Self-standing Janus nanofiber heterostructure photocatalyst with hydrogen production and degradation of methylene blue

A highly efficient, stable, easily recyclable carbon-based [g-C₃N₄/C]//[TiO₂/C] Janus nanofibers heterostructure photocatalyst (gT-JNHP) was first designed and constructed through the combination of conjugative electro-spinning with subsequent calcination procedure. gT-JNHP with novel Janus structure consists of two sides: one side is g-C₃N₄/C nanofiber that absorbs visible light (VL), and the other side is TiO₂/C nanofiber that can capture ultraviolet light (UL), and the two strands of nanofibers are tightly combined together to form the unique heterostructure Janus nanofiber, which can make full use of sunlight (SL). gT-JNHP presents better remarkably boosted photocatalytic performance in comparison with the counterpart g-C₃N₄/C, TiO₂/C, or their mechanical mixture, and the degradation efficiencies of methylene blue in gT-JNHP-2, respectively, are 95.1% (160 min) and 98.6% (140 min), as well as hydrogen evolution rates reach up to 12.40 and 16.72 mmol h^–1 g^–1 under VL and simulated SL, respectively, thereby displaying the excellent dual functions of high-efficient hydrogen release and removal of organic contaminant. The outstanding photocatalytic property is ascribed to the joint effect among the unique Janus-typed heterostructure, catalyst components, and electrically conductive carbon fiber, achieving close contact between the interfaces, effective separation of photo-excited carriers, strong light capture ability, and many more exposed active sites, etc. Feasible photocatalytic mechanisms are advanced. Moreover, gT-JNHP owns the characteristics of flexible self-standing, easy recycling, and superb durability. The constructing mechanisms of Janus nanofibers and gT-JNHP are discussed in detail, and the novel fabricating techniques are established. The designing idea and construction techniques adopted in this paper are popularized for research and development of other peculiar uni-dimensional dual-functional nanofibrous photocatalysts.     

Facile fabrication of 3D interconnected porous boron doped polymeric g-C3N4 with enhanced visible light photocatalytic hydrogen evolution and dye contaminant elimination

Researchers have attempted to developing high-efficiency catalysts for photocatalytic hydrogen evolution and organic pollution elimination simultaneously to alleviate the issues of energy shortage and water pollution. In this work, we fabricated 3D interconnected porous boron doped polymeric g-C₃N₄ catalysts with efficient photocatalytic activity for hydrogen evolution and dye contaminant elimination under visible-light irradiation. The as-fabricated catalysts exhibited significantly enhanced hydrogen evolution (4.37 mmol g ^?1 h^?1) and RhB contaminant elimination (96.37%) activity. Based on characterization and photocatalytic tests, an enhanced mechanism of the superior photocatalytic performance was proposed: 3D interconnected porous structure and B-doping have a synergistic effect on the greatly improved photocatalytic activity. The 3D interconnected structures endowed g-C₃N₄ with a higher specific surface area and abundant active sites and improved the capacity of rapid absorption to facilitate the photocatalytic process. B doping provided enhanced visible-light absorption capacity and a narrowed bandgap and served as a “highway” for electron-hole pairs to facilitate migration and separation and suppress the combination of photogenerated carriers. Besides, the possible mechanism of enhanced photocatalytic performance was elucidated according to the results of characterization measurements and active species analysis.     

异质结构g-C3N4@AM层状膜构筑及纳滤性能研究

随着化工行业的迅速发展,利用纳滤膜对有机溶剂进行高效分离受到了越来越多的关注,但有机溶剂纳滤膜通量和选择性之间普遍存在 trade-off 效应的限制。以相对疏水的g-C₃N₄纳米片和亲水的直链淀粉（amylose,AM）为构筑单元,利用双针头静电雾化技术制备了异质结构的g-C₃N₄@AM 层状膜。亲水的直链淀粉促进了极性溶剂的溶解,相对疏水的g-C₃N₄纳米片实现了通道对极性溶剂的低阻力扩散;两者协同,极大地增强了膜对极性溶剂的渗透性能,而不降低分离能力。与纯g-C₃N₄层状膜相比,g-C₃N₄@AM 层状膜对极性溶剂的渗透系数提高了1~2倍,对于尺寸大于 1.5 nm 的染料分子可以实现 99% 以上的截留率。在操作稳定性、压力循环和耐酸碱测试后,膜的渗透性能和截留能力基本保持不变,衰减 < 6%,具有较好的操作稳定性。     

Facile synthesis of carbon self-doped g-C3N4 for enhanced photocatalytic hydrogen evolution

Graphite carbon nitride (g-C₃N₄) is an appealing metal-free photocatalyst for hydrogen evolution, but the potential has been limited by its poor visible-light absorption and unsatisfactory separation of photo-induced carriers. Herein, a facile one-pot strategy to fabricate carbon self-doped g-C₃N₄ composite through the calcination of dicyanamide and trace amounts of dimethylformamide is presented. The as-obtained carbon self-doped catalyst is investigated by X-ray photoelectron spectroscopy (XPS), confirming the substitution of carbon atoms in original sites of bridging nitrogen. We demonstrate that the as-prepared materials display remarkably improved visible-light absorption and optimized electronic structure under the premise of principally maintaining the tri-s-triazine based crystal framework and surface properties. Furthermore, the carbon doped g-C₃N₄ composite simultaneously weakens the transportation barrier of charge carriers, suppresses charge recombination and raises the separated efficiency of photoinduced holes and electrons on account of the extension of pi conjugated system. As a result, carbon self-doped g-C₃N₄ exhibits 4.3 times greater photocurrent density and 5.2 times higher hydrogen evolution rate compared with its bulk counterpart under visible light irradiation.     

Controlled preparation of P-doped g-C3N4 nanosheets for efficient photocatalytic hydrogen production

Hydrogen production by photolysis of water by sunlight is an environmentally-friendly preparation technology for renewable energy. Graphitic carbon nitride (g-C₃N₄), despite with obvious catalytic effect, is still unsatisfactory for hydrogen production. In this work, phosphorus element is incorporated to tune g-C₃N₄'s property through calcinating the mixture of g-C₃N₄ and NaH₂PO_2, sacrificial agent and co-catalyst also been supplied to help efficient photocatalytic hydrogen production. Phosphorus (P) doped g-C₃N₄ samples (PCN-S) were prepared, and their catalytic properties were studied. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and ultraviolet diffuse reflection (UV-DRS) were used to study their structures and morphologies. The results show that the reaction rate of PCN-S is 318 μmol h⁻¹ g⁻¹, which is 2.98 times as high as pure carbon nitride nanosheets (CN) can do. Our study paves a new avenue, which is simple, environment-friendly and sustainable, to synthesize highly efficient P doping g-C₃N₄ nanosheets for solar energy conversion.     

氮化碳的梯度热分解法制备与产氢研究

以三聚氰胺为原料,采用梯度升温热解法制备了石墨状氮化碳(g-C_3N_4),采用XRD、XPS、FTIR、SEM及UV-Vis、PL等技术手段对氮化碳材料的微观结构和光学性能进行了表征,并分析其光解水产氢性能。结果表明:采用梯度升温热解法制备的g-C_3N_4结构良好;620°C才开始快速分解,对热稳定性良好;几乎不溶于常见试剂,化学稳定性较好;在400~550 nm的可见光波长范围内对可见光有着明显吸收,禁带宽度达到2.42 e V,具有较高的光催化分解水制氢能力(18.95μmol/h).     

Preparation of heterostructure g-C3N4/ZnO nanorods for high photocatalytic activity on different pollutants (MB,RhB, Cr(VI) and eosin)

The g-C₃N₄/ZnO nanorods were prepared by simple hydrothermal, grinding and calcination methods. The characterization of g-C₃N₄/ZnO nanorods was done by different analytical techniques such as SEM, TEM, XRD, XPS, FT-IR and UV–Vis. g-C₃N₄/ZnO nanorods with heterostructures have been successfully synthesized without changing the structure between the monomers, which broadens the visible light response range and improves several major pollutants in water degradation rate. Photocatalytic studies were done for the degradation of MB, RhB, Cr(VI) and eosin which are almost fully degraded. The experimental results show that the photocatalytic performance of the nanorods is much better than others. The g-C₃N₄/ZnO photocatalyst has excellent stability and repeated cycle performance. Basing on the results of comprehensive free radical trapping test and ESR tests, it is proposed that the main active substance of the catalyst for degrading dyes is ·0₂^-, and ·OH played significant roles in the degradation process. A good photocatalytic mechanism has been proven.     

Ternary Ni2P/Bi2MoO6/g-C3N4 composite with Z-scheme electron transfer path for enhanced removal broad-spectrum antibiotics by the synergistic effect of adsorption and photocatalysis

Constructing the stable, low-cost, efficient, and highly adaptable visible light-driven photocatalyst to implement the synergistic effect of photocatalysis and adsorption has been excavated a promising strategy to deal with antibiotic pollution in water bodies. Herein, a novel 3D ternary Z-scheme heterojunction photocatalyst Ni₂P/Bi₂MoO₆/g-C₃N₄ (Ni₂P/BMO/CN) was fabricated by a simple solvothermal method in which the broad spectrum antibiotics (mainly tetracyclines and supplemented by quinolones) were used as target pollution sources to evaluate its adsorption and photocatalytic performance. Notably, the Z-scheme composite significantly exhibit the enhancement for degradation efficiency of tetracycline and other antibiotic by using Ni₂P nanoparticles as electron conductor. Active species capture experiment and electron spin resonance (ESR) technology reveal the mechanism of Z-scheme Ni₂P/BMO/CN photocatalytic reaction in detail. In addition, based on the identification of intermediates by liquid chromatography–mass spectroscopy (LC–MS), the possible photocatalytic degradation pathways of TC were proposed.     

Phase evolution,structure, and electrochemical performance of Al-, Ga- and Ta- substituted Li7La3Zr2O12 ceramic electrolytes by a modified wet chemical route

Garnet-type Li₇La₃Zr₂O₁₂ (LLZO) is one of the most promising solid-state electrolytes (SSEs) for advanced solid-state lithium batteries (SSLBs). In this work, Li_6.25Al_0.25La₃Zr₂O₁₂, Li_6.4Ga_0.2La₃Zr₂O₁₂, and Li_6.4La₃Zr_1.4Ta_0.6O₁₂ ceramics are prepared by a modified wet chemical route. The composition of the black mixtures derived from the precursors is ascertained. The phase evolution and structural properties from the ceramic mother powders to the final ceramic electrolytes are discussed in detail. The characteristic of cubic LLZO with the space group I-43d arises in the Li_6.4Ga_0.2La₃Zr₂O₁₂ ceramic electrolyte pellet after the secondary higher-temperature (1200 °C) sintering. The Rietveld refinement reveals the roles of Al³⁺ substitution at the Li⁺ sites and Ta⁵⁺ substitution at the Zr⁴⁺ sites to adjust crystal structure. In addition, the electrochemical performance of the ceramic pellets is also investigated. Remarkably, the Li_6.4La₃Zr_1.4Ta_0.6O₁₂ ceramic electrolyte has the most outstanding electrochemical performance, showing the high ionic conductivity of 6.88 × 10^?4 S cm^?1 (25 °C), the low activation energy of 0.42 eV and an extremely low electronic conductivity of 1.77 × 10^?8 S cm^?1 (25 °C). Overall, it is supposed that this work may help to achieve high-quality modified LLZO ceramic electrolytes, especially using the wet chemical strategy.