Understanding the cascade heterojunction of CuPc/Bi-MOF for photoelectrochemical nitrate reduction.

Herein, a CuPc/Bi-MOF cascade heterojunction is synthesized exhibiting an excellent NH3 yield (7.13 µg h-1 cm-2) and stability. Characterization studies show that the cascade heterostructure with a unique morphology and oxygen vacancies offers new insights into future photoelectrocatalytic material design.

Understanding the Z-scheme heterojunction of BiVO4/PANI for photoelectrochemical nitrogen reduction.

Based on the idea that a heterojunction can significantly promote photoelectrochemical (PEC) efficiency, BiVO4/PANI (polyaniline), as a Z-scheme heterojunction, was designed in this work. BiVO4/PANI achieved a desirable NH3 yield rate (rNH3 = 0.93 µg h-1 cm-2) and faradaic efficiency (FE = 26.43%). This study presents novel insight into PEC NRR research, and it could be extended to the modification of other catalysts for boosting PEC N2 reduction reaction performance.

A NIR-Responsive Phytic Acid Nickel Biomimetic Complex Anchored on Carbon Nitride for Highly Efficient Solar Hydrogen Production.

A challenge in photocatalysis consists in improving the efficiency by harnessing a large portion of the solar spectrum. We report the design and realization of a robust molecular-semiconductor photocatalytic system (MSPS) consisting of an earth-abundant phytic acid nickel (PA-Ni) biomimetic complex and polymeric carbon nitride (PCN). The MSPS exhibits an outstanding activity at λ=940 nm with high apparent quantum efficiency (AQE) of 2.8 %, particularly λ>900 nm, as it outperforms all reported state-of-the-art near-infrared (NIR) hybrid photocatalysts without adding any noble metals. The optimum hydrogen (H2 ) production activity was about 52 and 64 times higher with respect to its pristine counterpart under the AM 1.5 G and visible irradiation, respectively, being equivalent to the platinum-assisted PCN. This work sheds light on feasible avenues to prepare highly active, stable, cheap NIR-harvesting photosystems toward sustainable and scalable solar-to-H2 production.

Multiple Doped Carbon Nitrides with Accelerated Interfacial Charge/Mass Transportation for Boosting Photocatalytic Hydrogen Evolution.

The interaction of water molecule with catalysts is crucial to photocatalysis, but the surface property manipulation still remains a great challenge. In this study, we report an in situ multiple heteroelement (sodium, oxygen, and iodide) doping strategy based on a molten salt-assisted route to prepare a green-colored carbon nitride (GCN). The as-prepared GCN yields 25.5 times higher H2 evolution rate than that of bulk polymeric carbon nitride under visible light. Experimental characterization data demonstrate that the GCN delivers upshift of the conduction band and increased specific surface area and hydrophilicity. As confirmed by time-resolved PL spectra, DMPO spin-trapping EPR analysis, and so on, the excellent activity is dominantly ascribed to the greatly enhanced hydrophilicity and, subsequently, efficient interfacial charge transfer and hydrogen liberation. Moreover, through surface charge modification, the GCN also shows an increased degradation activity of rhodamine B. This work highlights the importance of surface modulation through multiple earth-abundant element incorporation for designing of advanced and practical photocatalysts.

One-Step Nickel Foam Assisted Synthesis of Holey G-Carbon Nitride Nanosheets for Efficient Visible-Light Photocatalytic H2 Evolution.

Graphitic carbon nitride (g-C3N4) with layered structure represents one of the most promising metal-free photocatalysts. As yet, the direct one-step synthesis of ultrathin g-C3N4 nanosheets remains a challenge. Here, few-layered holey g-C3N4 nanosheets (CNS) were fabricated by simply introducing a piece of nickel foam over the precursors during the heating process. The as-prepared CNS with unique structural advantages exhibited superior photocatalytic water splitting activity (1871.09 µmol h-1 g-1) than bulk g-C3N4 (BCN) under visible light (λ > 420 nm) (≈31 fold). Its outstanding photocatalytic performance originated from the high specific surface area (240.34 m2 g-1) and mesoporous structure, which endows CNS with more active sites, efficient exciton dissociation, and prolonged charge carrier lifetime. Moreover, the obvious upshift of the conduction band leads to a larger thermodynamic driving force for photocatalytic proton reduction. This methodology not only had the advantages for the direct and green synthesis of g-C3N4 nanosheets but also paved a new avenue to modify molecular structure and textural of g-C3N4 for advanced applications.

Precisely tunable thickness of graphitic carbon nitride nanosheets for visible-light-driven photocatalytic hydrogen evolution.

Graphitic carbon nitride (GCN) nanosheets with unique physicochemical properties have received increasing attention in the area of photocatalysis, yet tunable thickness for the straightforward production of this graphite-like two-dimensional (2D) nanomaterial remains a challenge. In this work, GCN nanosheets with different thicknesses were firstly prepared by a direct calcination of melamine supramolecular aggregates (MSA) obtained from a hydrochloric acid (HCl)-induced hydrothermal assembly approach. The resultant nanosheets over nanometer scale thickness could be precisely controlled via simply adjusting the HCl concentration. Compared to the bulk GCN (BGCN), the thinner nanosheets possessed a high specific surface area, a large electronic-band structure, and fast charge separation ability. The thinnest nanosheets with a thickness of approximately 4 nm exhibited excellent visible-light-driven photocatalytic water splitting performance in hydrogen evolution (524 µmol h-1 g-1), which is over 9-fold higher than the BGCN powder. This work provides a thickness-dependent strategy for the preparation of metal-free GCN nanosheets and develops a promising 2D photocatalyst for application in solar energy conversion.