrew R T Morrison; Tom Breugelmans; Leo J P van den Broeke; J P Martin Trusler; Ruud Kortlever; Wiebren de Jong; Othonas A Moultos; Penny Xiao; Paul A Webley; Thijs J H Vlugt Journal: Ind Eng Chem Res Date: 2021-11-30 Impact factor: 3.720