Selective CO 2 photoreduction to hydrocarbon fuels such as CH 4 is promising and sustainable for carbonneutral future. However, lack of proper binding strengths with reaction intermediates makes it still a challenge for photocatalytic CO 2 methanation with both high activity and selectivity. Here, low-coordination single Au atoms (Au 1 -S 2 ) on ultrathin ZnIn 2 S 4 nanosheets was synthesized by a complex-exchange route, enabling exceptional photocatalytic CO 2 reduction performance. Under visible light irradiation, Au 1 /ZnIn 2 S 4 catalyst exhibits a CH 4 yield of 275 μmol g À 1 h À 1 with a selectivity as high as 77 %. As revealed by detailed characterizations and density functional theory calculations, Au 1 / ZnIn 2 S 4 with Au 1 -S 2 structure not only display fast carrier transfer to underpin its superior activity, but also greatly reduce the energy barrier for protonation of *CO and stabilize the *CH 3 intermediate, thereby leading to the selective CH 4 generation from CO 2 photoreduction.
Single-atom catalysts (SACs) have recently emerged as promising photocatalysts for CO 2 reduction; however, understanding their interplay between the local electronic structure and the overall performance at an atomic level still remains elusive. Here, we construct two Ni-SACs at different sites of WO 2.72 nanowires, i.e., bulk doping of single Ni atoms in WO 2.72 (B-Ni 1 /WO 2.72 ) and surface anchoring of single Ni atoms on WO 2.72 (S-Ni 1 /WO 2.72 ), to unravel the electronic structure manipulation for boosting CO 2 photoreduction. Impressively, B-Ni 1 /WO 2.72 displays superior photocatalytic CO 2 reduction performance to S-Ni 1 /WO 2.72 , reaching a CO yield of 80.5 mmol g −1 h −1 with a selectivity of 98.7%. Experimental results and computational calculations reveal that compared to S-Ni 1 /WO 2.72 , B-Ni 1 /WO 2.72 is endowed with improved charge transfer and a more upshifted d-band center, thereby leading to CO production with concurrent high activity and selectivity. This work provides deeper insights into the exploration of efficient SACs for artificial photosynthesis to targeted products by optimization of their site-related electronic structures.
Photoconversion of CO2 and H2O into ethanol is an ideal strategy to achieve carbon neutrality. However, the production of ethanol with high activity and selectivity is challenging owing to the less efficient reduction half‐reaction involving multi‐step proton‐coupled electron transfer (PCET), a slow C−C coupling process, and sluggish water oxidation half‐reaction. Herein, a two‐dimensional/two‐dimensional (2D/2D) S‐scheme heterojunction consisting of black phosphorus and Bi2WO6 (BP/BWO) was constructed for photocatalytic CO2 reduction coupling with benzylamine (BA) oxidation. The as‐prepared BP/BWO catalyst exhibits a superior photocatalytic performance toward CO2 reduction, with a yield of 61.3 μmol g−1 h−1 for ethanol (selectivity of 91 %).In situ spectroscopic studies and theoretical calculations reveal that S‐scheme heterojunction can effectively promote photogenerated carrier separation via the Bi−O−P bridge to accelerate the PCET process. Meanwhile, electron‐rich BP acts as the active site and plays a vital role in the process of C−C coupling. In addition, the substitution of BA oxidation for H2O oxidation can further enhance the photocatalytic performance of CO2 reduction to C2H5OH. This work opens a new horizon for exploring novel heterogeneous photocatalysts in CO2 photoconversion to C2H5OH based on cooperative photoredox systems.
Selective CO 2 photoreduction to hydrocarbon fuels such as CH 4 is promising and sustainable for carbonneutral future. However, lack of proper binding strengths with reaction intermediates makes it still a challenge for photocatalytic CO 2 methanation with both high activity and selectivity. Here, low-coordination single Au atoms (Au 1 -S 2 ) on ultrathin ZnIn 2 S 4 nanosheets was synthesized by a complex-exchange route, enabling exceptional photocatalytic CO 2 reduction performance. Under visible light irradiation, Au 1 /ZnIn 2 S 4 catalyst exhibits a CH 4 yield of 275 μmol g À 1 h À 1 with a selectivity as high as 77 %. As revealed by detailed characterizations and density functional theory calculations, Au 1 / ZnIn 2 S 4 with Au 1 -S 2 structure not only display fast carrier transfer to underpin its superior activity, but also greatly reduce the energy barrier for protonation of *CO and stabilize the *CH 3 intermediate, thereby leading to the selective CH 4 generation from CO 2 photoreduction.
Direct ammonia (NH3) synthesis from water and atmospheric nitrogen using sunlight provides an energy‐sustainable and carbon‐neutral alternative to the Haber–Bosch process. However, the development of such a route with high performance is impeded by the lack of effective charge transfer and abundant active sites to initiate the nitrogen reduction reaction (NRR). Here, the authors report efficient plasmon‐induced photoelectrochemical (PEC) NH3 synthesis on the hierarchical free‐standing Au/KxMoO3/Mo/KxMoO3/Au nanoarrays. Endowed with energetically hot electrons and catalytically active sites, the plasmonic nanoarrays exhibit an efficient PEC NH3 synthesis rate of 9.6 µg cm−2 h−1 under visible light irradiation, which is among the highest PEC NRR systems. This work demonstrates the rationally designed plasmonic nanoarrays for highly efficient NH3 synthesis, which paves a new path for PEC catalytic reactions driven by surface plasmons and future monolithic PEC devices for direct artificial photosynthesis.
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