Simultaneous Efficient Photocatalytic Hydrogen Evolution and Degradation of Dye Wastewater without Cocatalysts and Sacrificial Agents Based on g-C3 N5 and Hybridized Ni-MOF Derivative-CdS-DETA.

Inspired by energy conversion and waste reuse, hybridized Ni-MOF derivative-CdS-DETA/g-C3 N5 , a type-II heterojunction photocatalyst, is synthesized by a hydrothermal method for simultaneous and highly efficient photocatalytic degradation and hydrogen evolution in dye wastewater. Without the addition of cocatalysts and sacrificial agents, the optimal MOF-CD(2)/CN5 (i.e. Ni-MOF derivative-CdS-DETA (20 wt.%)/g-C3 N5 ) exhibit good bifunctional catalytic activity, with a H2 evolution rate of 2974.4 µmol g-1  h-1 during the degradation of rhodamine B (RhB), and a removal rate of 99.97% for RhB. In the process of H2 -evolution-only, triethanolamine is used as a sacrificial agent, exhibiting a high H2 evolution rate (19663.1 µmol g-1  h-1 ) in the absence of a cocatalyst, and outperforming most similar related materials (such as MOF/g-C3 N5 , MOF-CdS, CdS/g-C3 N5 ). With the help of type-II heterojunction, holes are scavenged for the oxidative degradation of RhB, and electrons are used in the decomposition of water for H2 evolution during illumination. This work opens a new path for photocatalysts with dual functions of simultaneous efficient degradation and hydrogen evolution.

Construction of Ni3S4@ZIS@C3N5 photocatalyst with type II and Z-type heterojunctions by self-assembly for efficient photocatalytic hydrogen evolution.

A novel ternary photocatalyst Ni3S4@ZIS@C3N5 with type II and Z-type heterojunctions was synthesized for the first time by hydrothermal and electrostatic self-assembly methods, effectively avoiding the thermal decomposition of C3N5 during the synthesis of the complex. The best ternary catalyst Ni3S4@ZIS@C3N5 is capable of achieving an optimal hydrogen evolution rate of 9750 mmol g-1 h-1, which is approximately 10.89 times as high as that of C3N5, indicating that the complex effectively enhanced the photocatalytic properties of the monomer. The coexistence of two types of heterojunctions in the complex effectively enhances photocatalytic performance, in which the monomer ZIS constructs type II scheme with Ni3S4 and Z-type scheme with C3N5, respectively. The two heterojunctions complement each other and jointly promote the rapid electron transfer from Ni3S4 and C3N5 to the ZIS surface. In conclusion, the cooperation of the two heterojunctions efficiently facilitates the migration of photogenerated carriers, thus enhancing the photocatalytic hydrogen generation performance of Ni3S4@ZIS@C3N5.

4-Methyl-5-vinyl thiazole modified Ni-MOF/g-C3N4/CdS composites for efficient photocatalytic hydrogen evolution without precious metal cocatalysts.

The construction of heterojunction systems is an effective way to efficiently generate hydrogen by water photolysis. In this work, Ni-MOF (trimesic acid, (BTC)) and g-C3N4 (denoted as CN) were combined, and then Ni-MOF/CN was modified by 4-Methyl-5-vinyl thiazole (denoted as MVTh). Finally, CdS was loaded on the surface of Ni-MOF/CN/MVTh to prepare the photocatalyst Ni-MOF/g-C3N4/MVTh/CdS (denoted as Ni/CN/M/Cd) with a triangular closed-loop path heterojunction for the first time. As a photocatalyst without precious metal cocatalysts, Ni/CN/M/Cd displayed high H2 evolution (17.844 mmol·g-1·h-1) under an optimum CdS loading of 40 wt%. The H2 evolution rate was approximately 79 times that of Ni-MOF/CN and exceeded those of almost all catalysts based on MOF/CN in the literature. The triangular closed-loop heterojunction formed between Ni-MOF, g-C3N4, and CdS could realize the directional migration of photocarriers and significantly diminished the transfer resistance of carriers. The Ni2+ in Ni-MOF provided many cocatalytic sites for H2 evolution via g-C3N4 and CdS. Furthermore, charge carrier separation in Ni-MOF/CN/CdS improved after the innovative addition of MVTh. This study provides a reference for the construction of a closed-loop heterojunction system without precious metal cocatalysts.