Bifunctional Cu₃P Decorated g-C₃N₄ Nanosheets as a Highly Active and Robust Visible-Light Photocatalyst for H₂ Production

Abstract

The rational design of sustainable noble-metal-free heterojunctions remains a key challenge for highly efficient and durable photocatalytic H2 production. In this study, it was revealed that the robust copper phosphide (Cu3P) nanoparticles may serve as a cocatalyst and a p-type semiconductor at low (1.5 wt %) and high (10 wt %) loading contents, respectively. Both Cu3P cocatalyst and semiconductor could evidently boost visible-light-driven photocatalytic H2 production over graphitic carbon nitride (g-C3N4) nanosheets. Comparably speaking, the heterojunction effects between p-type Cu3P and n-type g-C3N4 are speculated to play a more prominent role in dramatically boosting photocatalytic H2 production than the electron-sink roles of surface Cu3P cocatalysts. Impressively, among all the as-fabricated photocatalysts, high quality 10 wt % g-C3N4–Cu3P could achieve the highest photocatalytic H2-production rate of 159.41 μmol g–1 h–1, which is approximately 1014 times higher than that of pristine g-C3N4. In cycling experiments, g-C3N4–10 wt % Cu3P exhibited an acceptable photostability. More importantly, it was further demonstrated that earth-abundant dual-functional Cu3P nanoparticles could markedly facilitate the separation of electron–hole pairs and H2-evolution kinetics, thus achieving distinctly boosted photocatalytic H2 generation. This work will provide new insights into the rational design of environmentally friendly g-C3N4-based hybrid nanoheterojunctions for visible-light-responsive photocatalytic H2 generation through loading noble-metal-free bifunctional cocatalysts on semiconductors.

Acid‐treated g‐C3N4‐Cu2O composite catalyst with enhanced photocatalytic activity under visible‐light irradiation

“…Semiconductor‐based photocatalysis has been recognized as one of the most promising technologies for addressing environmental pollution and the energy crisis that our current global concerns . At the time of writing, the development of visible‐light‐driven photocatalysts is attracting considerable attention from researchers.…”

3D‐Graphene Decorated with g‐C3N4/Cu3P Composite: A Noble Metal‐free Bifunctional Electrocatalyst for Overall Water Splitting

“…(Figure d–i) The structure and morphology of the 3DG‐Mix sample are characterized via SEM (Figure b) and high‐resolution TEM (HR‐TEM) shown in Figure c where lattice fringes of individual material are clearly been observed. The lattice fringes of 0.24 nm, 0.20 nm, 0.17 nm correspond to the plan of (112), (300) and (220) of hexagonal Cu 3 P and that of 0.33 nm for the graphitic layers refers to (002) plane of both graphene and g‐C 3 N 4 . Nevertheless, it is very difficult to visualize the g‐C 3 N 4 nanosheet lattice spacing separately in the 3DG‐graphene matrix due to the presence of a very low amount of g‐C 3 N 4 compared to graphene.…”

Apparent Potential Difference Boosting Directional Electron Transfer for Full Solar Spectrum‐Irradiated Catalytic H2 Evolution

“…In time‐resolved fluorescence spectra (Figure f), the decay spectra of the samples have been fitted into two lifetime steps of τ 1 and τ 2 , in which τ 1 corresponds to the radiative lifetime (recombination process), and τ 2 reflects the nonradiative lifetime of charge carriers (utilization process). The relative proportion of charge carriers (Rel%) involved in the two steps were also presented . All these parameters for samples were collected in Table S3 (Supporting Information).…”