Constructing a heterojunction by combining two semiconductors with similar band structures is a successful approach to obtaining photocatalysts with high efficiency. Herein, a CuPc/DR-MoS2 heterojunction involving copper phthalocyanine (CuPc) and molybdenum disulfide with S-rich vacancies (13.66%) is successfully prepared by the facile hydrothermal method. Experimental results and theoretical calculations firmly demonstrated that photoelectrons exhibit an S-scheme charge transfer mechanism in the CuPc/DR-MoS2 heterojunction. The S-scheme heterojunction system has proven significant advantages in promoting the charge separation and transfer of photogenerated carriers, enhancing visible-light responsiveness, and achieving robust photoredox capability. As a result, the optimized 3CuPc/DR-MoS2 S-scheme heterojunction exhibits photocatalytic yields of CO and CH4 at 200 and 111.6 µmol g-1h-1, respectively. These values are four times and 4.5 times greater than the photocatalytic yields of pure DR-MoS2. This study offers novel perspectives on the advancement of innovative and highly effective heterojunction photocatalysts.
Semiconductor-based photocatalysis has attracted significant interest due to its capacity to directly exploit solar energy and generate solar fuels, including water splitting, CO2 reduction, pollutant degradation, and bacterial inactivation. However, achieving the maximum efficiency in photocatalytic processes remains a challenge owing to the speedy recombination of electron-hole pairs and the limited use of light. Therefore, significant endeavours have been devoted to addressing these issues. Specifically, well-designed heterojunction photocatalysts have been demonstrated to exhibit enhanced photocatalytic activity through the physical distancing of electron-hole pairs generated during the photocatalytic process. In this review, we provide a systematic discussion ranging from fundamental mechanisms to material strategies, focusing on TiO2-based heterojunction photocatalysts. Current efforts are focused on developing heterojunction photocatalysts based on TiO2 for a variety of photocatalytic applications, and these projects are explained and assessed. Finally, we offer a concise summary of the main insights and challenges in the utilization of TiO2-based heterojunction photocatalysts for photocatalysis. We expect that this review will serve as a valuable resource to improve the efficiency of TiO2-based heterojunctions for energy generation and environmental remediation.
Constructing Van der Waals heterojunction is a crucial strategy to achieve excellent photocatalytic activity. However, in most Van der Waals heterojunctions synthesized by ex situ assembly, electron transfer encounters huge hindrances at the interface between the two components due to the large spacing and potential barrier. Herein, a phosphate-bridged Van der Waals heterojunction of cobalt phthalocyanine (CoPc)/tungsten disulfide (WS2 ) bridged by phosphate (xCoPc-nPO4 - -WS2 ) is designed and prepared by the traditional wet chemistry method. By introducing a small phosphate molecule into the interface of CoPc and WS2 , creates an electron "bridge", resulting in a compact combination and eliminating the space barrier. Therefore, the phosphate (PO4 - ) bridge can serve as an efficient electron transfer channel in heterojunction and can efficiently transmit photoelectrons from WS2 to CoPc under excited states. These excited photoelectrons are captured by the catalytic central Co2+ in CoPc and subsequently convert CO2 molecules into CO and CH4 products, achieving 17-fold enhancement on the 3CoPc-0.6PO4 - -WS2 sample compared to that of pure WS2 . Introducing a small molecule "bridge" to create an electron transfer channel provides a new perspective in designing efficient photocatalysts for photocatalytic CO2 reduction into valuable products.
Ammonia and nitrates are the most fundamental and significant raw ingredients in human society. Till now, industrial synthetic ammonia by Haber-Bosch process and industrial synthetic nitrates by the Ostwald process have encountered increasingly serious challenges, i.e., high energy consumption, high cost, and environment-harmful gas emissions. Therefore, developing alternative approaches to achieve nitrogen fixation to overcome the inherent deficiencies of the well-established Haber-Bosch and Ostwald processes has fascinated scientists for many years, especially the simultaneous formation of ammonia and nitrate directly from N2 molecules, which has been rarely studied. Herein, a heterojunction-based photocatalytic system is designed to successfully achieve "overall nitrogen fixation," a sustainable and simultaneous conversion of N2 molecules into ammonia and nitrate products under mild conditions. In this heterojunction, interfacial charge redistribution (ICR) promotes selective accumulations of photogenerated electrons and holes in the CdS and WO3 components. As a result, N2 molecules can be activated and reduced to ammonia products with yields of 35.8 µmol h-1 g-1 by a multi-electron process, and synchronously oxidized into nitrate products with yields of 14.2 µmol h-1 g-1 by a hole-induced oxidation coupling process. This work provides a novel insight and promising approach to realize artificial nitrogen fixation under mild condition.
