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Carbon nitride (CN) has attracted intensive attention as a visible light photocatalyst, but the rapid recombination of photogenerated charge carriers limits its photocatalytic activity. Herein, we develop a new strategy to construct both homojunction and ohmic junction into CN via selectively introducing metallized CN (MCN), which leads to rapid separation and transfer of photogenerated charge carriers. The polymerization of urea in the presence of KOH creates CN homojunction with amino and cyano groups. The subsequent molten salt treatment induces a new type of cyano-terminated CN that can be converted to MCN through photodoping, forming homojunction and ohmic contact coexisting CN (HOCN). The formed HOCN photocatalyst exhibits a high photocatalytic H2 evolution rate of 18.5 mmol·g−1·h−1 under visible light irradiation, 45-fold higher than that of bulk CN. This strategy provides a new idea for designing ohmic contact between semiconductor and metal, and realizing efficient photocatalysis by improving charge separation and transfer. [ABSTRACT FROM AUTHOR]

Cadmium sulfide has attracted wide attention in photocatalytic hydrogen production, due to its appropriate bandgap and band positions. However, high‐rate photogenerated electron–hole recombination and few active sites on CdS lead to its low photocatalytic activity. Herein, a PANI/NCPP/CdS (PANI/NiCoP/NiCoPi/CdS) hybrid as a noble metal‐free visible light‐driven photocatalyst is reported, with metal phosphides, metal phosphates, and polyaniline (PANI) as reduction and oxidation cocatalysts, respectively. This hybrid not only facilitates the charge separation and transfer owing to the formation of heterojunction, but also improves the local concentration of H+ on the surface of catalysts due to the formation of the protonated amine groups on PANI, beneficial to hydrogen evolution reaction. As a result, the as‐prepared photocatalyst could show a high hydrogen evolution rate of 170.3 mmol g−1 h−1 and an apparent quantum efficiency of 41.37% at 420 nm, representing one of the best performances of all‐CdS‐based photocatalysts. [ABSTRACT FROM AUTHOR]

[Display omitted] • The AgBr/HCCN photocatalyst was fabricated using an electric self-assembly approach. • The hybrid photocatalyst features an all-solid-state direct Z-scheme heterojunction. • The Z-scheme heterojunction improves the photogenerated charge carriers' separation. • The contact level of the heterojunction affects the performance of the photocatalyst. • The AgBr/HCCN photocatalyst exhibits a 5.4-fold enhancement in hydrogen evolution. Constructing a Z-scheme heterojunction with enhanced photocatalytic hydrogen evolution for graphitic carbon nitride-based (g-C 3 N 4) composites is challenging because integrating g-C 3 N 4 with other semiconductors, without specific band structure design, typically results in type I or type II heterojunctions. These heterojunctions have lower redox ability and limited enhancement in photocatalysis. Herein, we select highly crystalline carbon nitride (HCCN) as a proof-of-concept substrate. For the first time, we develop a AgBr nanosphere/HCCN composite photocatalyst that features an all-solid-state direct Z-scheme heterojunction for visible-light photocatalytic hydrogen evolution. The electron transfer mechanism is initially studied from the band structures and Fermi levels of HCCN and AgBr. It is subsequently confirmed by X-ray photoelectron spectroscopy (XPS), and electron microscopy. The close heterojunction contact and the built-in electron field of the Z-scheme heterojunction promote the migration and separation of photogenerated electrons and holes in the composite photocatalyst. Due to the redistribution of charge carriers, the photocatalyst shows superior redox capability and a markedly enhanced hydrogen evolution performance compared to its individual components. Combining all the advantages, AgBr nanosphere/HCCN reached an apparent quantum efficiency (AQE) of 6 % under the illumination of 410 nm, which is 4 times higher than that of the single HCCN component. [ABSTRACT FROM AUTHOR]

[Display omitted] • A sufficient and tunable ohmic junction can be built in allochroic Pt/CN. • The ohmic contact is formed by the photoconversion of semiconducting CN to metalloid. • The reversible photoconversion of CN is accompanied with a color change. • The ohmic contact between Pt and CN significantly enhances the HER activity. • The deactivation and regeneration mechanisms of the allochroic Pt/CN are proposed. The direct hybridization of Pt and g-C 3 N 4 generally forms a Schottky barrier between the two components, which unavoidably hinders the migration of photogenerated electrons from g-C 3 N 4 to the Pt cocatalyst. Herein, we report the first efficient allochroic Pt/g-C 3 N 4 photocatalyst that can form an ohmic contact through photoconversion of semiconducting g-C 3 N 4 to metalloid, accompanied with the charge carrier storage and photocatalyst color change, which is proved experimentally and theoretically. Through intermittent exposure of Pt/g-C 3 N 4 photocatalyst to air for a few minutes during photocatalysis, the photocatalyst shows the highest hydrogen evolution performances. The ohmic contacts greatly promote the electron transfer from the semiconducting g-C 3 N 4 to the Pt cocatalyst driven by the built-in electric field. In addition, the mechanism for the photocatalyst deactivation and activation is presented. The compositional tuning of the allochroic g-C 3 N 4 through light irradiation and exposure to air can control over the photocatalytic activity and long-term stability for hydrogen evolution. This report for the first time unveils the deactivation and regeneration mechanisms of SCN. [ABSTRACT FROM AUTHOR]