Show simple item record

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.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.publisherThe Royal Society of Chemistry
dc.sourceChemical Science
dc.subjectMetal-organic frameworksen_US
dc.subjectsupramolecular photocatalystsen_US
dc.subjectphotoelectrochemical cellsen_US
dc.subjectmolecular assembliesen_US
dc.titleA donor-chromophore-catalyst assembly for solar CO2 reductionen_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)

Files in this item

This item appears in the following Collection(s)

Show simple item record
Except where otherwise noted, this item's license is described as