Decorating Phosphorus‐Doped g‐C₃N₄ with Zinc Porphyrin Metal–Organic Framework via an Electrostatic Self‐Assembly Process: An Efficient Strategy to Boost Photocatalytic Hydrogen Evolution Performance

Abstract

Herein, a novel 2D/2D heterostructure, phosphorus‐doped carbon nitride nanosheet/zinc porphyrin metal–organic framework (MOF) (HPCNN/ZnPMOF), is elaborately fabricated through an electrostatic self‐assembly process for photocatalytic H2 evolution from water splitting. The as‐prepared HPCNN/ZnPMOF 2D/2D photocatalyst displays the highest H2 evolution rate of 65.3 mmol g−1 h−1 under simulated solar irradiation, which is 2.2 and 49.1 times higher than that of HPCNN and ZnPMOF, respectively. The enhanced photocatalytic activity can be ascribed to the intimate contact interface and the shortened migration distance formed by the unique 2D/2D structure, resulting in dramatically enhanced separation and transfer efficiencies of hole–electron pairs. Furthermore, P doping endows carbon nitride with more separation sites of photoinduced charge carriers and consequently establishes type‐II heterojunction with ZnPMOF. This work shed lights on the potential of designing the highly efficient MOF/g‐C3N4 2D/2D system for water splitting H2 evolution.

Porphyrin-based MOFs for photocatalysis in water: advancements in solar fuels generation and pollutants degradation

“…The fundamentals of heterojunctions can be found elsewhere. 82,83 In this context, several heterojunctions using PMOFs with other inorganic materials like TiO 2 , 86 titanate nanotubes (TNTs), 87 ZnIn 2 S 4 , 88 Nb 6 O 17 , 89 and CdS 90 and recently using metal-free materials such as carbon nitrides 84,85 and covalentorganic frameworks (COFs) 91,92 were reported. Table 2 summarizes the results in terms of photocatalytic activity/stability.…”

“…In recent years, a couple of studies have been reported on the development of 2D/2D heterojunctions based on PMOFs and carbon nitride (CN)-based materials for the HER. 84,85 One of the intrinsic properties of these 2D/2D heterojunctions is to facilitate the interface contact between the counterparts and, thus, the photocatalytic activity. Similarly, some studies have described the possibility of preparing MOF/COF composite photocatalysts.…”

Improving the photocatalytic activity of porphyrins for hydrogen evolution from water splitting through combined effects inspired by meso-carboxyfuryl substitution

“…[7][8][9][10] The primary advantage of porphyrins in photocatalytic applications lies in their wide absorption of light from ultraviolet to visible light, presenting the potential for comprehensive utilization of solar energy. 11,12 Meanwhile, the chemical and physical properties of porphyrins can be easily modulated through substitution, to provide appropriate electron transfer pathways for various photocatalytic reactions. 13,14 Meso-substitution is more favorable and feasible for porphyrins relative to b-substitution, and is often used to modulate the properties of porphyrins.…”

A novel graphdiyne (CnH2n−2) synthesis strategy: design and application of an organic/inorganic conjugated system for photocatalytic hydrogen production

“…Improving the performance by constructing reasonable heterojunctions may be an important means to develop the application of graphdiyne in photocatalytic hydrogen production. 20 Graphitic phase carbon nitride (g-C 3 N 4 ) has attracted a lot of attention as a non-metallic semiconductor catalyst since it became available. 21 It has a suitable band gap, stable chemical properties as well as inexpensive raw materials and simple preparation, showing excellent applicability in the field of photocatalysis.…”

“…Improving the performance by constructing reasonable heterojunctions may be an important means to develop the application of graphdiyne in photocatalytic hydrogen production. 20…”