title: Electrochemical Water Oxidation by a Catalyst-Modified Metal-Organic Framework Thin Film.
abstract: Water oxidation, a key component in artificial photosynthesis, requires high overpotentials and exhibits slow reaction kinetics that necessitates the use of stable and efficient heterogeneous water-oxidation catalysts (WOCs). Here, we report the synthesis of UiO-67 metal-organic framework (MOF) thin films doped with [Ru(tpy)(dcbpy)OH2]2+(tpy=2,2':6',2''-terpyridine, dcbpy=5,5'-dicarboxy-2,2'-bipyridine) on conducting surfaces and their propensity for electrochemical water oxidation. The electrocatalyst oxidized water with a turnover frequency (TOF) of (0.2±0.1) s-1at 1.71 V versus the normal hydrogen electrode (NHE) in buffered solution (pH∼7) and exhibited structural and electrochemical stability. The electroactive sites were distributed throughout the MOF thin film on the basis of scan-ratedependent voltammetry studies. This work demonstrates a promising way to immobilize large concentrations of electroactive WOCs into a highly robust MOF scaffold and paves the way for future photoelectrochemical water-splitting systems.
authors.affiliation: Department of Chemistry, Virginia Polytechnic Institute and State University, Blacksburg, Virginia, 24061, United States.
authors.forename: Shaoyang
authors.initials: S
authors.lastname: Lin
authors.affiliation: Department of Physics, Purdue University, 525 Northwestern Avenue, West Lafayette, Indiana, 47907, United States.
authors.forename: Yuliana
authors.initials: Y
authors.lastname: Pineda-Galvan
authors.affiliation: Department of Chemistry, Virginia Polytechnic Institute and State University, Blacksburg, Virginia, 24061, United States.
authors.forename: William A
authors.initials: WA
authors.lastname: Maza
authors.affiliation: Department of Chemistry, Virginia Polytechnic Institute and State University, Blacksburg, Virginia, 24061, United States.
authors.forename: Charity C
authors.initials: CC
authors.lastname: Epley
authors.affiliation: Department of Chemistry, Virginia Polytechnic Institute and State University, Blacksburg, Virginia, 24061, United States.
authors.forename: Jie
authors.initials: J
authors.lastname: Zhu
authors.affiliation: Department of Chemistry, Virginia Polytechnic Institute and State University, Blacksburg, Virginia, 24061, United States.
authors.forename: Matthew C
authors.initials: MC
authors.lastname: Kessinger
authors.affiliation: Department of Physics, Purdue University, 525 Northwestern Avenue, West Lafayette, Indiana, 47907, United States.
authors.forename: Yulia
authors.initials: Y
authors.lastname: Pushkar
authors.affiliation: Department of Chemistry, Virginia Polytechnic Institute and State University, Blacksburg, Virginia, 24061, United States.
authors.forename: Amanda J
authors.initials: AJ
authors.lastname: Morris
mesh_terms: D015082:2,2'-Dipyridyl / Q000737:chemistry; D002384:Catalysis; D004563:Electrochemistry; D004566:Electrodes; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D012428:Ruthenium / Q000737:chemistry; D014867:Water / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D014867:Water; D015082:2,2'-Dipyridyl; D012428:Ruthenium
keywords: electrochemistry; metal-organic frameworks; ruthenium; thin films; water splitting