TY - JOUR
T1 - Bioinspired multimetal electrocatalyst for selective methane oxidation
AU - Al-Attas, Tareq
AU - Khan, M. A.
AU - Goncalves, Tiago J.
AU - Yasri, Nael G.
AU - Roy, Soumyabrata
AU - Zeraati, Ali Shayesteh
AU - Kumar, Pawan
AU - Miller, Kristen A.
AU - Ajayan, Pulickel M.
AU - Gates, Ian D.
AU - Hu, Jinguang
AU - Thangadurai, Venkataraman
AU - Siahrostami, Samira
AU - Kibria, Md Golam
N1 - This work was financially supported by the Canada First Research Excellence Fund (CFREF) at the University of Calgary. We thank the Canadian Light Source (CLS) synchrotron for the general access provided under project number 35G12344 ∼ Kibria. We thank T. Regier, J. Dynes, and Z. Arthur for technical support at the 11ID-1 (SGM) beamline in CLS. We thank N. Chen and W. Chen for technical support at the 06ID-1(HXMA) beamline in CLS. We thank W. White from the Department of Chemistry at the University of Calgary for NMR support. We thank H. Shaker Shiran for the help during in situ XANES experiments. T.A. thanks CFREF, Alberta Innovates, and the Government of Alberta for their support through graduate scholarships.
PY - 2023/10/15
Y1 - 2023/10/15
N2 - Selective partial electrooxidation of methane (CH4) to liquid oxygenates has been a long-sought goal. However, the high activation energy of C–H bonds and competing oxygen evolution reaction limit product selectivity and reaction rates. Inspired by iron (IV)-oxo containing metalloenzymes’ functionality to activate the C–H bond, here we report on the design of a copper-iron-nickel catalyst for selective oxidation of CH4 to formate via a peroxide-assisted pathway. Each catalyst serves a specific role which is confirmed via electrochemical, in situ, and theoretical studies. A combination of electrochemical and in situ spectroelectrochemical studies revealed that H2O2 oxidation on nickel led to the formation of active oxygen species which trigger the formation of iron (IV) at low voltages. Density functional theory analysis helped reveal the role of iron (IV)-oxo species in reducing the activation energy barrier for CH4 deprotonation and the critical role of copper to suppress overoxidation. Our multimetal catalyst exhibits a formate faradaic efficiency of 42% at an applied potential of 0.9 V versus a reversible hydrogen electrode.
AB - Selective partial electrooxidation of methane (CH4) to liquid oxygenates has been a long-sought goal. However, the high activation energy of C–H bonds and competing oxygen evolution reaction limit product selectivity and reaction rates. Inspired by iron (IV)-oxo containing metalloenzymes’ functionality to activate the C–H bond, here we report on the design of a copper-iron-nickel catalyst for selective oxidation of CH4 to formate via a peroxide-assisted pathway. Each catalyst serves a specific role which is confirmed via electrochemical, in situ, and theoretical studies. A combination of electrochemical and in situ spectroelectrochemical studies revealed that H2O2 oxidation on nickel led to the formation of active oxygen species which trigger the formation of iron (IV) at low voltages. Density functional theory analysis helped reveal the role of iron (IV)-oxo species in reducing the activation energy barrier for CH4 deprotonation and the critical role of copper to suppress overoxidation. Our multimetal catalyst exhibits a formate faradaic efficiency of 42% at an applied potential of 0.9 V versus a reversible hydrogen electrode.
UR - https://www.scopus.com/pages/publications/85170409884
U2 - 10.1016/j.cej.2023.145827
DO - 10.1016/j.cej.2023.145827
M3 - Article
AN - SCOPUS:85170409884
SN - 1385-8947
VL - 474
JO - Chemical Engineering Journal
JF - Chemical Engineering Journal
M1 - 145827
ER -