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Titanium dioxide nanoparticles co-modified with CuOx (0≤x≤2) and carbonaceous materials were prepared with a simple hydrolysis and photo-reduction method for photocatalytic hydrogen generation. SEM/TEM and XPS analysis indicated that the carbonaceous materials were mostly coated on the TiO2 surface and clearly revealed that the Cu species exhibited multivalence states, existing as CuOx (0≤x≤2). The optimal catalyst showed a 56-fold enhanced hydrogen evolution rate compared with that of the pure C/TiO2 catalyst. Further, an intensive multiple electron transfer effect originating from CuOx and the carbonaceous materials is proposed to be responsible for the elevated photoactivity. CuOx species serve as electron donors facilitating charge carrier transfer and proton reduction sites. The carbonaceous materials function as the “bridge” that transfers the electrons of TiO2 to the CuOx species, which provides a new route for electron transfer and reinforces the effect of CuOx as a co-catalyst. In this study, the CuOx and C co-modified TiO2 catalyst was prepared with multiple electron transport pathways and enhanced hydrogen production evolution, which provides a deep understanding for the design of co-catalyst-based photocatalysts. [ABSTRACT FROM AUTHOR]

Extensively spectral-responsive photocatalytic hydrogen production was achieved over g-C3N4 photo-sensitized by Au nanoparticles. The photo-sensitization, which was achieved by a facile photo-assisted reduction route, resulted in an extended spectral range of absorption from 460 to 640 nm. The photo-sensitized g-C3N4 (Au/g-C3N4) photocatalysts exhibit significantly enhanced photocatalytic hydrogen evolution with a TOF value of 223 μmol g-1 h-1, which is a 130-fold improvement over g-C3N4. The hydrogen production result confirms that Au nanoparticles are effective photo-sensitizers for the visible light-responsive substrate g-C3N4. UV–vis diffuse reflection spectra (DRS), photoluminescence spectra (PL), electron spin resonance (ESR), and electrochemical measurements were used to investigate the transfer process of photogenerated electrons. The optimal Au/g-C3N4 photocatalyst displays the lowest charge transfer resistance of 18.45 Ω cm-2 and a high electron transfer efficiency, as determined by electrochemical impedance spectroscopy (EIS). The photo-sensitized g-C3N4 shows a broad range of response to visible light (400–640 nm), with significantly high incident photon-to-current efficiency (IPCE) values of 14.52%, 2.9%, and 0.74% under monochromatic light irradiation of 400, 550, and 640 nm, respectively. ESR characterization suggests that Au nanoparticles are able to absorb visible light of wavelengths higher than 460 nm and to generate hot electrons due to the SPR effect. [ABSTRACT FROM AUTHOR]