Semiconductor polymeric graphitic carbon nitride (g-C3N4) photocatalysts have attracted dramatically growing attention in the field of the visible-light-induced hydrogen evolution reaction (HER) because of their facile synthesis, easy functionalization, attractive electronic band structure, high physicochemical stability and photocatalytic activity. This review article presents a panorama of the latest advancements in the rational design and development of g-C3N4 and g-C3N4-based composite photocatalysts for HER application. Concretely, the review starts with the development history, synthetic strategy, electronic structure and physicochemical characteristics of g-C3N4 materials, followed by the rational design and engineering of various nanostructured g-C3N4 (e.g. thinner, highly crystalline, doped, and porous g-C3N4) photocatalysts for HER application. Then a series of highly efficient g-C3N4 (e.g., metal/g-C3N4, semiconductor/g-C3N4, metal organic framework/g-C3N4, carbon/g-C3N4, conducting polymer/g-C3N4, sensitizer/g-C3N4) composite photocatalysts are exemplified. Lastly, this review provides a comprehensive summary and outlook on the major challenges, opportunities, and inspiring perspectives for future research in this hot area on the basis of pioneering works. It is believed that the emerging g-C3N4-based photocatalysts will act as the “holy grail” for highly efficient photocatalytic HER under visible-light irradiation.

Semiconductor polymeric graphitic carbon nitride photocatalysts: the “holy grail” for the photocatalytic hydrogen evolution reaction under visible light

Graphitic carbon nitride (g-C3N4) has enormous potential for photocatalysis, but only possesses moderate activity because of excitonic effects and sluggish charge transfer. Herein, metal-free heterostructure photocatalyst constructed by boron nitride quantum dots (BNQDs) and ultrathin porous g-C3N4 (UPCN) was successfully developed for overcoming these defects. Results showed that the BNQDs loaded UPCN can simultaneously promote the dissociation of excitons and accelerate the transfer of charges owing to the negatively charged functional groups on the surface of BNQDs as well as the ultrathin and porous nanostructure of g-C3N4. Benefiting from the intensified exciton dissociation and charge transfer, the BNQDs/UPCN (BU) photocatalyst presented superior visible-light-driven molecular oxygen activation ability, such as superoxide radical ( O2−) generation and hydrogen peroxide (H2O2) production. The average O2− generation rate of the optimal sample (BU-3) was estimated to be 0.25 μmol L−1 min−1, which was about 2.3 and 1.6 times than that of bulk g-C3N4 and UPCN. Moreover, the H2O2 production by BU-3 was also higher than that of bulk g-C3N4 (22.77 μmol L−1) and UPCN (36.13 μmol L−1), and reached 72.30 μmol L−1 over 60 min. This work reveals how rational combination of g-C3N4 with BNQDs can endow it with improved photocatalytic activity for molecular oxygen activation, and provides a novel metal-free and highly efficient photocatalyst for environmental remediation and energy conversion.

Boron nitride quantum dots decorated ultrathin porous g-C3N4: Intensified exciton dissociation and charge transfer for promoting visible-light-driven molecular oxygen activation

Hydrogen peroxide (H2 O2 ) has received increasing attention because it is not only a mild and environmentally friendly oxidant for organic synthesis and environmental remediation but also a promising new liquid fuel. The production of H2 O2 by photocatalysis is a sustainable process, since it uses water and oxygen as the source materials and solar light as the energy. Encouraging processes have been developed in the last decade for the photocatalytic production of H2 O2 . In this Review we summarize research progress in the development of processes for the photocatalytic production of H2 O2 . After a brief introduction emphasizing the superiorities of the photocatalytic generation of H2 O2 , the basic principles of establishing an efficient photocatalytic system for generating H2 O2 are discussed, highlighting the advanced photocatalysts used. This Review is concluded by a brief summary and outlook for future advances in this emerging research field.

Production of Hydrogen Peroxide by Photocatalytic Processes

The development of efficient photocatalysts for the production of hydrogen peroxide (H2O2) is a promising strategy to realize solar-to-chemical energy conversion. Graphitic carbon nitride (g-C3N4) presents giant potential for photocatalytic H2O2 production, but the sluggish charge separation depresses its photocatalytic performance. Herein, an interfacial Schottky junction composed of Ti3C2 nanosheets and porous g-C3N4 nanosheets (TC/pCN) is constructed by a facile electrostatic self-assembly route to significantly boost the spatial charge separation to promote the activation of molecular oxygen for H2O2 production. As the optimal sample, TC/pCN-2 possesses the highest H2O2 production rate (2.20 μmol L−1 min−1) under visible light irradiation (λ > 420 nm), which is about 2.1 times than that of the porous g-C3N4. The results of superoxide radical detection and rotating disk electrode measurement suggest that the two-step single-electron reduction of oxygen is the predominant reaction step during this photocatalytic H2O2 production process. The enhanced photocatalytic performance is ascribed to the formation of Schottky junction and subsequent built-in electric field at their interface, which accelerate the spatial charge separation and restrain the charge recombination. This work provides an in-depth understanding of the mechanism of photocatalytic H2O2 production, and gives ideas for the design of highly active materials for photocatalytic H2O2 production.

Ti3C2 Mxene/porous g-C3N4 interfacial Schottky junction for boosting spatial charge separation in photocatalytic H2O2 production

g-C3N4界面改性:掺杂金属硫化物构建新型异质结光催化剂的能源转换展望

H2O2 is a green, environmentally friendly potential energy source. The photocatalytic reduction of molecular oxygen to synthesise H2O2 is an eco-friendly strategy compared with the anthraquinone method and H2/O2 direct synthesis. We proposed oxygen-enriched carbon nitride polymer (OCN) models, which were proven to more easily produce 1,4-endoperoxide species and have a high selectivity for molecular oxygen reduction to H2O2, rather than superoxide radicals, through theoretical calculations and experiments. The apparent quantum yield for H2O2 production by OCNs reached 10.2% at 420 nm under an O2 atmosphere, which was 3.5 times higher than that of g-C3N4 and the activity did not decay over 20 h. OCN has a better oxygen reducibility and electron–hole separation efficiency than g-C3N4 and is more prone to 2-electron reduction in the ORR. This work promotes understanding of the mechanism of photocatalytic oxygen reduction and provides a new idea for the design and synthesis of new materials for the preparation of H2O2.

Meili Liu

Papers

Efficient visible-light-driven selective oxygen reduction to hydrogen peroxide by oxygen-enriched graphitic carbon nitride polymers