Nanoscale Janus Z-Scheme Heterojunction for Boosting Artificial Photosynthesis.

Artificial photosynthesis for CO2 reduction coupled with water oxidation currently suffers from low efficiency due to inadequate interfacial charge separation of conventional Z-scheme heterojunctions. Herein, an unprecedented nanoscale Janus Z-scheme heterojunction of CsPbBr3 /TiOx is constructed for photocatalytic CO2 reduction. Benefitting from the short carrier transport distance and direct contact interface, CsPbBr3 /TiOx exhibits significantly accelerated interfacial charge transfer between CsPbBr3 and TiOx (8.90 × 108 s-1 ) compared with CsPbBr3 :TiOx counterpart (4.87 × 107 s-1 ) prepared by traditional electrostatic self-assembling. The electron consumption rate of cobalt doped CsPbBr3 /TiOx can reach as high as 405.2 ± 5.6 µmol g-1 h-1 for photocatalytic CO2 reduction to CO coupled with H2 O oxidation to O2 under AM1.5 sunlight (100 mW cm-2 ), over 11-fold higher than that of CsPbBr3 :TiOx , and surpassing the reported halide-perovskite-based photocatalysts under similar conditions. This work provides a novel strategy to boost charge transfer of photocatalysts for enhancing the performance of artificial photosynthesis.

Constructing S-scheme heterojunction Cs3Bi2Br9/BiOBr via in-situ partial conversion to boost photocatalytic N2 fixation.

The judicious construction of interfaces with swift charge communication to enhance the utilization efficiency of photogenerated carriers is a viable strategy for boosting the photocatalytic performance of heterojunctions. Herein, an in-situ partial conversion strategy is reported for decorating lead-free halide perovskite Cs3Bi2Br9 nanocrystals onto BiOBr hollow nanotube, resulting in the formation of an S-scheme heterojunction Cs3Bi2Br9/BiOBr. This unique in-situ growth approach imparts a closely contacted interface to the Cs3Bi2Br9/BiOBr heterojunction, facilitating interfacial electron transfer and spatial charge separation compared to a counterpart (Cs3Bi2Br9:BiOBr) fabricated via traditional electrostatic self-assembly. Additionally, the establishment of an S-scheme charge transfer pathway preserves the robust redox capability of photogenerated carriers. Furthermore, the free electron transfer from Cs3Bi2Br9 to BiOBr promotes the activation of the NN bond and diminishes the energy barrier associated with the rate-determining step in the N2 reduction process. Consequently, the Cs3Bi2Br9/BiOBr heterojunction exhibits highly selective photocatalytic N2 reduction to NH3 (nearly 100 %) at a rate of 130 µmol g-1 h-1 under simulated sunlight (100 mW cm-2), surpassing BiOBr, Cs3Bi2Br9, and Cs3Bi2Br9:BiOBr by factors of 6, 4, and 2, respectively.