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.     

Influence of doped platinum nanoparticles on photocatalytic performance of CuO–SiO2 for degradation of Acridine orange dye

Preparation of cupric oxide-silicon dioxide nanoparticles was carried out using a sol-gel method. Cupric oxide-silicon dioxide nanoparticles were decorated by different weight percent of platinum (0.5, 1.0, 3.0 and 5.0 wt %) using method of photoassisted deposition. XRD remarks revealed that XRD patterns for all samples are composed of cupric oxide. Therefore, silicon dioxide is amorphous and decoration of cupric oxide-silicon dioxide nanoparticles by platinum has no effect on the formed phase. Also, due to low percent of platinum there are no peaks for platinum oxide or platinum. Cupric oxide has bandgap energy absorb in visible region but has high e-h recombination rate. Decoration of cupric oxide-silicon dioxide nanoparticles by platinum was decreased bandgap energy from 2.38 to 1.91 eV and also decrease rate of e-h recombination rate. The photocatalytic activity of platinum decorated cupric oxide-silicon dioxide nanoparticles was measured under visible light for Acridine orange dye degradation. 100% of Acridine orange dye can be degraded using 3.0 wt % of platinum decorated cupric oxide-silicon dioxide photocatalyst, 1.2 g/L dose of platinum decorated cupric oxide-silicon dioxide photocatalyst and 30 min reaction time. 3.0 wt % of platinum decorated cupric oxide-silicon dioxide photocatalyst has photocatalytic stability for five times.     

钒掺杂二氧化钛光催化活性研究

二氧化钛凭借优异的光催化性能,越来越受到人们的广泛关注和重视。以钛酸四丁酯为原料,利用水解-水热-干燥/煅烧工艺制备得到未掺杂TiO₂光催化剂和掺钒TiO₂光催化剂,利用其对甲基橙溶液的降解率做了比较分析。结果表明,以钛酸四丁酯为原料,采用溶胶-凝胶法制备钒掺杂TiO₂光催化剂是可行的。制备V/TiO₂产品的最佳工艺条件：钒钛质量比为6∶100、水热温度为160 ℃、水热时间为12 h,120 ℃下干燥14 h。紫外光照射条件下,甲基橙光催化降解效率达到99.10%,降解时间小于45 min。     

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.     

质子化氮化碳的制备及其复合材料的光催化性能

分别采用硫酸、盐酸和硝酸对尿素热解得到的体相块状石墨相氮化碳(g-C_3N_4)进行质子化改性,超声剥离得到氮化碳纳米片,考察3种质子化氮化碳纳米片对亚甲基蓝染料的光催化降解性能,利用XRD、FT-IR、SEM、BET、UV-DRS、UV-VIS等对其结构、形貌、比表面积、禁带宽度进行分析。结果表明,硫酸改性后的g-C_3N_4比表面积最大(60. 9 m~2·g~(-1)),亚甲基蓝降解效果最好,降解率为46. 7%,相比于体相块状g-C_3N_4的29. 2%提高了17. 5个百分点。以硫酸质子化改性的g-C_3N_4为前驱体,采用搅拌法制备得到质子化g-C_3N_4/石墨烯复合材料,其光催化降解亚甲基蓝的降解率为81. 7%,较硫酸质子化g-C_3N_4提高了35. 0个百分点。     

Fabrication and photocatalytic performance of one-dimensional Ag3PO4 sensitized SrTiO3 nanowire

The 1D Ag₃PO₄ sensitized SrTiO₃ nanowires are prepared by simple route of electrospinning-in situ deposition technique. The results of the thermogravimetry (TG), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive Spectrometer (EDS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and UV–Visible diffuse reflectance spectroscopy (UV–Vis) indicate that the Ag₃PO₄ nanoparticles has been deposited on the surface of the SrTiO₃ nanowires successfully. Experimental results showed that compared with pure SrTiO₃, the as-prepared 1D Ag₃PO₄ sensitized SrTiO₃ nanowires exhibit obvious enhancement of photocatalytic performance and stability. Especially, the Ag₃PO₄/SrTiO₃ (3AS sample) had a satisfactory photocatalytic activity for degrading methylene blue (MB) more than 98% under visible light irradiation. As to pure SrTiO₃ and Ag₃PO₄, only 9.8% and 49% of MB was decomposed after 35?min irradiation respectively. Furthermore, the mechanism of the enhancing photocatalytic activity could be ascribed to the nano-heterojunction of the Ag₃PO₄/SrTiO₃, the visible light response of the Ag₃PO₄, and the 1D structure of the nanowires.     

Fabrication of core–shell nanocomposites with enhanced photocatalytic efficacy

The current study establishes the unprecedented involvement in the evolution and production of novel core–shell nanocomposites composed of nanosized titanium dioxide and aniline‐o‐phenylenediamine copolymer. TiO₂@copoly(aniline and o‐phenylenediamine) (TiO₂@PANI‐o‐PDA) core–shell nanocomposites were chemically synthesized in a molar ratio of 5:1 of the particular monomers and several weights of nano‐TiO₂ via oxidative copolymerization. The construction of the TiO₂@PANI‐o‐PDA core–shell nanocomposites was ascertained from Fourier transform IR spectroscopy, UV–visible spectroscopy and XRD. A reasonable thermal behavior for the original copolymer and the TiO₂@PANI‐o‐PDA core–shell nanocomposites was investigated. The bare PANI‐o‐PDA copolymer was thermally less stable than the TiO₂@PANI‐o‐PDA nanocomposites. The core–shell feature of the nanocomposites was found to have core and shell sizes of 17 nm and 19–26 nm, respectively. In addition, it was found that the addition of a high ratio of TiO₂ nanoparticles increases the electrical conductivity and consequently lowers the electrical resistivity of the TiO₂@PANI‐o‐PDA core–shell nanocomposites. The hybrid photocatalysts exhibit a dramatic photocatalytic efficacy of methylene blue degradation under solar light irradiation. A plausible interpretation of the photocatalytic degradation results of methylene blue is also demonstrated. Our setup introduces a facile, inexpensive, unique and efficient technique for developing new core–shell nanomaterials with various required functionalities and colloidal stabilities. © 2018 Society of Chemical Industry     

机械涂覆技术在光催化材料制备中的应用进展

机械球磨技术因工艺简单、成本低廉而受到广泛关注,特别在粉体材料的混合、细化及合金化等领域有着广阔的应用前景。综述了由机械球磨原理发展而成机械涂覆技术的应用现状,包括用于材料表面改性的功能涂层和光催化降解的薄膜材料制备。分析了工艺参数、涂覆材料及涂覆基底等因素对涂覆效果（厚度）的影响规律,并对该技术在薄膜制备中表现出的简便、廉价且可在球形等形状复杂基底上成膜的独特优势做了讨论。基于当前机械涂覆技术制备的薄膜形貌、厚度不可控且成膜基底材质受限等现状,指出今后应该向拓展成膜基底材料类型和加快推进光催化薄膜材料的实际应用方向发展。