2D/2D Heterojunction of Ultrathin MXene/Bi2WO6 Nanosheets for Improved Photocatalytic CO2 Reduction

The generation of green hydrogen (H2 ) energy using sunlight is of great significance to solve the worldwide energy and environmental issues. Particularly, photocatalytic H2 production is a highly promising strategy for solar-to-H2 conversion. Recently, various heterostructured photocatalysts with high efficiency and good stability have been fabricated. Among them, 2D/2D van der Waals (VDW) heterojunctions have received tremendous attention, since this architecture can promote the interfacial charge separation and transfer and provide massive reactive centers. On the other hand, currently, most photocatalysts are composed of metal elements with high cost, limited reserves, and hazardous environmental impact. Hence, the development of metal-free photocatalysts is desirable. Here, a novel 2D/2D VDW heterostructure of metal-free phosphorene/graphitic carbon nitride (g-C3 N4 ) is fabricated. The phosphorene/g-C3 N4 nanocomposite shows an enhanced visible-light photocatalytic H2 production activity of 571 µmol h-1 g-1 in 18 v% lactic acid aqueous solution. This improved performance arises from the intimate electronic coupling at the 2D/2D interface, corroborated by the advanced characterizations techniques, e.g., synchrotron-based X-ray absorption near-edge structure, and theoretical calculations. This work not only reports a new metal-free phosphorene/g-C3 N4 photocatalyst but also sheds lights on the design and fabrication of 2D/2D VDW heterojunction for applications in catalysis, electronics, and optoelectronics.

Metal-free 2D/2D phosphorene/g-C₃N₄ van der Waals heterojunction for highly enhanced visible-light photocatalytic H₂ production

Photocatalysis is the most promising method for achieving artificial photosynthesis, but a bottleneck is encountered in finding materials that could efficiently promote the water splitting reaction. The nontoxicity, low cost, and versatility of photocatalysts make them especially attractive for this application. This study demonstrates that small amounts of α-Fe2O3 nanosheets can actively promote exfoliation of g-C3N4, producing 2D hybrid that exhibits tight interfaces and an all-solid-state Z-scheme junction. These nanostructured hybrids present a high H2 evolution rate >3 × 104 µmol g-1 h-1 and external quantum efficiency of 44.35% at λ = 420 nm, the highest value so far reported among the family of g-C3N4 photocatalysts. Besides effectively suppressing the recombination of electron–hole pairs, this Z-scheme junction also exhibits activity toward overall water splitting without any sacrificial donor. The proposed synthetic route for controlled production of 2D g-C3N4-based structures provides a scalable alternative toward the development of highly efficient and active photocatalysts.

High Efficiency Photocatalytic Water Splitting Using 2D α-Fe2O3/g-C3N4 Z-Scheme Catalysts

Two-dimensional (2D) materials have attracted increasing attention for photocatalytic applications because of their unique thickness dependent physical and chemical properties. This review gives a brief overview of the recent developments concerning the chemical synthesis and structural design of 2D materials at the nanoscale and their applications in photocatalytic areas. In particular, recent progress on the emerging strategies for tailoring 2D material-based photocatalysts to improve their photo-activity including elemental doping, heterostructure design and functional architecture assembly is discussed.

Recent advances in 2D materials for photocatalysis

N2 fixation by the electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions is regarded as a potential approach to achieve NH3 production, which still heavily relies on the Haber-Bosch process at the cost of huge energy and massive production of CO2 . A noble-metal-free Bi4 V2 O11 /CeO2 hybrid with an amorphous phase (BVC-A) is used as the cathode for electrocatalytic NRR. The amorphous Bi4 V2 O11 contains significant defects, which play a role as active sites. The CeO2 not only serves as a trigger to induce the amorphous structure, but also establishes band alignment with Bi4 V2 O11 for rapid interfacial charge transfer. Remarkably, BVC-A shows outstanding electrocatalytic NRR performance with high average yield (NH3 : 23.21 μg h-1  mg-1cat. , Faradaic efficiency: 10.16 %) under ambient conditions, which is superior to the Bi4 V2 O11 /CeO2 hybrid with crystalline phase (BVC-C) counterpart.

An Amorphous Noble-Metal-Free Electrocatalyst that Enables Nitrogen Fixation under Ambient Conditions.

Two-dimensional-layered heterojunctions have attracted extensive interest recently due to their exciting behaviours in electronic/optoelectronic devices as well as solar energy conversion systems. However, layered heterojunction materials, especially those made by stacking different monolayers together by strong chemical bonds rather than by weak van der Waal interactions, are still challenging to fabricate. Here the monolayer Bi2WO6 with a sandwich substructure of [BiO](+)-[WO4](2-)-[BiO](+) is reported. This material may be characterized as a layered heterojunction with different monolayer oxides held together by chemical bonds. Coordinatively unsaturated Bi atoms are present as active sites on the surface. On irradiation, holes are generated directly on the active surface layer and electrons in the middle layer, which leads to the outstanding performances of the monolayer material in solar energy conversion. Our work provides a general bottom-up route for designing and preparing novel monolayer materials with ultrafast charge separation and active surface.

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Yongfan Zhang

Papers

Monolayered Bi2WO6 nanosheets mimicking heterojunction interface with open surfaces for photocatalysis.