Renewable energy-driven hydrogen production from electrocatalytic and photocatalytic water splitting has been widely recognized as a promising approach to utilize green energy resources and hence reduces our dependence on legacy fossil fuels as well as alleviates net carbon dioxide emissions. The realization of large-scale water splitting, however, is mainly impeded by its slow kinetics, particularly because of its sluggish anodic half reaction, the oxygen evolution reaction (OER), whose product O 2 is ironically not of high value. In fact, the co-production of H 2 and O 2 in conventional water electrolysis may result in the formation of explosive H 2 /O 2 gas mixtures due to gas crossover and reactive oxygen species (ROS); both pose safety concerns and shorten the lifetimes of water splitting cells. With these considerations in mind, replacing the OER with thermodynamically more favorable organic oxidation reactions is much more preferred, which will not only substantially reduce the voltage input for H 2 evolution from water and avoid the generation of H 2 /O 2 gas mixtures and ROS, but also possibly lead to the co-production of value-added organic products on the anode. Indeed, such an innovative strategy for H 2 production integrated with valuable organic oxidation has attracted increasing attention in both electrocatalysis and photocatalysis. This feature article showcases the most recent examples along this endeavor. As exemplified in the main text, the oxidative transformation of a variety of organic substrates, including alcohols, ammonia, urea, hydrazine, and biomass-derived intermediate chemicals, can be integrated with energy-efficient H 2 evolution. We specifically highlight the importance of oxidative biomass valorization coupled with H 2 production, as biomass is the only green carbon source whose scale is comparable to fossil fuels. Finally, the remaining challenges and future opportunities are also discussed.
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Visible-light-driven organic transformations integrated with H 2 production on semiconductors
Due to its clean and sustainable nature, solar energy has been widely recognized as a green energy source in driving a variety of reactions, ranging from small molecule activation and organic transformation to biomass valorization. Within this context, organic reactions coupled with H 2 evolution via semiconductor-based photocatalytic systems under visible light irradiation have gained increasing attention in recent years, which utilize both excited electrons and holes generated on semiconductors and produce two types of value-added products, organics and H 2 , simultaneously. Based on the nature of the organic reactions, in this review article we classify semiconductor-based photocatalytic organic transformations and H 2 evolution into three categories: (i) photocatalytic organic oxidation reactions coupled with H 2 production, including oxidative upgrading of alcohols and biomass-derived intermediate compounds; (ii) photocatalytic oxidative coupling reactions integrated with H 2 generation, such as C–C, C–N, and S–S coupling reactions; and (iii) photo-reforming reactions together with H 2 formation using organic plastics, pollutants, and biomass as the substrates. Representative heterogeneous photocatalytic systems will be highlighted. Specific emphasis will be placed on their synthesis, characterization, and photocatalytic mechanism, as well as the organic reaction scope and practical application.
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- Award ID(s):
- 1914546
- NSF-PAR ID:
- 10207452
- Date Published:
- Journal Name:
- Materials Advances
- Volume:
- 1
- Issue:
- 7
- ISSN:
- 2633-5409
- Page Range / eLocation ID:
- 2155 to 2162
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Aluminyl anions are low‐valent, anionic, and carbenoid aluminum species commonly found stabilized with potassium cations from the reaction of Al‐halogen precursors and alkali compounds. These systems are very reactive toward the activation of
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D0MA00327A
