Cu₇S₄/M_xS_y (M=Cd, Ni, and Mn) Janus Atomic Junctions for Plasmonic Energy Upconversion Boosted Multi‐Functional Photocatalysis

Abstract

Rational design/synthesis of atomic‐level‐engineered Janus junctions for sunlight‐impelled high‐performance photocatalytic generation of clean fuels (e.g., H2O2 and H2) and valuable chemicals are of great significance. Especially, it is appealing but challenging to acquire accurately‐engineered Janus atomic junctions (JAJs) for simultaneously realizing the plasmonic energy upconversion with near‐infrared (NIR) light and direct Z‐scheme charge transfer with visible light. Here, a range of new Cu7S4/MxSy (M=Cd, Ni, and Mn) JAJs are designed/synthesized via a cation‐exchange route using Cu7S4 hexagonal nanodisks as templates. All Cu7S4/MxSy JAJs show apparently‐enhanced photocatalytic H2O2 evolution compared to Cu7S4 in pure water. Notably, optimized Cu7S4/CdS (CCS) JAJ exhibits the outstanding H2O2 evolution rate (2.93 mmol g−1 h−1) in benzyl alcohol aqueous solution, due to the following factors: i) NIR light‐impelled plasmonic energy upconversion induced H2O2 evolution, revealed by ultrafast transient absorption spectroscopy; ii) visible‐light‐driven direct Z‐scheme charge migration, confirmed by in situ X‐ray photoelectron spectroscopy. Besides, three different reaction pathways for H2O2 evolution are disclosed by in situ electron spin resonance spectroscopy and quenching experiments. Finally, CCS JAJ also exhibits super‐high rates on H2 and benzaldehyde co‐generation using visible‐NIR light or NIR light. This work highlights the significance of atomic‐scale interface engineering for solar‐to‐chemical conversion.

Engineering Reaction Pathway to Harmonize the Competition between NRR and HER for Efficient Photocatalytic Ammonia Synthesis

“…Such trade-off between the product yield and reaction selectivity severely limits the overall efficiency of NRR. Similar situations also occur in numerous oxidation/reduction reactions including carbon dioxide reduction reaction (CO 2 RR) , and oxygen reduction reaction (ORR). − …”

Plasmon-Enhanced Perovskite Photocatalysts for CO2 Reduction: A Mini Review

“…Therefore, to improve the photocatalytic performance of the pure plasmon–perovskite system, further developments are necessary. These improvements may be realized through the integration of various strategies, including heterojunction engineering, structural engineering, atomic-scale interface engineering, and surface engineering. ,,,, …”

“…These improvements may be realized through the integration of various strategies, including heterojunction engineering, structural engineering, atomic-scale interface engineering, and surface engineering. 24,28,47,100,101 Fortunately, the current development and application in the field of artificial intelligence seem to be able to achieve theoretical predictions and self-design of plasmon−perovskite photocatalysts, thereby saving a lot of time and cost to rapidly screen and effectively design more novel photocatalytic systems, which inspires further research and exploration. 102,103 Moreover, molecular dynamics simulation calculation is also very attractive for a deeper understanding of the photocatalyst reaction mechanism.…”

Recent advancement on photocatalytic plastic upcycling

“…1–33 Among these techniques, photocatalysis stands out as a cost-effective, environmentally-benign and green strategy able to upcycle plastic wastes at ambient temperature and pressure utilizing renewable sunlight. 34–79 A photocatalysis reaction conducted in mild conditions is anticipated to accurately activate target chemical bonds, while reserving the other functional groups, thus realizing high selectivity to desirable products. 34–49…”