Ni1−xCoxSe2?C/ZnIn2S4 Hybrid Nanocages with Strong 2D/2D Hetero-Interface Interaction Enable Efficient H2-Releasing Photocatalysis

Designing a semiconductor-based heterostructure photocatalyst for achieving the efficient separation of photogenerated electron-hole pairs is highly important for enhancing H₂ releasing photocatalysis. Here, a new class of Ni_1−xCo_xSe₂–C/ZnIn₂S₄ hierarchical nanocages with abundant and compact ZnIn₂S₄ nanosheets/Ni_1−xCo_xSe₂^ C nanosheets 2D/2D hetero–interfaces, is designed and synthesized. The constructed heterostructure photocatalyst exposes rich hetero-junctions, supplying the broad and short transfer paths for charge carriers. The close contacts of these two kinds of nanosheets induce a strong interaction between ZnIn₂S₄ and Ni_1−xCo_xSe₂ C, improving the separation and transfer of photo-generated electron-hole pairs. As a consequence, the distinctive Ni_1−xCo_xSe₂ C/ZnIn₂S₄ hierarchical nanocages without using additional noble-metal cocatalysts, display remarkable H₂-relaesing photocatalytic activity with a rate of 5.10 mmol g⁻¹ h⁻¹ under visible light irradiation, which is 6.2 and 30 times higher than those of fresh ZnIn₂S₄ nanosheets and bare Ni_1−xCo_xSe₂ C nanocages, respectively. Spectroscopic characterizations and theory calculations reveal that the strong interaction between ZnIn₂S₄ and Ni_1−xCo_xSe₂ C 2D/2D hetero-interfaces can powerfully promote the separation of photo-generated charge carriers and the electrons transfer from ZnIn₂S₄ to Ni_1−xCo_xSe₂ C.     

Graphitic-C3N4/ZnCr-layered double hydroxide 2D/2D nanosheet heterojunction: Mesoporous photocatalyst for advanced oxidation of azo dyes with in situ produced H2O2

In this study the constructional modification of Graphitic carbon nitride nanosheet (GCN-ns) has been made with the aid of ZnCr layered double hydroxide (ZC-LDH) in a unique 2D-2D structure to enhance its visible light absorption. Optical and morphological study presents successful incorporation of ZC-LDH on the surface of GCN-ns. Through adjusting of GCN-ns by ZC-LDH lower recombination rate of e^?/h⁺ pairs, longer lifetimes and an increase in contamination reduction was brought out. The binary nanocomposite was employed to effectively degrade Rhodamine B under UV/vis light irradiation. The improvement in photocatalytic abilities was proven to be related to in situ self-production of H₂O₂ on GCN-ns/ZC-LDH surface by Xe light irradiation which in return accounts for additional hydroxide radical generation. Radical quenching experiments specified the main active species involved while the consequent step-scheme (S-scheme) charge transfer mechanism was proposed.     

A review of hydrogen production processes by photocatalytic water splitting – From atomistic catalysis design to optimal reactor engineering

‘Renewable energy is an essential part of our strategy of decarbonization, decentralization, as well as digitalization of energy.’ – Isabelle Kocher.Current climate, health and economic condition of our globe demands the use of renewable energy and the development of novel materials for the efficient generation, storage and transportation of renewable energy. Hydrogen has been recognised as one of the most prominent carriers and green energy source with challenging storage, enabling decarbonization. Photocatalytic H₂ (green hydrogen) production processes are targeting the intensification of separated solar energy harvesting, storage and electrolysis, conventionally yielding O₂/H₂. While catalysis is being investigated extensively, little is done on bridging the gap, related to reactor unit design, optimisation and scaling, be it that of material or of operation. Herein, metals, oxides, perovskites, nitrides, carbides, sulphides, phosphides, 2D structures and heterojunctions are compared in terms of parameters, allowing for efficiency, thermodynamics or kinetics structure–activity relationships, such as the solar-to-hydrogen (STH). Moreover, prominent pilot systems are presented summarily.     

Near-Field Drives Long-Lived Shallow Trapping of Polymeric C3N4 for Efficient Photocatalytic Hydrogen Evolution

Undesired photoelectronic dormancy through active species decay is adverse to photoactivity enhancement. An insufficient extrinsic driving force leads to ultrafast deep charge trapping and photoactive species depopulation in carbon nitride (g-C₃N₄). Excitation of shallow trapping in g-C₃N₄ with long-lived excited states opens up the possibility of pursuing high-efficiency photocatalysis. Herein, a near-field-assisted model is constructed consisting of an In₂O₃-cube/g-C₃N₄ heterojunction associated with ultrafast photodynamic coupling. This In₂O₃-cube-induced near-field assistance system provides catalytic “hot areas”, efficiently enhances the lifetimes of excited states and shallow trapping in g-C₃N₄ and this favors an increased active species density. Optical simulations combined with time-resolved transient absorption spectroscopy shows there is a built-in charge transfer and the active species lifetimes are longer in the In₂O₃-cube/g-C₃N₄ hybrid. Besides these properties, the estimated overpotential and interfacial kinetics of the In₂O₃-cube/g-C₃N₄ hybrid co-promotes the liquid phase reaction and also helps in boosting the photocatalytic performance. The photocatalytic results exhibit a tremendous improvement (34-fold) for visible-light-driven hydrogen production. Near-field-assisted long-lived active species and the influences of trap states is a novel finding for enhancing (g-C₃N₄)-based photocatalytic performance.     

TiO_2/FeOOH/硅藻土纳米复合材料的制备和光催化性能研究

采用分子组装的方法,以硅藻土为基底制备TiO_2/硅藻土、TiO_2/FeOOH/硅藻土纳米复合材料,通过UV-Vis、TEM方法对材料进行表征,以甲基橙溶液为目标降解物探究纳米复合材料的光催化性能,结果表明,基底制备TiO_2/硅藻土、TiO_2/FeOOH/硅藻土纳米复合材料对甲基橙均有不错的降解率,其中TiO_2/FeOOH/硅藻土纳米复合材料降解率达到67.16%。     

Controlled synthesis of Ag2O/g-C3N4 heterostructures using soft and hard templates for efficient and enhanced visible-light degradation of ciprofloxacin

Pluronic 31R1 surfactant and MCM-41 silica were used to fabricate mesoporous Ag₂O/g-C₃N₄ heterostructures with improved surface areas. The fabricated mesoporous nanocomposite was used to photo oxidize ciprofloxacin. The TEM images of Ag₂O/g-C₃N₄ indicated a uniform dispersion of spherical approximately 4-nm Ag₂O nanoparticles on g-C₃N₄. The mesoporous 0.9% Ag₂O@g-C₃N₄ heterostructure exhibited 100% efficiency in ciprofloxacin oxidation within 60 min when compared with the 25% efficiency in 120 min of pure mesoporous Ag₂O and 10% efficiency in 120 min of pure g-C₃N₄. The highest ciprofloxacin oxidation efficiency achieved was 100%, which was four and ten times better than those of Ag₂O and g-C₃N₄, respectively. This superior performance of the mesoporous Ag₂O/g-C₃N₄ was attributed to the high dispersion of nano-sized mesoporous Ag₂O particles on the g-C₃N₄ surface, narrow bandgap, and significantly high surface areas. The powerful interaction between Ag₂O and g-C₃N₄ ensured robust durability of Ag₂O/g-C₃N₄ heterostructures, which is evident in the fact that five recycling trials of the photocatalyst rendered a minimal loss of efficiency.     

Covalent triazine framework with efficient photocatalytic activity in aqueous and solid media

Covalent triazine frameworks (CTFs) have been recently employed for visible light-driven photocatalysis due to their unique optical and electronic properties. However, the usually highly hydrophobic nature of CTFs, which originates from their overall aromatic backbone, leads to limitations of CTFs for applications in aqueous media. In this study, we aim to extend the range of the application media of CTFs and design hybrid material of a CTF and mesoporous silica (SBA-15) for efficient photocatalysis in aqueous medium. A thiophene-containing CTF was directly synthesized in mesopores of SBA-15. Due to the high surface area and the added hydrophilic properties by silica, the hybrid material demonstrated excellent adsorption of organic molecules in water. This leads not only to high photocatalytic performance of the hybrid material for the degradation of organic dyes in water, but also for efficient photocatalysis in solvent-free and solid state. Furthermore, the reusability, stability and easy recovery of the hybrid material offers promising metal-free heterogeneous photocatalyst for broader applications in different reaction media.     

Enhanced visible-light-assisted photocatalytic hydrogen generation by MoS2/g-C3N4 nanocomposites

A facile, one-pot, solvothermal synthesis of MoS₂ microflowers (S1) and the heterostructures MoS₂/g-C₃N₄ with varying ratios of 1:1 (S2), 1:2 (S3) and 1:3 (S4) exhibiting enhanced visible-light-assisted H₂ generation by water splitting has been reported. The compounds were thoroughly characterized by PXRD, FESEM, HRTEM, EDS, UV–vis and XPS techniques. FESEM and HRTEM analyses showed the presence of microflowers composed of nano-sized petals in case of pure MoS₂ (S1), while the MoS₂ microflowers covered with g-C₃N₄ nanosheets in case of MoS₂/g-C₃N₄ heterostructure, S4. XPS analysis of S2 showed the presence of 2H phase of MoS₂ with g-C₃N₄. The Eosin-Y/dye-sensitized visible-light-assisted photocatalytic investigation of the samples in the absence of any noble metal co-catalyst revealed very good water splitting activity of MoS₂/g-C₃N₄ heterostructure, S2 with hydrogen generation rate of 1787 μmol h⁻¹g⁻¹ which is about 6 and 40 times higher than pure MoS₂ and g-C₃N₄ respectively. The relatively higher catalytic activity of the heterostructure, S2 has been ascribed to the efficient spatial separation of photo-induced charge carriers owing to the synergistic interaction between MoS₂ and g-C₃N₄. A possible mechanism for the Eosin-Y-sensitized photocatalytic H₂ generation activity of MoS₂/g-C₃N₄ heterostructures has also been presented. The enhanced activity of S2 was further supported by fluorescence measurements. Thus, the present study highlights the importance of non-noble metal based MoS₂/g-C₃N₄ heterojunction photocatalysts for efficient visible-light-driven H₂ production from water splitting.     

聚丙烯腈/醋酸纤维素/TiO2复合纳米纤维膜的制备及其光催化降解性能

为研究碱改性前后复合纳米纤维膜的光催化降解性能,首先利用静电纺丝技术制备聚丙烯腈/醋酸纤维素/二氧化钛(PAN/CA/TiO₂)复合纳米纤维膜,依次用0.05、0.10 mol/L的氢氧化钠溶液对其进行碱处理,制得聚丙烯腈/再生纤维素/二氧化钛(PAN/RC/TiO₂)复合纳米纤维膜,并应用于染料废水处理。借助扫描电子显微镜、傅里叶红外光谱仪及接触角测量仪等手段表征了复合纳米纤维膜的结构与亲水性;同时研究了复合纳米纤维膜的力学与光催化降解性能。结果表明:经碱处理后,复合纳米纤维膜的静态接触角由125.30°减小到10.20°,亲水性能得到很大的改善;PAN/RC/TiO₂复合纳米纤维膜对亚甲基蓝(MB)溶液的降解率达到91.2%,而空白对照样对MB溶液的降解率仅为10.1%,且重复使用3次后,复合纳米纤维膜对MB溶液的降解率仍达74.7%。