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Issue 16, 2019
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A donor-chromophore-catalyst assembly for solar CO2 reduction

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Abstract

We 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 × 105 s−1).

Graphical abstract: A donor-chromophore-catalyst assembly for solar CO2 reduction

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Supplementary files

Article information


Submitted
26 Jul 2018
Accepted
13 Mar 2019
First published
14 Mar 2019

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2019,10, 4436-4444
Article type
Edge Article

A donor-chromophore-catalyst assembly for solar CO2 reduction

D. Wang, Y. Wang, M. D. Brady, Matthew V. Sheridan, B. D. Sherman, B. H. Farnum, Y. Liu, S. L. Marquard, G. J. Meyer, C. J. Dares and T. J. Meyer, Chem. Sci., 2019, 10, 4436
DOI: 10.1039/C8SC03316A

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    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
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    [Original citation] - Published by The Royal Society of Chemistry.

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