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dc.creatorWang, Degao
dc.creatorWang, Ying
dc.creatorBrady, Matthew D.
dc.creatorSheridan, Matthew V.
dc.creatorSherman, Benjamin D.
dc.creatorFarnum, Byron H.
dc.creatorLiu, Yanming
dc.creatorMarquard, Seth L.
dc.creatorMeyer, Gerald J.
dc.creatorDares, Christopher J.
dc.creatorMeyer, Thomas J.
dc.date.accessioned2019-07-12T16:01:53Z
dc.date.available2019-07-12T16:01:53Z
dc.date.issued2019-03-14
dc.identifier.urihttps://doi.org/10.1039/c8sc03316a
dc.identifier.urihttps://repository.tcu.edu/handle/116099117/26413
dc.identifier.urihttps://pubs.rsc.org/en/content/articlelanding/2019/SC/C8SC03316A
dc.description.abstractWe describe here the preparation and characterization of a photocathode assembly for CO2 reduction to CO in 0.1 M LiClO4 acetonitrile. The assembly was formed on 1.0 µm thick mesoporous films of NiO using a layer-by-layer procedure based on Zr(IV)-phosphonate bridging units. The structure of the Zr(IV) bridged assembly, abbreviated as NiO|-DA-RuCP22+-Re(I), where DA is the dianiline-based electron donor (N,N,N',N'-((CH2)3PO3H2)4-4,4'-dianiline), RuCP2+ is the light absorber [Ru((4,4'-(PO3H2CH2)2-2,2'-bipyridine)(2,2'-bipyridine))2]2+, and Re(I) is the CO2 reduction catalyst, ReI((4,4'-PO3H2CH2)2-2,2'-bipyridine)(CO)3Cl. Visible light excitation of the assembly in CO2 saturated solution resulted in CO2 reduction to CO. A steady-state photocurrent density of 65 µA cm^-2 was achieved under one sun illumination and an IPCE value of 1.9% was obtained with 450 nm illumination. The importance of the DA aniline donor in the assembly as an initial site for reduction of the RuCP2+ excited state was demonstrated by an 8 times higher photocurrent generated with DA present in the surface film compared to a control without DA. Nanosecond transient absorption measurements showed that the expected reduced one-electron intermediate, RuCP+, was formed on a sub-nanosecond time scale with back electron transfer to the electrode on the microsecond timescale which competes with forward electron transfer to the Re(I) catalyst at t1/2 = 2.6 µs (kET = 2.7 x 105 s^-1).en_US
dc.language.isoenen_US
dc.publisherThe Royal Society of Chemistry
dc.rights.urihttps://creativecommons.org/licenses/by-nc/3.0/
dc.sourceChemical Science
dc.subjectMetal-organic frameworksen_US
dc.subjectelectron-transferen_US
dc.subjectsupramolecular photocatalystsen_US
dc.subjectphotoelectrochemical cellsen_US
dc.subjectmolecular assembliesen_US
dc.subjectenergy-conversionen_US
dc.subjectdyeen_US
dc.subjectlighten_US
dc.subjectphotocathodesen_US
dc.subjectcomplexesen_US
dc.titleA donor-chromophore-catalyst assembly for solar CO2 reductionen_US
dc.typeArticleen_US
dc.rights.holderWang et al.
dc.rights.licenseCC BY-NC 3.0
local.collegeCollege of Science and Engineering
local.departmentChemistry & Biochemistry
local.personsSherman (CHEM)


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