CO 2 Reduction to Methanol on TiO 2 -Passivated GaP Photocatalysts
Abstract
In the past, the electrochemical instability of III–V semiconductors has severely limited their applicability in photocatlaysis. As a result, a vast majority of the research on photocatalysis has been done on TiO 2, which is chemically robust over a wide range of pH. However, TiO 2 has a wide band gap (3.2 eV) and can only absorb ∼4% of the solar spectrum, and thus, it will never provide efficient solar energy conversion/storage on its own. Here, we report photocatalytic CO 2 reduction with water to produce methanol using TiO 2 -passivated GaP photocathodes under 532 nm wavelength illumination. The TiO 2 layer prevents corrosion of the GaP, as evidenced by atomic force microscopy and photoelectrochemical measurements. Here, the GaP surface is passivated using a thin film of TiO 2 deposited by atomic layer deposition (ALD), which provides a viable, stable photocatalyst without sacrificing photocatalytic efficiency. In addition to providing a stable photocatalytic surface, the TiO 2 passivation provides substantial enhancement in the photoconversion efficiency through passivation of surface states, which cause nonradiative carrier recombination. In addition to passivation effects, the TiO 2 deposited by ALD is n-type due to oxygen vacancies and forms a pn-junction with the underlying p-type GaP photocathode. This creates a built-in field that assists in the separation of photogenerated electron–hole pairs, further reducing recombination. This reduction in the surface recombination velocity (SRV) corresponds to a shift in the overpotential of almost 0.5 V. No enhancement is observed for TiO 2 thicknesses above 10 nm, due to the insulating nature of the TiO 2, which eventually outweighs the benefits of passivation.
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Valuable fuels such as CO, CH4, CH3OH, HCOOH, and C2+ products have been generated through proton-assisted multiple electron-transfer processes.
“Many valuable fuels, such as CO, CH4, CH3OH, HCOOH, and C2+ products have been generated through proton-assisted multiple electron-transfer processes.306, 307, 308, 309, 310”
From Technologies and perspectives for achieving carbon neutrality (2021) · cites this paper as [308]
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Technologies and perspectives for achieving carbon neutrality
Wang, F., Harindintwali, J. D., Yuan, Z., Wang, M., Wang, F., Li, S., Yin, Z., Huang, L., Fu, Y., Li, L., et al. (2021) · The Innovation · doi:10.1016/j.xinn.2021.100180 · Cited by 1,330 · see citing works
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- Authors
- Zeng, G., Qiu, J., Li, Z., Pavaskar, P., & Cronin, S. B.
- Affiliations
- University of Southern California (US)
- Corresponding author
- Cronin, Stephen B.
- Venue
- ACS Catalysis
- Publisher
- American Chemical Society (ACS)
- Published
- 2014-09-08
- Volume
- 4
- Issue
- 10
- Pages
- 3512-3516
- ISSN
- 2155-5435 (ISSN-L)
- OpenAlex
- W2328500204
- Cited by
- 154
- References
- 39
- Citations by year
- 2026: 4 · 2025: 7 · 2024: 12 · 2023: 23 · 2022: 18 · 2021: 17 · 2020: 12 · 2019: 19 · 2018: 16 · 2017: 10 · 2016: 8 · 2015: 8
- FWCI
- 2.86
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- ACS Catalysis (publishedVersion)
- Funders
- Office of Naval Research (N00014-12-1-0570)
- Division of Chemical, Bioengineering, Environmental, and Transport Systems (CBET-0854118)
- Topics
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Advanced Photocatalysis Techniques
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › TiO2 Photocatalysis and Solar Cells
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › CO2 Reduction Techniques and Catalysts
- Keywords
- photocatalytic CO2 reduction, methanol synthesis, atomic layer deposition, surface state passivation, p-n junction, built-in electric field, surface recombination velocity, oxygen vacancies, photoelectrochemical stability, solar energy conversion
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