title: Tailoring the Edge Structure of Molybdenum Disulfide toward Electrocatalytic Reduction of Carbon Dioxide.
abstract: Electrocatalytic conversion of carbon dioxide (CO2) into energy-rich fuels is considered to be the most efficient approach to achieve a carbon neutral cycle. Transition-metal dichalcogenides (TMDCs) have recently shown a very promising catalytic performance for CO2reduction reaction in an ionic liquid electrolyte. Here, we report that the catalytic performance of molybdenum disulfide (MoS2), a member of TMDCs, can be significantly improved by using an appropriate dopant. Our electrochemical results indicate that 5% niobium (Nb)-doped vertically aligned MoS2in ionic liquid exhibits 1 order of magnitude higher CO formation turnover frequency (TOF) than pristine MoS2at an overpotential range of 50-150 mV. The TOF of this catalyst is also 2 orders of magnitude higher than that of Ag nanoparticles over the entire range of studied overpotentials (100-650 mV). Moreover, the in situ differential electrochemical mass spectrometry experiment shows the onset overpotential of 31 mV for this catalyst, which is the lowest onset potential for CO2reduction reaction reported so far. Our density functional theory calculations reveal that low concentrations of Nb near the Mo edge atoms can enhance the TOF of CO formation by modifying the binding energies of intermediates to MoS2edge atoms.
authors.affiliation: Department of Mechanical and Industrial Engineering, University of Illinois at Chicago , Chicago, Illinois 60607, United States.
authors.forename: Pedram
authors.identifier: 0000-0001-6835-3062
authors.initials: P
authors.lastname: Abbasi
authors.affiliation: Department of Mechanical and Industrial Engineering, University of Illinois at Chicago , Chicago, Illinois 60607, United States.
authors.forename: Mohammad
authors.initials: M
authors.lastname: Asadi
authors.affiliation: Materials Science Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Cong
authors.initials: C
authors.lastname: Liu
authors.affiliation: Department of Mechanical and Industrial Engineering, University of Illinois at Chicago , Chicago, Illinois 60607, United States.
authors.forename: Soroosh
authors.identifier: 0000-0003-0441-9231
authors.initials: S
authors.lastname: Sharifi-Asl
authors.affiliation: Department of Mechanical and Industrial Engineering, University of Illinois at Chicago , Chicago, Illinois 60607, United States.
authors.forename: Baharak
authors.identifier: 0000-0003-0200-6636
authors.initials: B
authors.lastname: Sayahpour
authors.affiliation: Department of Mechanical and Industrial Engineering, University of Illinois at Chicago , Chicago, Illinois 60607, United States.
authors.forename: Amirhossein
authors.initials: A
authors.lastname: Behranginia
authors.affiliation: Materials Science Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Peter
authors.identifier: 0000-0003-0570-9169
authors.initials: P
authors.lastname: Zapol
authors.affiliation: Department of Mechanical and Industrial Engineering, University of Illinois at Chicago , Chicago, Illinois 60607, United States.
authors.forename: Reza
authors.initials: R
authors.lastname: Shahbazian-Yassar
authors.affiliation: Materials Science Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Larry A
authors.initials: LA
authors.lastname: Curtiss
authors.affiliation: Department of Mechanical and Industrial Engineering, University of Illinois at Chicago , Chicago, Illinois 60607, United States.
authors.forename: Amin
authors.initials: A
authors.lastname: Salehi-Khojin
keywords: CO2 reduction reaction; atomic doping; electrocatalysis; ionic liquid; transition-metal dichalcogenides