RGO/TiO2光催化降解2,4-二氯苯氧乙酸研究

通过Hummers法及紫外光/热还原工艺制得还原氧化石墨烯(RGO),采用溶胶-凝胶-煅烧法,以RGO和钛酸酊脂为前驱体制备出RGO/TiO2光催化复合材料,并利用XRD、FT-IR等对其进行了表征.对RGO/TiO2光催化降解性能的研究发现,复合光催化剂RGO/TiO2对2,4-二氯苯氧乙酸(2,4-D)的光催化降解活性显著优于纯TiO2,并且发现负载量和pH值对光催化降解性能有较大的影响:RGO/TiO2投加量为1.2g·L~(-1)、RGO负载量2%、pH为3、初始浓度为50 mg·L~(-1)反应12 h,2,4-D去除率达到98.75%;2,4-D降解率随着RGO/TiO2投加量的增大先增大后减小;RGO/TiO2对2,4-D的降解为脱氯还原和催化氧化过程,产生氯酚、苯酚等中间产物.     

N-TiO_2/RGO催化剂的制备及其光催化性能的研究

以三乙胺为氮源,HF为形貌控制剂,采用水热法一步合成了N掺杂(001)面锐钛矿TiO_2纳米片/还原氧化石墨烯(N-Ti O2/RGO)复合催化剂,通过XRD、FTIR、SEM、TEM和Raman对样品的组成结构和形貌进行表征。以罗丹明B(Rh B)为模拟污染物,研究了不同掺N量和氧化石墨烯加入量下制备的复合材料的光催化性能。实验结果表明:当n(N)∶n(Ti)为0.5,氧化石墨烯加入量为15 m L时,N-TiO)2/RGO复合材料的光催化性能最好。在催化剂用量为0.5 g/L,罗丹明B溶液初始浓度为20 mg/L时,紫外光催化反应30 min后,罗丹明B的降解率可达94.02%。     

Bi2O3-TiO2复合光催化剂协同处理铬-邻苯二甲酸酯复合污染

以硝酸铋和钛酸丁酯为前驱体,采用水热法制备了Bi_2O_3-TiO_2复合半导体材料,并利用X射线衍射(XRD)、紫外-可见吸收光谱(UVVis)、能谱分析(EDS)、X射线光电子能谱(XPS)等手段对复合材料的结构进行了表征.同时,考察了Bi_2O_3-TiO_2复合材料对重金属Cr(Ⅵ)和难降解邻苯二甲酸二丁酯(DBP)复合污染的处理性能,并探讨了复合催化剂协同处理复合污染的作用机制.结果表明:该复合催化剂在可见光下能同时降低重金属Cr(Ⅵ)和有机物DBP的浓度,抑制电子和空穴复合,表现出比对单一Cr(Ⅵ)及DBP污染物更高的处理效率.当Bi_2O_3含量为4%时,复合催化剂表现出最佳的光催化活性.     

部分还原氧化石墨烯-Fe3O4对水中Cd (Ⅱ)的吸附性能及机理

当前,治理可溶性重金属污染是环境保护的迫切任务.以氧化石墨烯(GO)和铁盐为前驱体,一步合成了部分还原氧化石墨烯-Fe_3O_4复合材料(rGO-Fe_3O_4),探索其作为Cd(II)高效吸附剂的潜力.同时,采用多种手段表征吸附剂结构和特性,重点研究了吸附剂对Cd(Ⅱ)的吸附特性和动力学.结果表明,在吸附剂中,纳米Fe_3O_4颗粒均匀地锚在石墨烯片层之间,避免了片层团聚,赋予其优良的吸附性能.在中性溶液中,使用rGO-Fe_3O_4(500 mg·L~(-1))吸附200.09 mg·L~(-1)Cd(II),5 min即可达到吸附平衡,吸附率和吸附量分别为90.88%和363.99 mg·g~(-1).另外,磁分离回收吸附剂仅需10 s,且循环吸附性良好.进一步研究显示,复合材料对Cd(II)的吸附为吸热、自发的化学吸附,过程受化学吸附和液膜扩散控制.     

g-C3N4协同光催化还原Cr(Ⅵ)及氧化磺基水杨酸

氮化碳是一种新型非金属半导体光催化剂,近年来发展成为一种理想的环境治理材料.通过热解三聚氰胺的方法制备出石墨相氮化碳(g-C_3N_4),利用XRD、TEM和UV-vis DRS对它的结构、形貌及光电特性进行表征,并进一步对其在协同光催化还原Cr(Ⅵ)及氧化磺基水杨酸(SSA)中的应用进行了研究,考察了催化剂投加量、初始pH以及Cr(Ⅵ)与SSA初始浓度比等条件对协同光催化反应的影响.结果表明,催化剂投加量为0.5 g·L~(-1),pH=2,初始Cr(Ⅵ)与SSA浓度比为1∶4(10 mg·L~(-1)∶40 mg·L~(-1))时,协同光催化反应达到最优化,比单独光还原或光氧化污染物的能力提高3倍以上,此时Cr(Ⅵ)的还原率为98.9%,SSA的氧化率为93.4%.本文还深入探讨了协同光催化机制,g-C3N4在可见光激发下,光生电子还原Cr(Ⅵ),同步产生的空穴、O_2~(·-)和·OH共同氧化SSA.     

TiO2光催化还原有机废水中Cr(Ⅵ)的研究

二氧化钛具有较高的光稳定性和反应活性,可以用于光催化还原去除水中的重金属离子,本文以含有Cr(Ⅵ)的有机废水为研究体系,分别考察了环糊精、pH值、反应物初始浓度、催化剂用量等对光催化还原反应的影响.结果表明,当催化剂浓度为0.5g/L,经过100分钟的紫外光照射时,Cr(Ⅵ)的光催化还原效率可达到92%;初始Cr(Ⅵ)浓度较低时,在相同条件下反应更加迅速,10min已经基本全部去除;β-CD对Cr(Ⅵ)的光催化还原有一定的促进作用;同时反应在酸性条件下可以获得较高的还原效率.     

凹凸棒石@C纳米复合材料对Cr(Ⅵ)吸附-还原作用

以凹凸棒石和葡萄糖为原料,通过设置凹凸棒石与葡萄糖不同质量比,采用水热碳化法制备凹凸棒石@C纳米复合材料,并选择出去除Cr(Ⅵ)效果最佳的凹凸棒石@C纳米复合材料.同时,利用傅里叶红外光谱(FT-IR)、X射线衍射(XRD)、Zeta电位仪(Zeta)、X光电子能谱(XPS)手段对复合材料进行了表征,考察了时间和p H对其去除水中Cr(Ⅵ)的影响,探讨了其吸附-还原机制.结果表明,最佳复合材料的凹凸棒石与葡萄糖质量比为1∶4;吸附平衡时间约为6 h,动力学过程符合准二级动力学模型.在p H为1~10时,Cr(Ⅵ)去除率随p H升高而减小,p H=1时Cr(Ⅵ)去除率最大,高达92.7%,吸附率为48.5%,还原率为44.2%;而总铬吸附率则随p H升高先增大后减小,p H=2时最大,吸附率为50.2%,还原率为13.0%,表明对Cr(Ⅵ)去除存在吸附-还原作用,酸性越强,越容易发生还原反应.FT-IR分析结果表明,凹凸棒石@C纳米复合材料表面存在含氧基团和还原性基团(Cx—OH、—CH等);XPS分析结果表明其对Cr(Ⅵ)的去除是吸附-还原相互作用的结果,包括Cr(Ⅵ)在复合材料表面与含氧基团络合配位吸附和静电吸附,以及Cr(Ⅵ)还原Cr(Ⅲ)再吸附,其中,Cr(Ⅲ)再吸附主要通过与Mg2+、Al3+等阳离子交换作用实现的.     

纳米Fe3C/炭纤维非均相电芬顿降解二甲基砷的研究

针对结构稳定且难以靠常规方法去除的二甲基砷,制备新型负载Fe_3C纳米粒子的炭纤维催化剂,并对其非均相电芬顿降解二甲基砷进行了研究.结果表明,纳米Fe_3C/CF与阴极产生的H2O2发生电芬顿催化反应产生羟基自由基将二甲基砷降解为一甲基砷和As(V),As(V)可被同步吸附在Fe_3C/CF催化剂表面.通过考察电催化过程中初始p H、反应物初始浓度、电流强度和催化剂投加量等因素对催化氧化DMA效果的影响,表明在初始p H为3,二甲基砷初始浓度为5 mg·L~(-1),Fe_3C/CF投量为500 mg·L~(-1)的最佳条件下,经非均相电芬顿反应360 min后,二甲基砷去除率高达96%.     

TiO_2光催化还原有机废水中Cr(VI)的研究

二氧化钛具有较高的光稳定性和反应活性,可以用于光催化还原去除水中的重金属离子,本文以含有Cr(Ⅵ)的有机废水为研究体系,分别考察了环糊精、pH值、反应物初始浓度、催化剂用量等对光催化还原反应的影响。结果表明,当催化剂浓度为0.5g/L,经过100分钟的紫外光照射时,Cr(Ⅵ)的光催化还原效率可达到92%;初始Cr(Ⅵ)浓度较低时,在相同条件下反应更加迅速,10min已经基本全部去除;β-CD对Cr(Ⅵ)的光催化还原有一定的促进作用;同时反应在酸性条件下可以获得较高的还原效率。     

壳聚糖/氧化石墨烯复合材料对Cr(Ⅵ)吸附性能研究

采用化学交联法制备了壳聚糖/氧化石墨烯(Cs/GO)复合材料,并用于含Cr(Ⅵ)废水的吸附研究。探讨了吸附剂组成、pH、吸附时间、Cr(Ⅵ)初始浓度对吸附剂去除Cr(Ⅵ)的影响。结果表明:Cs含量为GO质量的10%、溶液p H为2.00、Cr(Ⅵ)初始浓度为100 mg/L时吸附效果最好。吸附平衡时间为150 min。Langmuir吸附等温模型和拟二级吸附动力学方程能较好的拟合该吸附过程;该材料经过4次吸附-解吸循环吸附试验后,仍保持一定的吸附能力。因此,Cs/GO复合材料可用于含Cr(Ⅵ)废水的处理。     

Ag–AgBr/TiO2/RGO nanocomposite: Synthesis, characterization, photocatalytic activity and aggregation evaluation

Ag–AgBr/TiO_2 supported on reduced graphene oxide(Ag–AgBr/TiO_2/RGO) with different mass ratios of grapheme oxide(GO) to TiO_2 were synthesized via a facile solvothermal-photo reduction method. Compared to the single-, two-and three-component nanocomposites,the four-component nanocomposite, Ag–AgBr/TiO_2/RGO-1 with mass ratio of GO to TiO_2at 1%, exhibited a much higher photocatalytic activity for the degradation of penicillin G(PG)under white light-emitting diode(LED-W) irradiation. The PG degradation efficiency increased with the increase of mass ratio of GO to TiO_2 from 0.2% to 1%, then it decreased with the increase of mass ratio of GO to TiO_2 from 1% to 5%. The zeta potentials of RGO-nanocomposites became more negative with the presence of humic acid(HA) due to the negatively charged HA adsorption, resulting in the shift of points of zero charge to lower values of pH. The aggregations of nanocomposites were more significant due to the bridging effect of HA. Furthermore, the aggregated particle sizes were larger for RGO-nanocomposites compared to other nanoparticles, due to the bindings of the carboxylic and phenolic functional groups in HA with the oxygen-containing functional groups in the RGO-nanocomposites.The microfiltration(MF) membrane was effective for the nanocomposites separation. In the continuous flow through submerged membrane photoreactor(sMPR) system, backwashing operation could efficiently reduce membrane fouling and recover TiO_2, and thus indirectly facilitate the PG removal.     

Graphene TiO2 nanocomposites with high photocatalytic activity for the degradation of sodium pentachlorophenol

A series of graphene–TiO2photocatalysts was synthesized by doping TiO2 with graphene oxide via hydrothermal treatment. The photocatalytic capability of the catalysts under ultraviolet irradiation was evaluated in terms of sodium pentachlorophenol（PCP-Na） decomposition and mineralization. The structural and physicochemical properties of these nanocomposites were characterized by X-ray diffraction, N2adsorption–desorption, transmission electron microscopy, scanning electron microscopy, Ultraviolet–visible diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, electron paramagnetic resonance spectra, and Fourier-transform infrared spectroscopy. The graphene–TiO2nanocomposites exhibited higher photocatalytic efficiency than commercial P25 for the degradation of PCP-Na, and 63.4% to 82.9% of the total organic carbon was fully mineralized. The improved photocatalytic activity may be attributed to the accelerated interfacial electron-transfer process and the significantly prolonged lifetime of electron-hole pairs imparted by graphene sheets in the nanocomposites. However,excessive graphene and the inhomogeneous aggregation of TiO2 nanoparticles may decrease photodegradation efficiency.     

CuO-TiO2/导电聚合物纤维复合材料的制备及其光催化性能

利用高压静电纺丝技术,制得含羧基的导电聚合物纤维(聚偏氟乙烯/苯乙烯-马来酸酐共聚物/纳米石墨).水热条件下在纤维表面原位合成了纳米级的TiO2,再通过水热法在TiO2表面制备了微米级的球形CuO颗粒,得到CuO-TiO2/导电聚合物纤维复合材料.运用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、紫外-可见吸收光谱仪(UV-Vis)和热失重分析(TGA)对复合材料的结构与性能进行表征,并利用氙灯模拟太阳光进行光催化降解次甲基蓝实验.结果发现,CuO-TiO2/导电聚合物纤维复合材料的降解效率高于CuO-TiO2/非导电聚合物纤维、CuO-TiO2粉体和Degussa P25,光催化降解3.5h时,次甲基蓝的残留率为4.7％.     

SiO2纳米颗粒内嵌强化介孔TiO2单晶光催化降解盐酸四环素

吸附性能和光生载流子的分离效率是决定光催化降解抗生素的主要因素.为提高介孔TiO_2单晶(MSCs)的吸附性能和光生载流子的分离效率,在MSCs内部构建SiO_2纳米颗粒吸附结构.同时,利用表面光电压谱、氮气等温吸附-脱附、X射线衍射等研究其结构特性.最后,以盐酸四环素为抗生素代表,通过控制SiO_2纳米颗粒比表面积,考察SiO_2对复合材料吸附及光催化性能的影响.结果表明,SiO_2纳米颗粒与TiO_2单晶复合显著提高了材料的吸附性能,表面保护蚀刻进一步提升了材料的比表面积.实验条件下,高比表面积SiO_2-TiO_2单晶复合材料(KSiO_2@TiO_2)对盐酸四环素的平衡吸附量、降解效率、降解速率常数和矿化率分别达到了0.96 mg·g-1、90.2%、0.0079 min-1、54.4%,分别是MSCs的4.4、1.5、2.6和3.1倍.副产物分析表明,SiO_2复合介孔单晶材料更易将盐酸四环素降解为小分子物质.     

四环素光催化降解特性与选择性研究

研究了盐酸四环素的光催化降解行为,结果表明四环素光催化降解反应符合一级反应动力学方程,吸附过程为整个光催化降解的控制步骤,推断四环素的主要降解途径是吸附在二氧化钛(TiO2)表面发生光催化氧化反应.同时,通过对四环素与磺胺甲唑或阿莫西林混合样品的降解实验表明,改变pH、TiO2投加量等因素,两种抗生素的降解表现出了明显的选择性.     

Enhanced photocatalytic activity of fish scale loaded TiO2 composites under solar light irradiation

Fish scale (FS) loaded TiO₂ composites were investigated as photocatalysts in degradation of Methyl Orange under solar light irradiation. Composites were prepared through sol-gel method by varying mass ratio of TiO₂/FS at 90:10, 70:30 and 50:50, respectively. The catalysts prepared in this study were characterized by using XRD, SEM, FT-IR and nitrogen sorption. The effects of solar irradiation, mass ratio of TiO₂/FS composites, irradiation time and catalyst loadings were studied. Synergistic effect was found in TiO₂/FS of 90:10 composite which performed higher photocatalytic degradation than synthesized TiO₂ under solar light irradiation. However, further increasing fish scale content in the composites reduced the photocatalytic activity drastically. Under solar light irradiation, all the catalysts in this study exhibited photocatalytic activity, except TiO₂/FS of 50:50 composite that only acted as a weak biosorbent without performing any photocatalytic property. Photocatalytic degradation increased with increasing catalyst loading and irradiation time but decreased with increased of initial dye concentration.     

Fe2O3/TiO2负载膨胀珍珠岩光催化降解罗丹明B

为获得高效催化活性的光催化材料,研究不同煅烧氛围对材料在可见光下催化性能的影响,以膨胀珍珠岩（EP）为载体,采用溶胶-凝胶法,在不同煅烧氛围（O₂和/或NH₃）下制备Fe₂O₃/TiO₂负载EP的光催化复合材料〔Fe₂O₃-TEP（O₂）、Fe₂O₃-TEP（NH₃）、Fe₂O₃-TEP（O₂,NH₃）、Fe₂O₃-TEP（NH₃,O₂）〕,采用EDS（X-射线色散能谱）、BET（比表面积及孔径分析）、XRD（X射线衍射）、SEM（扫描电子显微镜）、XPS（X射线光电子能谱）等对复合材料进行表征,并研究了其在可见光下对罗丹明B的光催化降解效果.结果表明:①复合材料成功负载了Ti、Fe元素,负载的TiO₂以锐钛矿型存在,Fe₂O₃的掺杂增强了TiO₂对可见光的响应能力;②不同的煅烧氛围明显影响复合材料的晶粒尺寸、比表面积和光催化性能,其中,Fe₂O₃-TEP（O₂,NH₃）的光催化性能最好,4 h后罗丹明B降解率达到87.59%,Fe₂O₃-TEP（NH₃,O₂）、Fe₂O₃-TEP（O₂）和Fe₂O₃-TEP（NH₃）4 h后对罗丹明B的降解率则分别为65.02%、62.48%和47.48%;③在试验条件下,复合材料的光催化反应符合一阶反应动力学方程,Fe₂O₃-TEP（O₂,NH₃）、Fe₂O₃-TEP（NH₃,O₂）、Fe₂O₃-TEP（O₂）和Fe₂O₃-TEP（NH₃）相应的降解速率常数分别为0.008 3、0.004 3、0.004 3和0.002 7 min-1.研究显示,通过溶胶-凝胶法所制备的复合材料（Fe₂O₃-TEP）经煅烧后所得矿相均一;Fe₂O₃掺杂TiO₂可形成Ti—O—Fe键,减小TiO₂固有的禁带宽度;复合材料光催化性能也受到煅烧氛围的影响,先O₂后NH₃煅烧条件下所得材料的光催化性能最佳.      

In situ preparation of visible-light-driven carbon quantum dots/NaBiO3 hybrid materials for the photoreduction of Cr(VI)

In this study, different carbon quantum dots (CQDs)/NaBiO₃ hybrid materials were synthesized as photocatalysts to effectively utilize visible light for the photocatalytic degradation of contaminants effectively. These hybrid materials exhibit an enhanced photocatalytic reduction of hexavalent chromium (Cr(VI)) in the aqueous medium. Zero-dimensional nanoparticles of CQDs were embedded within the two-dimensional NaBiO₃ nanosheets by the hydrothermal process. Compared with that of the pure NaBiO₃ nanosheets, the photocatalytic performance of the hybrid catalysts was significantly high and 6 wt.% CQDs/NaBiO₃ catalyst exhibited better photocatalytic performance. We performed the first-principles density functional theory calculations to study the interfacial properties of pure NaBiO₃ nanosheets and hybrid photocatalysts, and confirmed the CQDs played an important role in the CQDs/NaBiO₃ composites. The experimental results indicated that the enhanced reduction of Cr(VI) was probably due to the high loading of CQDs (electron acceptor) on NaBiO_3, which made NaBiO₃ nanomaterials to respond in visible light and significantly improved their electron-hole separation efficiency.