Polymer Donor with a Simple Skeleton and Minor Siloxane Decoration Enables 19% Efficiency of Organic Solar Cells.

Development of polymer donors with simple chemical structure and low cost is of great importance for commercial application of organic solar cells (OSCs). Here, side-chain random copolymer PMQ-Si605 with a simply 6,7-difluoro-3-methylquinoxaline-thiophene backbone and 5% siloxane decoration of side chain is synthesized in comparison with its alternating copolymer PTQ11. Relative to molecular weight (Mn) of 28.3 kg mol-1 for PTQ11, the random copolymer PMQ-Si605 with minor siloxane decoration is beneficial for achieving higher Mn up to 51.1 kg mol-1. In addition, PMQ-Si605 can show stronger aggregation ability and faster charge mobility as well as more efficient exciton dissociation in active layer as revealed by femtosecond transient absorption spectroscopy. With L8-BO-F as acceptor, its PMQ-Si605 based OSCs display power conversion efficiency (PCE) of 18.08%, much higher than 16.21% for PTQ11 based devices. With another acceptor BTP-H2 to optimize the photovoltaic performance of PMQ-Si605, further elevated PCEs of 18.50% and 19.15% can be achieved with the binary and ternary OSCs, respectively. Furthermore, PMQ-Si605 based active layers are suitable for processing in high humidity air, an important factor for massive production of OSCs. Therefore, the siloxane decoration on polymer donors is promising, affording PMQ-Si605 as a high-performing and low cost candidate.

Photocatalytic Co-Reduction of N2 and CO2 with CeO2 Catalyst for Urea Synthesis.

The effective conversion of carbon dioxide (CO2 ) and nitrogen (N2 ) into urea by photocatalytic reaction under mild conditions is considered to be a more environmentally friendly and promising alternative strategies. However, the weak adsorption and activation ability of inert gas on photocatalysts has become the main challenge that hinder the advancement of this technique. Herein, we have successfully established mesoporous CeO2-x nanorods with adjustable oxygen vacancy concentration by heat treatment in Ar/H2 (90 % : 10 %) atmosphere, enhancing the targeted adsorption and activation of N2 and CO2 by introducing oxygen vacancies. Particularly, CeO2 -500 (CeO2 nanorods heated treatment at 500 °C) revealed high photocatalytic activity toward the C-N coupling reaction for urea synthesis with a remarkable urea yield rate of 15.5 µg/h. Besides, both aberration corrected transmission electron microscopy (AC-TEM) and Fourier transform infrared (FT-IR) spectroscopy were used to research the atomic surface structure of CeO2 -500 at high resolution and to monitor the key intermediate precursors generated. The reaction mechanism of photocatalytic C-N coupling was studied in detail by combining Density Functional Theory (DFT) with specific experiments. We hope this work provides important inspiration and guiding significance towards highly efficient photocatalytic synthesis of urea.

Type II Heterojunction Formed between {010} or {012} Facets Dominated Bismuth Vanadium Oxide and Carbon Nitride to Enhance the Photocatalytic Degradation of Tetracycline.

Both type II and Z schemes can explain the charge transfer behavior of the heterojunction structure well, but the type of heterojunction structure formed between bismuth vanadium oxide and carbon nitride still has not been clarified. Herein, we rationally prepared bismuth vanadium oxide with {010} and {012} facets predominantly and carbon nitride as a decoration to construct a core-shell structure with bismuth vanadium oxide wrapped in carbon nitride to ensure the same photocatalytic reaction interface. Through energy band establishment and radical species investigation, both {010} and {012} facets dominated bismuth vanadium oxide/carbon nitride composites exhibit the type II heterojunction structures rather than the Z-scheme heterojunctions. Furthermore, to investigate the effect of type II heterojunction, the photocatalytic tetracycline degradations were performed, finding that {010} facets dominated bismuth vanadium oxide/carbon nitride composite demonstrated the higher degradation efficiency than that of {012} facets, due to the higher conduction band energy. Additionally, through the free radical trapping experiments and intermediate detection of degradation products, the superoxide radical was proven to be the main active radical to decompose the tetracycline molecules. Therein, the tetracycline molecules were degraded to water and carbon dioxide by dihydroxylation-demethylation-ring opening reactions. This work investigates the effect of crystal planes on heterojunction types through two different exposed crystal planes of bismuth vanadate oxide, which can provide some basic research and theoretical support for the progressive and controlled synthesis of photocatalysts with heterojunction structures.