Abstract
The hydrogenation of CO2 to hydrocarbon fuels via solar radiation offers a sustainable pathway towards a carbon-neutral energy cycle. However, the reaction is hindered by the intermittent availability of sunlight. This critical issue could be mitigated by engineering a materials system, known as persistent photocatalysis, that prolongs solar fuel production during overcast periods and into the evenings. During illumination, charge can be stored in a suitable capacitor or battery-like material that interfaces with the photocatalyst, while discharging occurs postillumination to continue driving the catalytic reaction. We discuss emerging trends and materials strategies to develop these catalyst systems and prolong the operation of photocatalysis.
This is a preview of subscription content, access via your institution
Relevant articles
Open Access articles citing this article.
-
Conjugated cross-linked phosphine as broadband light or sunlight-driven photocatalyst for large-scale atom transfer radical polymerization
Nature Communications Open Access 20 May 2023
-
Room-temperature photosynthesis of propane from CO2 with Cu single atoms on vacancy-rich TiO2
Nature Communications Open Access 27 February 2023
-
Grave-to-cradle upcycling of Ni from electroplating wastewater to photothermal CO2 catalysis
Nature Communications Open Access 09 September 2022
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 digital issues and online access to articles
$119.00 per year
only $9.92 per issue
Rent or buy this article
Get just this article for as long as you need it
$39.95
Prices may be subject to local taxes which are calculated during checkout




References
Lüthi, D. et al. High-resolution carbon dioxide concentration record 650,000–800,000 years before present. Nature 453, 379–382 (2008).
Vega, E., Chalk, T. B., Wilson, P. A., Bysani, R. P. & Foster, G. L. Atmospheric CO2 during the Mid-Piacenzian Warm Period and the M2 glaciation. Sci. Rep. 10, 11002 (2020).
Net Zero by 2050: From Whether to How (European Climate Foundation, 2018); https://europeanclimate.org/
Li, X., Yu, J., Jaroniec, M. & Chen, X. Cocatalysts for selective photoreduction of CO2 into solar fuels. Chem. Rev. 119, 3962–4179 (2019).
Ganesh, I. Conversion of carbon dioxide into methanol—a potential liquid fuel: fundamental challenges and opportunities (a review). Renew. Sustain. Energy Rev. 31, 221–257 (2014).
Lewis, N. S. An integrated, systems approach to the development of solar fuel generators. Electrochem. Soc. Interface 22, 43–49 (2013).
Matuszko, D. Influence of the extent and genera of cloud cover on solar radiation intensity. Int. J. Climatol. 32, 2403–2414 (2012).
Detz, R. J., Reek, J. N. H. & Van Der Zwaan, B. C. C. The future of solar fuels: when could they become competitive? Energy Environ. Sci. 11, 1653–1669 (2018).
McCormick, P. G. & Suehrcke, H. The effect of intermittent solar radiation on the performance of PV systems. Sol. Energy 171, 667–674 (2018).
Suri, M., Cebecauer, T. & Skoczek, A. Cloud cover impact on photovoltaic power production in South Africa. S. Afr. Sol. Energy Conf. 8, 1–8 (2014).
Sakar, M., Nguyen, C. C., Vu, M. H. & Do, T. O. Materials and mechanisms of photo‐assisted chemical reactions under light and dark conditions: can day–night photocatalysis be achieved? ChemSusChem 11, 809–820 (2018).
Augustyn, V., Simon, P. & Dunn, B. Pseudocapacitive oxide materials for high-rate electrochemical energy storage. Energy Environ. Sci. 7, 1597–1614 (2014).
Costentin, C., Porter, T. R. & Savéant, J. M. How do pseudocapacitors store energy? Theoretical analysis and experimental illustration. ACS Appl. Mater. Interfaces 9, 8649–8658 (2017).
Takahashi, Y. & Tatsuma, T. Oxidative energy storage ability of a TiO2–Ni(OH)2 bilayer photocatalyst. Langmuir 21, 12357–12361 (2005).
Kim, S., Park, Y., Kim, W. & Park, H. Harnessing and storing visible light using a heterojunction of WO3 and CdS for sunlight-free catalysis. Photochem. Photobiol. Sci. 15, 1006–1011 (2016).
Liu, L., Sun, W., Yang, W., Li, Q. & Shang, J. K. Post-illumination activity of SnO2 nanoparticle-decorated Cu2O nanocubes by H2O2 production in dark from photocatalytic “memory”. Sci. Rep. 6, 20878 (2016).
Liu, L., Yang, W., Li, Q., Gao, S. & Shang, J. K. Synthesis of Cu2O nanospheres decorated with TiO2 nanoislands, their enhanced photoactivity and stability under visible light illumination, and their post-illumination catalytic memory. ACS Appl. Mater. Interfaces 6, 5629–5639 (2014).
Chatten, R., Chadwick, A. V., Rougier, A. & Lindan, P. J. D. The oxygen vacancy in crystal phases of WO3. J. Phys. Chem. B 109, 3146–3156 (2005).
Wang, S., Fan, W., Liu, Z., Yu, A. & Jiang, X. Advances on tungsten oxide based photochromic materials: strategies to improve their photochromic properties. J. Mater. Chem. C. 6, 191–212 (2018).
Xiong, L.-B., Li, J.-L., Yang, B. & Yu, Y. Ti3+ in the surface of titanium dioxide: generation, properties and photocatalytic application. J. Nanomater. 5, 1–14 (2012).
Lira, E. et al. The importance of bulk Ti3+ defects in the oxygen chemistry on titania surfaces. J. Am. Chem. Soc. 133, 6529–6532 (2011).
Zhang, Q., Wang, H., Li, Z., Geng, C. & Leng, J. Metal-free photocatalyst with visible-light-driven post-illumination catalytic memory. ACS Appl. Mater. Interfaces 9, 21738–21746 (2017).
Xu, Y. et al. Atomic-scale marriage of light-harvesting and charge-storing components for efficient photoenergy storage catalysis. Nano Energy 28, 407–416 (2016).
Li, J. et al. A full-sunlight-driven photocatalyst with super long-persistent energy storage ability. Sci. Rep. 3, 2409 (2013).
Ling, T. et al. Atomic-level structure engineering of metal oxides for high-rate oxygen intercalation pseudocapacitance. Sci. Adv. 4, eaau6261 (2018).
Kim, H. S. et al. Oxygen vacancies enhance pseudocapacitive charge storage properties of MoO3-x. Nat. Mater. 16, 454–462 (2017).
Yan, L. et al. Experimental and theoretical investigation of the effect of oxygen vacancies on the electronic structure and pseudocapacitance of MnO2. ChemSusChem 12, 3571–3581 (2019).
Lee, J., Sorescu, D. C. & Deng, X. Electron-induced dissociation of CO2 on TiO2(110). J. Am. Chem. Soc. 133, 10066–10069 (2011).
Wang, L., Ha, M. N., Liu, Z. & Zhao, Z. Hydrogen-treated mesoporous WO3 as a reducing agent of CO2 to fuels (CH4 and CH3OH) with enhanced photothermal catalytic performance. J. Mater. Chem. A 4, 5314–5322 (2016).
Yu, X. et al. Emergent pseudocapacitance of 2D nanomaterials. Adv. Energy Mater. 8, 1702930 (2018).
Cong, S., Tian, Y., Li, Q., Zhao, Z. & Geng, F. Single‐crystalline tungsten oxide quantum dots for fast pseudocapacitor and electrochromic applications. Adv. Mater. 26, 4260–4267 (2014).
Sun, S., Watanabe, M., Wu, J., An, Q. & Ishihara, T. Ultrathin WO3·0.33H2O nanotubes for CO2 photoreduction to acetate with high selectivity. J. Am. Chem. Soc. 140, 6474–6482 (2018).
Sun, S., Watanabe, M., Wu, J., An, Q. & Ishihara, T. Ultrathin W18O49 nanowires with diameters below 1 nm: synthesis, near-infrared absorption, photoluminescence, and photochemical reduction of carbon dioxide. Angew. Chem. Int. Ed. 51, 2395–2399 (2012).
Voiry, D., Shin, H. S., Loh, K. P. & Chhowalla, M. Low-dimensional catalysts for hydrogen evolution and CO2 reduction. Nat. Rev. Chem. 2, 0105 (2018).
Tu, W. et al. Investigating the role of tunable nitrogen vacancies in graphitic carbon nitride nanosheets for efficient visible-light-driven H2 evolution and CO2 reduction. ACS Sustain. Chem. Eng. 5, 7260–7268 (2017).
Safaei, J. et al. Graphitic carbon nitride (g-C3N4) electrodes for energy conversion and storage: a review on photoelectrochemical water splitting, solar cells and supercapacitors. J. Mater. Chem. A. 6, 22346–22380 (2018).
Liang, L. et al. Infrared light-driven CO2 overall splitting at room temperature. Joule 2, 1004–1016 (2018).
Wang, L., Ha, M. N., Liu, Z. & Zhao, Z. Mesoporous WO3 modified by Mo for enhancing reduction of CO2 to solar fuels under visible light and thermal conditions. Integr. Ferroelectr. 172, 97–108 (2016).
Li, Q. et al. Memory antibacterial effect from photoelectron transfer between nanoparticles and visible light photocatalyst. J. Mater. Chem. 20, 1068–1072 (2010).
Han, D. S. et al. Sunlight-charged heterojunction TiO2 and WO3 particle-embedded inorganic membranes for night-time environmental applications. Photochem. Photobiol. Sci. 17, 491–498 (2018).
Wan, L. et al. Cu2O nanocubes with mixed oxidation-state facets for (photo)catalytic hydrogenation of carbon dioxide. Nat. Catal. 2, 889–898 (2019).
Jia, J. et al. Visible and near-infrared photothermal catalyzed hydrogenation of gaseous CO2 over nanostructured Pd@Nb2O5. Adv. Sci. 3, 1600189 (2016).
Jing, H. et al. Metallic MoO2-modified graphitic carbon nitride boosting photocatalytic CO2 reduction via Schottky junction. Sol. RRL 8, 1900416 (2019).
Li, J. et al. Sunlight induced photo-thermal synergistic catalytic CO2 conversion: via localized surface plasmon resonance of MoO3−x. J. Mater. Chem. A 7, 2821–2830 (2019).
Vickers, S. M., Gholami, R., Smith, K. J. & MacLachlan, M. J. Mesoporous Mn- and La-doped cerium oxide/cobalt oxide mixed metal catalysts for methane oxidation. ACS Appl. Mater. Interfaces 7, 11460–11466 (2015).
Jampaiah, D., Venkataswamy, P., Coyle, V. E., Reddy, B. M. & Bhargava, S. K. Low-temperature CO oxidation over manganese, cobalt, and nickel doped CeO2 nanorods. RSC Adv. 6, 80541–80548 (2016).
Watanabe, K., Menzel, D., Nilius, N. & Freund, H. J. Photochemistry on metal nanoparticles. Chem. Rev. 106, 4301–4320 (2006).
Chu, W., Zheng, Q., Prezhdo, O. V. & Zhao, J. CO2 photoreduction on metal oxide surface is driven by transient capture of hot electrons: ab initio quantum dynamics simulation. J. Am. Chem. Soc. 142, 3214–3221 (2020).
Watson, A. M. et al. Rhodium nanoparticles for ultraviolet plasmonics. Nano Lett. 15, 1095–1100 (2015).
Yu, S. & Jain, P. K. Plasmonic photosynthesis of C1–C3 hydrocarbons from carbon dioxide assisted by an ionic liquid. Nat. Commun. 10, 2022 (2019).
Zhang, X. et al. Product selectivity in plasmonic photocatalysis for carbon dioxide hydrogenation. Nat. Commun. 8, 14542 (2017).
Ghuman, K. K. et al. Photoexcited surface frustrated Lewis pairs for heterogeneous photocatalytic CO2 reduction. J. Am. Chem. Soc. 138, 1206–1214 (2016).
Ghuman, K. K. et al. Illuminating CO2 reduction on frustrated Lewis pair surfaces: investigating the role of surface hydroxides and oxygen vacancies on nanocrystalline In2O3−x(OH)y. Phys. Chem. Chem. Phys. 17, 14623–14635 (2015).
Hoch, L. B. et al. Carrier dynamics and the role of surface defects: designing a photocatalyst for gas-phase CO2 reduction. Proc. Natl Acad. Sci. USA 50, 1609374113 (2016).
Loh, J. Y. Y., Mohan, A., Flood, A. G., Ozin, G. A. & Kherani, N. P. Waveguide photoreactor enhances solar fuels photon utilization towards maximal optoelectronic–photocatalytic synergy. Nat. Commun. 12, 402 (2021).
Simon, P. & Gogotsi, Y. Perspectives for electrochemical capacitors and related devices. Nat. Mater. 19, 1151–1163 (2020).
Chen, S. et al. Semiconductor-based photocatalysts for photocatalytic and photoelectrochemical water splitting: will we stop with photocorrosion? J. Mater. Chem. A 8, 2286–2322 (2020).
Tatsuma, T., Saitoh, S., Ohko, Y. & Fujishima, A. TiO2–WO3 photoelectrochemical anticorrosion system with an energy storage ability. Chem. Mater. 13, 2838–2842 (2001).
Acknowledgements
We thank the Connaught Foundation, NSERC and University of Toronto for their support.
Author information
Authors and Affiliations
Contributions
J.Y.Y.L. conceptualized and prepared the manuscript. G.A.O. and N.P.K. edited the manuscript and are principal investigators.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Peer review information Nature Sustainability thanks Ding Ma and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Loh, J.Y.Y., Kherani, N.P. & Ozin, G.A. Persistent CO2 photocatalysis for solar fuels in the dark. Nat Sustain 4, 466–473 (2021). https://doi.org/10.1038/s41893-021-00681-y
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41893-021-00681-y
This article is cited by
-
Conjugated cross-linked phosphine as broadband light or sunlight-driven photocatalyst for large-scale atom transfer radical polymerization
Nature Communications (2023)
-
Room-temperature photosynthesis of propane from CO2 with Cu single atoms on vacancy-rich TiO2
Nature Communications (2023)
-
High-loading single cobalt atoms on ultrathin MOF nanosheets for efficient photocatalytic CO2 reduction
Science China Chemistry (2023)
-
Linking oxidative and reductive clusters to prepare crystalline porous catalysts for photocatalytic CO2 reduction with H2O
Nature Communications (2022)
-
Grave-to-cradle upcycling of Ni from electroplating wastewater to photothermal CO2 catalysis
Nature Communications (2022)