Solar CO2 Reduction Enabled by Cascade Hole Migration.

Solar-powered photocatalytic conversion of CO2 to hydrocarbon fuels represents an emerging approach to solving the greenhouse effect. However, low charge separation efficiency, deficiency of surface catalytic active sites, and sluggish charge-transfer kinetics, together with the complicated reaction pathway, concurrently hinder the CO2 reduction. Herein, we show the rational construction of transition metal chalcogenides (TMCs) heterostructure CO2 reduction photosystems, wherein the TMC substrate is tightly integrated with amorphous oxygen-containing cobalt sulfide (CoSOH) by a solid non-conjugated polymer, i.e., poly(vinyl alcohol) (PVA), to customize the unidirectional charge-transfer pathway. In this well-defined multilayered nanoarchitecture, the PVA interim layer intercalated between TMCs and CoSOH acts as a hole-relaying mediator and meanwhile boosts CO2 adsorption capacity, while CoSOH functions as a terminal hole-collecting reservoir, stimulating the charge transport kinetics and boosting the charge separation over TMCs. This peculiar interface configuration and charge transport characteristics endow TMC/PVA/CoSOH heterostructures with significantly enhanced visible-light-driven photoactivity and CO2 conversion. Based on the intermediates probed during the photocatalytic CO2 reduction reaction, the photocatalytic mechanism was determined. Our work would inspire sparkling ideas to mediate the charge transfer over semiconductor for solar carbon neutral conversion.

Self-Transformation of Atomically Precise Alloy Nanoclusters to Plasmonic Alloy Nanocrystals: Evaluating Photosensitization in Solar Water Oxidation.

Atomically precise alloy nanoclusters (NCs) inherit the advantages of homometal NC counterparts such as atomic stacking fashion, quantum confinement effect, and enriched catalytic active sites and simultaneously possess the advantageous physicochemical properties such as significantly enhanced photostability, ideal photosensitization efficiency, and favorable energy band structure. Nevertheless, elucidation of the roles of alloy NCs and alloy nanocrystals (NYs) in boosting solar water oxidation has so far not yet been reported owing to the deficiency of applicable alloy NC photosystems. Herein, utilizing the generic thermal-induced self-transformation of alloy NCs to alloy NYs, we comprehensively explore the photosensitization properties of glutathione (GSH)-capped alloy NCs (AgxAu1-x@GSH and CuxAu1-x@GSH) and the corresponding alloy NY (AgAu and CuAu) counterparts in solar water oxidation reaction. The results imply that photoelectrons of alloy NCs surpass the hot electrons over plasmonic alloy NYs in stimulating the PEC water oxidation reaction. The photoelectrons of alloy NCs demonstrate lower interfacial charge-transfer resistance, longer carrier lifetime, and a more enhanced photosensitization effect with respect to the plasmonic alloy NYs, contributing to the significantly boosted photoelectrochemical water oxidation activities. Moreover, we found that our result is universal.

[Pollution Characteristics and Sources of Wintertime Atmospheric Brown Carbon at a Background Site of the Yangtze River Delta Region in China].

To investigate the pollution characteristics and sources of atmospheric brown carbon (BrC) in Chongming Island, a background site of the Yangtze River Delta (YRD) region in China, PM2.5 samples collected from December 2018 to January 2019 were analyzed to determine their chemical compositions and optical properties. The results showed that the light absorption coefficient (Abs365,M) of BrC extracted by methanol at 365 nm was (5.39±3.33) M-1·m-1, which was 1.3 times of the water extracted BrC. Both increased significantly with the increase of pH values, suggesting that less acidic conditions can enhance the light absorption ability of BrC. In winter, both Abs365 and MAE365 (mass absorption efficiency) were higher in the nighttime than in the daytime. A strong linear correlation observed between Abs365 and levoglucosan (R2=0.72) indicated that many light absorbing substances in Chongming Island were derived from biomass burning emissions. During the campaign, nitro-aromatic compounds (NACs) and PAHs accounted for (1.5±1.1) ng·m-3 and (8.3±4.7) ng·m-3, respectively, contributing to 0.1% and 0.067% of the absorption of the total BrC at 365 nm, respectively. Positive matrix factorization (PMF) analysis further showed that biomass and fossil fuel combustions were the main sources of BrC in Chongming Island in winter, accounting for 56% of the total BrC, followed by secondary formation, accounting for 24% of the total BrC, with road dust contributing only 6%.