Photocatalysis may provide an intriguing approach to nitrogen fixation, which relies on the transfer of photoexcited electrons to the ultrastable N≡N bond. Upon N chemisorption at active sites (e.g., surface defects), the N molecules have yet to receive energetic electrons toward efficient activation and dissociation, often forming a bottleneck. Herein, we report that the bottleneck can be well tackled by refining the defect states in photocatalysts via doping. As a proof of concept, WO ultrathin nanowires are employed as a model material for subtle Mo doping, in which the coordinatively unsaturated (CUS) metal atoms with oxygen defects serve as the sites for N chemisorption and electron transfer. The doped low-valence Mo species play multiple roles in facilitating N activation and dissociation by refining the defect states of WO: (1) polarizing the chemisorbed N molecules and facilitating the electron transfer from CUS sites to N adsorbates, which enables the N≡N bond to be more feasible for dissociation through proton coupling; (2) elevating defect-band center toward the Fermi level, which preserves the energy of photoexcited electrons for N reduction. As a result, the 1 mol % Mo-doped WO sample achieves an ammonia production rate of 195.5 μmol g h, 7-fold higher than that of pristine WO. In pure water, the catalyst demonstrates an apparent quantum efficiency of 0.33% at 400 nm and a solar-to-ammonia efficiency of 0.028% under simulated AM 1.5 G light irradiation. This work provides fresh insights into the design of photocatalyst lattice for N fixation and reaffirms the versatility of subtle electronic structure modulation in tuning catalytic activity.
Single-atom photocatalysts have shown their compelling potential and arguably become the most active research direction in photocatalysis due to their fascinating strengths in enhancing light-harvesting, charge transfer dynamics, and surface reactions of a photocatalytic system. While numerous comprehensions about the single-atom photocatalysts have recently been amassed, advanced characterization techniques and vital theoretical studies are strengthening our understanding on these fascinating materials, allowing us to forecast their working mechanisms and applications in photocatalysis. In this review, we begin by describing the general background and definition of the single-atom photocatalysts. A brief discussion of the metal−support interactions on the single-atom photocatalysts is then provided. Thereafter, the current available characterization techniques for single-atom photocatalysts are summarized. After having some fundamental understanding on the single-atom photocatalysts, their advantages and applications in photocatalysis are discussed. Finally, we end this review with a look into the remaining challenges and future perspectives of single-atom photocatalysts. We anticipate that this review will provide some inspiration for the future discovery of the single-atom photocatalysts, manifestly stimulating the development in this emerging research area.
Photocatalytic conversion of CO to CH, a carbon-neutral fuel, represents an appealing approach to remedy the current energy and environmental crisis; however, it suffers from the large production of CO and H by side reactions. The design of catalytic sites for CO adsorption and activation holds the key to address this grand challenge. In this Article, we develop highly selective sites for photocatalytic conversion of CO to CH by isolating Cu atoms in Pd lattice. According to our synchrotron-radiation characterizations and theoretical simulations, the isolation of Cu atoms in Pd lattice can play dual roles in the enhancement of CO-to-CH conversion: (1) providing the paired Cu-Pd sites for the enhanced CO adsorption and the suppressed H evolution; and (2) elevating the d-band center of Cu sites for the improved CO activation. As a result, the PdCu-TiO photocatalyst achieves the high selectivity of 96% for CH production with a rate of 19.6 μmol g h. This work provides fresh insights into the catalytic site design for selective photocatalytic CO conversion, and highlights the importance of catalyst lattice engineering at atomic precision to catalytic performance.
A heterogeneous catalyst made of well-defined Co3 O4 hexagonal platelets with varied exposed facets is coupled with [Ru(bpy)3 ]Cl2 photosensitizers to effectively and efficiently reduce CO2 under visible-light irradiation. Systematic investigation based on both experiment and theory discloses that the exposed {112} facets are crucial for activating CO2 molecules, giving rise to significant enhancement of photocatalytic CO2 reduction efficiency.
Visible-light-driven conversion of CO into chemical fuels is an intriguing approach to address the energy and environmental challenges. In principle, light harvesting and catalytic reactions can be both optimized by combining the merits of homogeneous and heterogeneous photocatalysts; however, the efficiency of charge transfer between light absorbers and catalytic sites is often too low to limit the overall photocatalytic performance. In this communication, it is reported that the single-atom Co sites coordinated on the partially oxidized graphene nanosheets can serve as a highly active and durable heterogeneous catalyst for CO conversion, wherein the graphene bridges homogeneous light absorbers with single-atom catalytic sites for the efficient transfer of photoexcited electrons. As a result, the turnover number for CO production reaches a high value of 678 with an unprecedented turnover frequency of 3.77 min , superior to those obtained with the state-of-the-art heterogeneous photocatalysts. This work provides fresh insights into the design of catalytic sites toward photocatalytic CO conversion from the angle of single-atom catalysis and highlights the role of charge kinetics in bridging the gap between heterogeneous and homogeneous photocatalysts.
Heterogeneous catalysts have been widely used for photocatalysis, which is a highly important process for energy conversion, owing to their merits such as easy separation of catalysts from the reaction products and applicability to continuous chemical industry and recyclability. Yet, homogenous photocatalysis receives tremendous attention as it can offer a higher activity and selectivity with atomically dispersed catalytic sites and tunable light absorption. For this reason, there is a major trend to combine the advantages of both homogeneous and heterogeneous photocatalysts, in which coordination chemistry plays a role as the bridge. In this article, we aim to provide the first systematic review to give a clear picture of the recent progress from taking advantage of coordination chemistry. We specifically summarize the role of coordination chemistry as a versatile tool to engineer catalytically active sites, tune light harvesting and maneuver charge kinetics in heterogeneous photocatalysis. We then elaborate on the common fundamentals behind various materials systems, together with key spectroscopic characterization techniques and remaining challenges in this field. The typical applications of coordination chemistry in heterogeneous photocatalysis, including proton reduction, water oxidation, carbon dioxide reduction and organic reactions, are highlighted.
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