skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: A donor-chromophore-catalyst assembly for solar CO 2 reduction

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 atmore » t1/2 = 2.6 μs (kET = 2.7 × 105 s−1).« less

Authors:
 [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [2];  [1];  [1];  [1];  [1]; ORCiD logo [3]; ORCiD logo [1]
  1. Department of Chemistry; University of North Carolina Chapel Hill; Chapel Hill; USA
  2. Department of Chemistry; Texas Christian University; Fort Worth; USA
  3. Department of Chemistry and Biochemistry; Florida International University; Miami; USA
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Alliance for Molecular PhotoElectrode Design for Solar Fuels (AMPED); Florida International Univ., Miami, FL (United States); Univ. of North Carolina, Chapel Hill, NC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Nuclear Energy (NE)
OSTI Identifier:
1566641
DOE Contract Number:  
NE0008539; SC0001011
Resource Type:
Journal Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 10; Journal Issue: 16; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
catalysis (homogeneous), catalysis (heterogeneous), electrocatalysis, solar (fuels), photosynthesis (natural and artificial), defects, charge transport, materials and chemistry by design, mesostructured materials, synthesis (novel materials), synthesis (self-assembly)

Citation Formats

Wang, Degao, Wang, Ying, Brady, Matthew D., Sheridan, Matthew V., Sherman, Benjamin D., Farnum, Byron H., Liu, Yanming, Marquard, Seth L., Meyer, Gerald J., Dares, Christopher J., and Meyer, Thomas J. A donor-chromophore-catalyst assembly for solar CO 2 reduction. United States: N. p., 2019. Web. doi:10.1039/c8sc03316a.
Wang, Degao, Wang, Ying, Brady, Matthew D., Sheridan, Matthew V., Sherman, Benjamin D., Farnum, Byron H., Liu, Yanming, Marquard, Seth L., Meyer, Gerald J., Dares, Christopher J., & Meyer, Thomas J. A donor-chromophore-catalyst assembly for solar CO 2 reduction. United States. doi:10.1039/c8sc03316a.
Wang, Degao, Wang, Ying, Brady, Matthew D., Sheridan, Matthew V., Sherman, Benjamin D., Farnum, Byron H., Liu, Yanming, Marquard, Seth L., Meyer, Gerald J., Dares, Christopher J., and Meyer, Thomas J. Tue . "A donor-chromophore-catalyst assembly for solar CO 2 reduction". United States. doi:10.1039/c8sc03316a.
@article{osti_1566641,
title = {A donor-chromophore-catalyst assembly for solar CO 2 reduction},
author = {Wang, Degao and Wang, Ying and Brady, Matthew D. and Sheridan, Matthew V. and Sherman, Benjamin D. and Farnum, Byron H. and Liu, Yanming and Marquard, Seth L. and Meyer, Gerald J. and Dares, Christopher J. and Meyer, Thomas J.},
abstractNote = {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).},
doi = {10.1039/c8sc03316a},
journal = {Chemical Science},
issn = {2041-6520},
number = 16,
volume = 10,
place = {United States},
year = {2019},
month = {1}
}

Works referenced in this record:

Powering the planet: Chemical challenges in solar energy utilization
journal, October 2006

  • Lewis, N. S.; Nocera, D. G.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735
  • DOI: 10.1073/pnas.0603395103