机械混合法制备TiO2/g-C3N4复合材料及其光催化降解双酚A的性能

本工作采用机械混合方法,将TiO₂纳米颗粒与不同质量的g-C₃N₄复合,制备了一系列具有不同g-C₃N₄含量的TiO₂/g-C₃N₄复合材料.运用X射线粉末衍射（XRD）、X射线光电子能谱（XPS）、拉曼光谱（Raman）、比表面积分析仪（BET）、扫描电镜（SEM）和透射电镜（TEM）对材料的化学组成和形貌特征进行了表征.比较了g-C₃N₄、TiO₂和一系列TiO₂/g-C₃N₄在可见光驱动下对水中双酚A（BPA）的降解效率和矿化能力差异,发现TiO₂/g-C₃N₄的光催化活性显著高于g-C₃N₄和TiO₂,其中以TiO₂/g-C...     

Heterostructuring noble-metal-free 1T' phase MoS2 with g-C3N4 hollow nanocages to improve the photocatalytic H2 evolution activity

In this work,we report the preparation of 1T’-MoS₂/g-C₃N₄ nanocage(NC) heterostructure by loading 2D semi-metal noble-metal-free 1T’-MoS₂ on the g-C₃N₄ nanocages(NCs).DFT calculation and experimental data have shown that the 1T’-MoS₂/g-C₃N₄ NC heterostructure has a stronger light absorption capacity and larger specific surface area than pure g-C₃N₄ NCs and g-C₃N     

g-C3N4-MoS2/WSe2自偏压系统构建与不同类型污染物同时去除性能研究

由于工业化进程的不断推进,染料与重金属废水被非法排入自然水体,水体污染问题日益严峻.为实现两种污染物的同时去除,本文通过调控合成MoS₂/WSe₂（MW）异质结复合催化材料,提高其催化活性.黑暗条件下,以MoS₂、WSe₂以及MW为阳极材料,g-C₃N₄为阴极材料组建自偏压燃料电池系统,实现在降解有机染料的同时,去除水体中的重金属离子.通过调控参数,探究影响染料与重金属去除的因素.研究表明,影响重金属和有机染料去除效果的因素有pH、电解质溶液浓度、重金属溶液浓度.当溶液pH=5,电解质溶液浓度为0.1 mol·L^-1,铜离子浓度为4 mg·L^-1时,重金属的去除率为64.3%.当溶液pH=5,电解质溶液浓度为0.2 mol·L^-1,铜离子浓度为2 mg·L^-1时,有机染料罗丹明B的去除率为99.5%.该系统在无外加光照条件下,实现不同类型污染物同时去除,并产生约240 ...     

Self-assembly synthesis of phosphorus-doped tubular g-C3N4/Ti3C2 MXene Schottky junction for boosting photocatalytic hydrogen evolution

Establishing highly effective charge transfer channels in carbon nitride(g-C₃N₄) to enhance its photocatalytic activity is still a challenging issue. Herein, the delaminated 2D Ti₃C₂ MXene nanosheets were employed to decorate the P-doped tubular g-C₃N₄(PTCN)for engineering 1D/2D Schottky heterojunction(PTCN/TC) through electrostatic self-assembly. The optimized PTCN/TC exhibited the highest hydrogen evolution rate(565 μmol h^-...     

Zn-TiO2纳米管的光催化活性

采用水热合成-浸渍法制备锌掺杂TiO2纳米管(Zn-TiO2纳米管),透射电镜照片显示Zn-TiO2纳米管为两端开口形貌均一的中空管状结构,管径约6～8 nm,壁厚约1 nm,长度约50～200 nm。研究了Zn-TiO2纳米管对甲基橙的光催化性能,结果表明:掺杂适量锌提高了TiO2纳米管对甲基橙的光催化降解性能,0.4%Zn-TiO2纳米管的光催化性能最佳。同时还探讨了Zn-TiO2纳米管用量和初始pH值等因素对光催化降解甲基橙的影响,结果显示Zn-TiO2纳米管能有效地降解甲基橙。随着光催化反应进行,CODCr去除率和脱色率变化规律不完全相同,可能是由于芳基和烷基降解速率不同所致。     

表面活性剂(十六烷基三甲基溴化铵)辅助合成Bi2MoO6光催化剂协同PMS降解AO7

采用CTAB辅助水热法合成钼酸铋(Bi₂MoO₆,BMO)微球,并将其用于活化过一硫酸盐(PMS),在可见光下降解废水中的偶氮染料金橙Ⅱ(AO7).利用X射线衍射(XRD),傅里叶红外光谱仪(FT-IR),扫描电子显微镜(SEM),X射线能谱(XPS),透射电子显微镜(TEM)和紫外-可见漫反射光谱(UV-vis)对催化剂进行了表征,并通过降解实验测试其催化性能.结果表明,合成的催化剂具有良好的吸附、催化降解AO7的性能.在中性条件下,催化剂投加量0.3 g·L^-1,AO7浓度0.1 mmol·L^-1,PMS浓度1 mmol·L^-1,可以在30 min内完全降解AO7.研究了催化剂含量、pH、共存阴离子等对AO7降解效果的影响.通过自由基消除实验,探索了0.10CTAB-BMO/光/PMS体系中存在的活性物种(h⁺、·O₂^-、¹O₂、·OH和SO₄...     

油酸铵改性的高活性TiO_2/V-TiO_2复合光催化剂的制备及光催化降解甲基橙的研究

采用溶胶-凝胶法,将经过油酸铵改性的掺钒二氧化钛粉末投入到纯TiO2溶胶中,烘干、煅烧,制得带有n-n异质结半导体结构的复合型高活性掺钒二氧化钛光催化剂,并通过XRD、TEM、XPS等技术对样品进行了表征。通过对甲基橙溶液的光催化降解实验来考察TiO2/V-TiO2催化剂的光催化活性。结果表明:TiO2/V-TiO2复合催化剂拥有比纯TiO2更高的光催化活性。其中,V的掺杂摩尔分数为0.5%、TiO2:V-TiO2的质量比为10∶1的最佳复合催化剂,其光催化活性是纯TiO2的5.1倍。     

TiO2/活性炭复合体对罗丹明B的光催化降解

以紫外灯为光源,通过对可溶性染料罗丹明B的降解反应,考察TiO2／活性炭复合体的光催化活性,探讨了光催化反应中溶液的pH值、光强、反应温度和罗丹明B的起始浓度对催化反应的影响,结果表明,TiO2／活性炭复合体具有很高的光催化活性,对罗丹明B的降解过程遵循Langmuir-Hinshelwood动力学方程,降解速率受pH值、罗丹明B起始浓度和入射光强度的影响很大,反应温度对降解速率影响很小．在研究范围内,pH6和40W的入射光强度有利于光催化降解．     

改性FeCo2O4活化PMS降解水中2,4-二氯苯氧乙酸

以离子液体为氮源、磷源和氟源,采用一步水热法将N、P、F的3种元素掺杂到FeCo₂O₄中合成了NPF-FeCo₂O₄催化剂,用于活化过一硫酸氢钾(PMS)降解水中2,4-二氯苯氧乙酸(2,4-D).分别采用透射电子显微镜(TEM)、X射线光电子能谱(XPS)、傅立叶红外光谱(FTIR)、X射线衍射(XRD)对催化剂进行表征.实验结果表明,当催化剂投加量为0.1 g·L^-1、PMS浓度为1 mmol·L^-1时,反应30 min后2,4-D的去除率可达100%;初始pH值在3到9的范围内,体系对2,4-D的去除效果不受影响,水中低浓度的Cl^-、HCO₃^-和腐殖酸对反应有轻微的抑制.通过电子自旋共振波谱(EPR)测试结果显示,相较于FeCo₂O₄和NP-FeCo₂O₄催化剂,NPF-FeCo₂     

AQS/PPy修饰石墨板阴极应用于罗丹明B的降解

采用恒电位法制备了蒽醌二磺酸钠(AQS)掺杂的聚吡咯(PPy)修饰石墨板阴极.石墨板阴极经修饰后,电化学活性得到显著提高,其电子转移内阻及电子转移量分别为未修饰的约50%和5.7倍.实验进一步考察了阴极电位、初始pH值以及Fe~(2+)含量对罗丹明B降解实验的影响,结果表明,在阴极电位为-0.1 V,pH值为3.0,Fe~(2+)浓度为0.2 mmol·L~(-1)的条件下,60 min内对罗丹明B的降解率最高可达85.76%,且长时间运行后,降解效果重复性较好.结合不同条件下的过氧化氢产量和自由基变化淬灭实验,推断了降解过程的机理,即AQS/PPy修饰的石墨板电极,有利于分子氧在电极表面被催化还原为H_2O_2,和体系中Fe~(2+)产生羟基自由基,故罗丹明B降解是以羟基自由基为主导的电芬顿反应过程.     

Size and shape effects of MnFe2O4 nanoparticles as catalysts for reductive degradation of dye pollutants

• Size and shape-dependent MnFe₂O₄ NPs were prepared via a facile method. • Ligand-exchange chemistry was used to prepare the hydrophilic MnFe₂O₄ NPs. • The catalytic properties of MnFe₂O₄ NPs toward dye degradation were fully studied. • The catalytic activities of MnFe₂O₄ NPs followed Michaelis–Menten behavior. • All the MnFe₂O₄ NPs exhibit selective degradation to different dyes. The magnetic nanoparticles that are easy to recycle have tremendous potential as a suitable catalyst for environmental toxic dye pollutant degradation. Rationally engineering shapes and tailoring the size of nanocatalysts are regarded as an effective manner for enhancing performances. Herein, we successfully synthesized three kinds of MnFe₂O₄ NPs with distinctive sizes and shapes as catalysts for reductive degradation of methylene blue, rhodamine 6G, rhodamine B, and methylene orange. It was found that the catalytic activities were dependent on the size and shape of the MnFe₂O₄ NPs and highly related to the surface-to-volume ratio and atom arrangements. Besides, all these nanocatalysts exhibit selectivity to different organic dyes, which is beneficial for their practical application in dye pollutant treatment. Furthermore, the MnFe₂O₄ NPs could be readily recovered by a magnet and reused more than ten times without appreciable loss of activity. The size and shape effects of MnFe₂O₄ nanoparticles demonstrated in this work not only accelerate further understanding the nature of nanocatalysts but also contribute to the precise design of nanoparticles catalyst for pollutant degradation.     

Mechanistic insights into the selective photocatalytic degradation of dyes over TiO2/ZSM-11

● TiO₂/ZSM-11 was prepared by a facile solid state dispersion method. ● Mechanism for photocatalytic degradation of dyes was investigated. ● Both experimental and MD simulations were conducted. ● Chemisorption instead of electrostatic interaction played a critical role. Photocatalytic degradation is a promising way to eliminate dye contaminants. In this work, a series of TiO₂/ZSM-11 (TZ) nanocomposites were prepared using a facile solid state dispersion method. Methyl orange (MO), methylene blue (MB), and rhodamine B (RhB) were intentionally chosen as target substrates in the photocatalytic degradation reactions. Compared to pristine TiO₂, negative effect was observed on MO degradation while promoted kinetics were collected on MB and RhB over TZ composites. Moreover, a much higher photocatalytic rate was interestingly achieved on RhB than MB, which indicated that a new factor has to be included other than the widely accepted electrostatic interaction mechanism to fully understand the selective photodegradation reactions. Systematic characterizations showed that TiO₂ and ZSM-11 physically mixed and maintained both the whole framework and local structure without chemical interaction. The different trends observed in surface area and the photo-absorption ability of TZ composites with reaction performance further excluded both as the promotion mechanism. Instead, adsorption energies predicted by molecular dynamics simulations suggested that differences in the adsorption strength played a critical role. This work provided a deep mechanistic understanding of the selective photocatalytic degradation of dyes reactions, which helps to rationally design highly efficient photocatalysts.     

基于席夫碱反应合成氮掺杂的碳活化PMS降解双酚A

基于石墨相氮化碳(g-C3N4)的热聚合形成过程和席夫碱反应,本文将尿素和2-萘甲醛作为前驱体,经一步热聚合反应制备了氮掺杂的碳材料(NCN-x),并以其作为催化剂活化过一硫酸盐(PMS)来降解双酚A(BPA).在催化剂特性研究部分,利用SEM、XRD、FTIR以及XPS对其表面形貌、结构与元素组成进行分析.结果 表明...     

Inhibition of bromate formation by reduced graphene oxide supported cerium dioxide during ozonation of bromide-containing water

GO or RGO promotes bromate formation during ozonation of bromide-containing water. CeO₂/RGO significantly inhibits bromate formation compared to RGO during ozonation. CeO₂/RGO shows an enhancement on DEET degradation efficiency during ozonation. Ozone (O₃) is widely used in drinking water disinfection and wastewater treatment. However, when applied to bromide-containing water, ozone induces the formation of bromate, which is carcinogenic. Our previous study found that graphene oxide (GO) can enhance the degradation efficiency of micropollutants during ozonation. However, in this study, GO was found to promote bromate formation during ozonation of bromide-containing waters, with bromate yields from the O₃/GO process more than twice those obtained using ozone alone. The promoted bromate formation was attributed to increased hydroxyl radical production, as confirmed by the significant reduction (almost 75%) in bromate yield after adding t-butanol (TBA). Cerium oxide (less than 5 mg/L) supported on reduced GO (xCeO₂/RGO) significantly inhibited bromate formation during ozonation compared with reduced GO alone, and the optimal Ce atomic percentage (x) was determined to be 0.36%, achieving an inhibition rate of approximately 73%. Fourier transform infrared (FT-IR) spectra indicated the transformation of GO into RGO after hydrothermal treatment, and transmission electron microscope (TEM) results showed that CeO₂ nanoparticles were well dispersed on the RGO surface. The X-ray photoelectron spectroscopy (XPS) spectra results demonstrated that the Ce³⁺/Ce⁴⁺ ratio in xCeO₂/RGO was almost 3‒4 times higher than that in pure CeO₂, which might be attributed to the charge transfer effect from GO to CeO₂. Furthermore, Ce³⁺ on the xCeO₂/RGO surface could quench Br⋅ and BrO⋅ to further inhibit bromate formation. Meanwhile, 0.36CeO₂/RGO could also enhance the degradation efficiency of N,N-diethyl-m-toluamide (DEET) in synthetic and reclaimed water during ozonation.     

Enhanced triallyl isocyanurate (TAIC) degradation through application of an O3/UV process: Performance optimization and degradation pathways

• UV/O₃ process had higher TAIC mineralization rate than O₃ process. • Four possible degradation pathways were proposed during TAIC degradation. • pH impacted oxidation processes with pH of 9 achieving maximum efficiency. • CO₃^2– negatively impacted TAIC degradation while HCO₃^– not. • Cl^– can be radicals scavenger only at high concentration (over 500 mg/L Cl^–). Triallyl isocyanurate (TAIC, C₁₂H₁₅N₃O₃) has featured in wastewater treatment as a refractory organic compound due to the significant production capability and negative environmental impact. TAIC degradation was enhanced when an ozone(O₃)/ultraviolet(UV) process was applied compared with the application of an independent O₃ process. Although 99% of TAIC could be degraded in 5 min during both processes, the O₃/UV process had a 70%mineralization rate that was much higher than that of the independent O₃ process (9%) in 30 min. Four possible degradation pathways were proposed based on the organic compounds of intermediate products identified during TAIC degradation through the application of independent O₃ and O₃/UV processes. pH impacted both the direct and indirect oxidation processes. Acidic and alkaline conditions preferred direct and indirect reactions respectively, with a pH of 9 achieving maximum Total Organic Carbon (TOC) removal. Both CO₃^2– and HCO₃^– decreased TOC removal, however only CO₃^2– negatively impacted TAIC degradation. Effects of Cl^– as a radical scavenger became more marked only at high concentrations (over 500 mg/L Cl^–). Particulate and suspended matter could hinder the transmission of ultraviolet light and reduce the production of HO· accordingly.     

Visible-light-driven heterostructured g-C3N4/Bi-TiO2 floating photocatalyst with enhanced charge carrier separation for photocatalytic inactivation of Microcystis aeruginosa

• Bi doping in TiO₂ enhanced the separation of photo-generated electron-hole. • The performance of photocatalytic degradation of MC-LR was improved. • Coexisting substances have no influence on algal removal performance. • The key reactive oxygen species were h⁺ and ^•OH in the photocatalytic process. The increase in occurrence and severity of cyanobacteria blooms is causing increasing concern; moreover, human and animal health is affected by the toxic effects of Microcystin-LR released into the water. In this paper, a floating photocatalyst for the photocatalytic inactivation of the harmful algae Microcystis aeruginosa (M. aeruginosa) was prepared using a simple sol-gel method, i.e., coating g-C₃N₄ coupled with Bi-doped TiO₂ on Al₂O₃-modified expanded perlite (CBTA for short). The impact of different molar ratios of Bi/Ti on CBTA was considered. The results indicated that Bi doping in TiO₂ inhibited photogenerated electron-hole pair recombination. With 6 h of visible light illumination, 75.9% of M. aeruginosa (initial concentration= 2.7 × 10⁶ cells/L) and 83.7% of Microcystin-LR (initial concentration= 100 μg/L) could be removed with the addition of 2 g/L CBTA-1% (i.e., Bi/Ti molar ratio= 1%). The key reactive oxygen species (ROSs) in the photocatalytic inactivation process are h⁺ and ^•OH. The induction of the Bi⁴⁺/Bi³⁺ species by the incorporation of Bi could narrow the bandgap of TiO₂, trap electrons, and enhance the stability of CBTA-1% in the solutions with coexisting environmental substances.     

One-pot hydrothermal fabrication of BiVO4/Fe3O4/rGO composite photocatalyst for the simulated solar light-driven degradation of Rhodamine B

• BiVO₄/Fe₃O₄/rGO has excellent photocatalytic activity under solar light radiation. • It can be easily separated and collected from water in an external magnetic field. • BiVO₄/Fe₃O₄/0.5% rGO exhibited the highest RhB removal efficiency of over 99%. • Hole (h⁺) and superoxide radical (O₂^•−) dominate RhB photo-decomposition process. • The reusability of this composite was confirmed by five successive recycling runs. Fabrication of easily recyclable photocatalyst with excellent photocatalytic activity for degradation of organic pollutants in wastewater is highly desirable for practical application. In this study, a novel ternary magnetic photocatalyst BiVO₄/Fe₃O₄/reduced graphene oxide (BiVO₄/Fe₃O₄/rGO) was synthesized via a facile hydrothermal strategy. The BiVO₄/Fe₃O₄ with 0.5 wt% of rGO (BiVO₄/Fe₃O₄/0.5% rGO) exhibited superior activity, degrading greater than 99% Rhodamine B (RhB) after 120 min solar light radiation. The surface morphology and chemical composition of BiVO₄/Fe₃O₄/rGO were studied by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV–visible diffuse reflectance spectroscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy. The free radicals scavenging experiments demonstrated that hole (h⁺) and superoxide radical (O₂^•−) were the dominant species for RhB degradation over BiVO₄/Fe₃O₄/rGO under solar light. The reusability of this composite catalyst was also investigated after five successive runs under an external magnetic field. The BiVO₄/Fe₃O₄/rGO composite was easily separated, and the recycled catalyst retained high photocatalytic activity. This study demonstrates that catalyst BiVO₄/Fe₃O₄/rGO possessed high dye removal efficiency in water treatment with excellent recyclability from water after use. The current study provides a possibility for more practical and sustainable photocatalytic process.     

Fe3O4@SA/Ce微球的表征及对染料的吸附特性

以天然高分子化合物海藻酸钠(sodium alginate,SA)为骨架,结合磁性Fe₃O₄和稀土铈离子Ce(Ⅲ)通过溶液反应制备出一种新型的磁性海藻酸铈复合微球(Fe₃O₄@SA;Ce).采用X射线衍射(XRD)、孔结构比表面积分析(BET)、扫描电子显微镜(SEM)、红外光谱(FT-IR)及振动样品强磁计(VSM)对Fe₃O₄@SA;Ce的结构进行了表征,并以直接桃红12B(direct red 12B,DR 12B)和直接橙S(direct orange S,DO S)两种染料为吸附对象,探讨了Fe₃O₄@SA;Ce的吸附剂性能、吸附动力学和热力学.结果表明,Fe₃O₄@SA;Ce对室温下自然pH染料溶液中DR 12B和DO S均表现出良好的吸附效果,吸附量分别可达464 mg·g^-1和730 mg·g^-1.在不同温度下(298、313、328 K),Fe₃O₄@SA;Ce对DR 12B和DO S的吸附过程均可用拟二级吸附动力学方程准确描述.通过等温吸附研究,发现Fe₃O₄@SA;Ce对两种染料的等温吸附较好地符合Freundlich模型.各种表征结果表明,SA与Ce(Ⅲ)和Fe₃O₄交联反应后生成的Fe₃O₄@SA;Ce凝胶球表面有大量深浅不一的褶皱沟纹,形貌发生了显著变化.作为一种绿色环保、制备方法简单、可高效吸附的磁性高分子复合吸附剂,Fe₃O₄@SA;Ce对高浓度染料具有很好的吸附效果,期望能够在染料废水处理中得到广泛应用.     

Enhanced activation of peroxymonosulfate by CNT-TiO2 under UV-light assistance for efficient degradation of organic pollutants

CNT-TiO₂ composite is used to activate PMS under UV-light assistance. Superior performance is due to the enhanced electron-transfer ability of CNT. SO₄•⁻, •OH and ¹O₂ play key roles in the degradation of organic pollutants. In this work, a UV-light assisted peroxymonosulfate (PMS) activation system was constructed with the composite catalyst of multi-walled carbon nanotubes (CNT) - titanium dioxide (TiO₂). Under the UV light irradiation, the photoinduced electrons generated from TiO₂ could be continuously transferred to CNT for the activation of PMS to improve the catalytic performance of organic pollutant degradation. Meanwhile, the separation of photoinduced electron-hole pairs could enhance the photocatalysis efficiency. The electron spin resonance spectroscopy (EPR) and quenching experiments confirmed the generation of sulfate radical (SO₄•⁻), hydroxyl radical (•OH) and singlet oxygen (¹O₂) in the UV/PMS/20%CNT-TiO₂ system. Almost 100% phenol degradation was observed within 20 min UV-light irradiation. The kinetic reaction rate constant of the UV/PMS/20%CNT-TiO₂ system (0.18 min⁻¹) was 23.7 times higher than that of the PMS/Co₃O₄ system (0.0076 min⁻¹). This higher catalytic performance was ascribed to the introduction of photoinduced electrons, which could enhance the activation of PMS by the transfer of electrons in the UV/PMS/CNT-TiO₂ system.     

Hydrophilic/underwater superoleophobic graphene oxide membrane intercalated by TiO2 nanotubes for oil/water separation

GO/TiO₂ membrane was prepared by assembling GO nanosheets and TiO₂ nanotubes. The intercalation of TiO₂ nanotubes enlarged the space of GO interlayers and modified the surface morphology. Hydrophilic/underwater superoleophobic property of GO/TiO₂ membrane was obtained. Water permeability, hydrophilicity, oleophobicity and antifouling ability of GO-based membrane were all enhanced by intercalating TiO₂ nontubes. Membrane technology for oil/water separation has received increasing attention in recent years. In this study, the hydrophilic/underwater superoleophobic membrane with enhanced water permeability and antifouling ability were fabricated by synergistically assembling graphene oxide(GO) nanosheets and titanium dioxide (TiO₂) nanotubes for oil/water separation. GO/TiO₂ membrane exhibits hydrophilic and underwater superoleophobic properties with water contact angle of 62° and under water oil contact angle of 162.8°. GO/TiO₂ membrane shows greater water permeability with the water flux up to 531 L/(m²·h·bar), which was more than 5 times that of the pristine GO membrane. Moreover, GO/TiO₂membrane had excellent oil/water separation efficiency and anti-oil-fouling capability, as oil residual in filtrate after separation was below 5 mg/L and flux recovery ratios were over 80%.The results indicate that the intercalation of TiO₂ nanotubes into adjacent GO nanosheets enlarged the channel structure and modified surface topography of the obtained GO/TiO₂ membranes, which improved the hydrophilicity, permeability and anti-oil-fouling ability of the membranes, enlightening the great prospects of GO/TiO₂ membrane in oil-water treatment.