title: Proton switch for modulating oxygen reduction by a copper electrocatalyst embedded in a hybrid bilayer membrane.
abstract: Molecular switches gate many fundamental processes in natural and artificial systems. Here, we report the development of an electrochemical platform in which a proton carrier switches the activity of a catalyst. By incorporating an alkyl phosphate in the lipid layer of a hybrid bilayer membrane, we regulate proton transport to a Cu-based molecular oxygen reduction reaction catalyst. To construct this hybrid bilayer membrane system, we prepare an example of a synthetic Cu oxygen reduction reaction catalyst that forms a self-assembled monolayer on Au surfaces. We then embed this Cu catalyst inside a hybrid bilayer membrane by depositing a monolayer of lipid on the self-assembled monolayer. We envisage that this electrochemical system can give a unique mechanistic insight not only into the oxygen reduction reaction, but into proton-coupled electron transfer in general.
authors.affiliation: 1] Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA [2].
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Barile
authors.affiliation: 1] Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA [2].
authors.forename: Edmund C M
authors.initials: EC
authors.lastname: Tse
authors.affiliation: Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.
authors.forename: Ying
authors.initials: Y
authors.lastname: Li
authors.affiliation: Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.
authors.forename: Thomas B
authors.initials: TB
authors.lastname: Sobyra
authors.affiliation: Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.
authors.forename: Steven C
authors.initials: SC
authors.lastname: Zimmerman
authors.affiliation: Department of Chemical and Materials Engineering, The University of Auckland, Auckland 1010, New Zealand.
authors.forename: Ali
authors.initials: A
authors.lastname: Hosseini
authors.affiliation: 1] Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA [2] International Institute for Carbon Neutral Energy Research (WPI-I2CNER), Kyushu University, Fukuoka 812-8581, Japan.
authors.forename: Andrew A
authors.initials: AA
authors.lastname: Gewirth
mesh_terms: D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D055664:Electrochemical Techniques; D008051:Lipid Bilayers / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D011522:Protons
chemical_list: D008051:Lipid Bilayers; D011522:Protons; D003300:Copper; D010100:Oxygen