钛基石墨烯复合材料的制备及其光催化还原Cr（VI）的研究

通过改进的Hummers法制备氧化石墨烯(GO),再将氧化石墨烯和钛酸四丁酯作为初始反应物,利用溶剂热法制备Ti O_2/RGO纳米复合材料.利用SEM、TEM、XPS、XRD等分析手段对Ti O_2/RGO纳米复合材料进行表征,考察其在可见光照射条件下光催化还原水中Cr(Ⅵ)的效能,并对光催化还原机制进行了初步探讨.结果表明,Ti O_2/RGO复合材料的光催化还原能力与单一Ti O_2(P25)相比有了显著提高;复合材料中RGO含量、溶液p H值、催化剂投加量、Cr(Ⅵ)初始浓度均对光催化还原过程有所影响,当复合材料中RGO含量比例为2%、溶液p H值为2,催化剂投加量为40 mg时,光催化还原Cr(Ⅵ)的效率可达98%.光催化还原Cr(Ⅵ)的过程是吸附过程和光催化还原过程的共同作用结果,RGO不但提高了复合材料的吸附能力,还作为复合材料的电子导体,抑制了光生电子-空穴对的复合,增强了复合材料的光催化性能.经过5次循环使用后,复合材料的光催化还原效率仍然保持在90%左右.     

C3N4/BiOBr复合可见光催化剂的性能及其作用机制

利用水热合成法制备了C_3N_4/BiOBr复合可见光催化剂,通过XRD、FT-IR、SEM、DRS、PL等手段对催化剂的物相组成和光化学性能进行了系统表征,利用对罗丹明B(RhB)的降解实验评价了催化剂在可见光照下的光催化降解活性和稳定性并通过ESR分析和自由基捕获实验探究了RhB的光催化降解机制.结果表明,水热合成法可成功制备结晶性能良好的C_3N_4/BiOBr复合可见光催化剂;C_3N_4的复合降低了BiOBr光催化剂的电子-空穴的复合,提高了光催化降解活性,其中15%C_3N_4/BiOBr的活性最佳,可见光照18 min后RhB的脱色率达100%,较纯BiOBr提高了1.5倍,且重复使用5次后仍具有较高的光催化降解活性;复合催化剂光催化降解RhB过程中参与降解的主要活性物种为空穴(h~+)和超氧自由基(·O_2~-),其中h~+影响更为显著.     

Synthesis of novel CeO2-BiVO4/FAC composites with enhanced visible-light photocatalytic properties

To utilize visible light more effectively in photocatalytic reactions, a fly ash cenosphere （FAC）-supported CeO2-BiV04 （CeO2-BiVO4/FAC） composite photocatalyst was prepared by modified metalorganic decomposition and impregnation methods. The physical and photophysical properties of the composite have been characterized by X-ray diffraction （XRD）, scanning electron microscope （SEM） and energy dispersive X-ray spectroscopy （EDX）, X-ray photoelectron spectroscopy （XPS）, and UV-Visible diffuse reflectance spectra. The XRD patterns exhibited characteristic diffraction peaks of both BiVO4 and Ce02 crystalline phases. The XPS results showed that Ce was present as both Ce4＋ and Ce3＋ oxidation states in Ce02 and dispersed on the surface of BiV04 to constitute a p-n heterojunction composite. The absorption threshold of the CeO2-BiVO4/FAC composite shifted to a longer wavelength in the UV-Vis absorption spectrum compared to the pure Ce02 and pure BiV04. The composites exhibited enhanced photocatalytic activity for Methylene Blue （MB） degradation under visible light irradiation. It was found that the 7.5 wt.% CeO2-BiVO4/FAC composite showed the highest photocatalytic activity for MB dye wastewater treatment.     

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.     

Solar photocatalytic decomposition of two azo dyes on multi-walled carbon nanotubes (MWCNTs)/TiO2 composites

Multi-walled carbon nanotubes (MWCNTs)/TiO₂ composite photocatalysts with high photoactivity were prepared by sol-gel process and further characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), and UV-vis absorption spectra. Compared to pure TiO₂, the combination of MWCNTs with titania could cause a significant absorption shift toward the visible region. The photocatalytic performances of the MWCNTs/TiO₂ composite catalysts were evaluated for the decomposition of Reactive light yellow K-6G (K-6G) and Mordant black 7 (MB 7) azo dyes solution under solar light irradiation. The results showed that the addition of MWCNTs enhanced the adsorption and photocatalytic activity of TiO₂ for the degradation of azo dyes K-6G and MB 7. The effect of MWCNTs content, catalyst dosage, pH, and initial dye concentration were examined as operational parameters. The kinetics of photocatalytic degradation of two dyes was found to follow a pseudo-first-order rate law. The photocatalyst was used for seven cycles with photocatalytic degradation efficiency still higher than 98%. A plausible mechanism is also proposed and discussed on the basis of experimental results.     

FeTiO3/TiO2纳米异质结的制备和可见光催化性能

采用水热法和溶胶凝胶法制备了新型FeTiO3/TiO2纳米异质结复合材料,并明确了最优的掺杂比例(0.5%).随后利用X射线衍射能谱(XRD)、紫外-可见漫反射光谱(UV-Vis DRS)、扫描电镜(SEM)和透射电镜(TEM)等手段对该复合材料进行表征,证实了其结晶度、吸光度随掺杂量的规律性变化.电镜照片显示,该复合材料具有蓬松多孔的微观结构,且晶格条纹清晰、分散度高,有利于光电子的传导.对苯的降解实验表明,相比于纯TiO2,该催化剂的气相可见光催化能力大幅提高,降解率提升了3倍,达到40%,而CO2生成量提升了5倍,超过300 ppm.同时,电化学测试和电子顺磁共振谱(ESR)等均证实,FeTiO3的窄能带能够提高TiO2的光响应,实现可见光激发;而二者的能带相互匹配,有助于转移光生载流子,实现电子-空穴的高效分离,进而其光生电子和自由基生成能力大幅增强,因此,表现出了较强、较稳定的光催化活性.     

g-C3N4/Bi2S3复合物的制备及可见光催化降解MO

采用简单溶剂热方法成功合成可见光催化剂g-C_3N_4/Bi_2S_3.合理地利用X射线衍射(XRD)、傅立叶红外光谱分析仪(FTIR)、场发射扫描电子显微镜(FESEM)、透射电子显微镜(TEM、HRTEM)、紫外可见漫反射光谱(UV-vis DRS)等表征手段对合成的样品进行了表征.与纯g-C_3N_4和Bi_2S_3相比,g-C_3N_4/Bi_2S_3复合物对甲基橙(MO)的可见光催化降解具有更高的降解效率.根据能带分析结果,电子-空穴对的有效分离增强了光催化效率.此外,提出了g-C_3N_4/Bi_2S_3对MO的光催化降解过程以阐明降解机制.提供了一种经济简单并易于规模化扩大开发可见光响应催化剂的方法,并在废水处理中具有潜在的应用价值.     

可见光响应漂浮式微球光催化剂及其光降解模拟海水中苯酚

为了将光催化技术应用于有机物污染海水的治理,本文首先利用水热还原得到了具有可见光响应的还原商用P25光催化剂,而后将还原后的P25作为活性组分负载在透明的有机玻璃空心微球表面,制成漂浮式微球光催化剂.还原后的P25的表征结果表明,水热条件下金属还原作用会将P25中少量Ti~(4+)还原成Ti~(3+),同时催化剂表面还形成了无序化-内部结晶的核壳结构.这两种结构变化都会显著拓展还原P25催化剂的可见光响应.含苯酚模拟污染海水的光降解实验发现,降解低浓度苯酚时,漂浮型微球光催化剂显示了优异的降解效率,降解5 h的去除率达到了95%以上.由于还原P25光催化剂的稳定性并且漂浮式微球光催化剂能简易回收,在多次重复实验中微球光催化剂都可以保持较高的催化活性.     

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.      

超薄g-C3N4在可见光下协同PDS降解双氯芬酸钠的机理研究

运用一步热聚合法成功制备出二维超薄g-C_3N_4(UCN)纳米片,通过透射电子显微镜、比表面测定仪、紫外可见漫反射光谱、荧光光谱对UCN的形貌及光学性能进行表征,并利用g-C_3N_4对水相中的双氯芬酸钠(DCF)进行了光催化降解实验.结果表明,UCN具有二维超薄纳米片结构,且具有较高的比表面积、较强的可见光吸收能力及空穴-电子转移能力.UCN的光催化活性优于块状g-C_3N_4,过硫酸盐(PDS)的加入对双氯芬酸钠的降解有促进作用,UCN/PDS体系中对双氯芬酸钠降解起主导作用的活性物种为O【math203z】,经过150 min的反应,双氯芬酸钠的矿化率达到78%.双氯芬酸钠在UCN/PDS体系下的光催化降解符合一级动力学规律和Langmuir-Hinshelwood模型,DCF的光催化降解在偏酸和偏碱性的情况下具有较快的反应速率.DCF在河水中的反应速率是超纯水中的3.4倍.循环实验表明,UCN具有很好的光催化稳定性.     

CH3O·引发的溴酸盐还原机制探究

针对溴酸盐(BrO-3)污染,本研究以三聚氰胺为前驱体制备石墨相氮化碳(g-C3N4)为自由基诱导催化材料.通过XRD、TEM、UV/Vis-DRS对其物相组成和光催化性能进行表征发现,制备的层状g-C3N4有稳定片层结构及可见光响应的禁带宽度(~2.70 e V).可见光照射下,g-C3N4表面产生的光生载流子不能直接还原溴酸盐.然而,若有有机小分子(如甲醇)存在,光催化还原效率迅速增大.通过原位电子顺磁共振谱(EPR)及对材料表面的光电化学测试分析,我们探索了该体系的光催化还原Br O-3的机制.结果表明,g-C3N4带隙较窄其空穴氧化能力较弱,在光催化过程中空穴只能将甲醇分子转化为CH3O·自由基,因而甲醇分子的存在提升了光生载流子的分离效率,加剧了自由基的累积.该自由基具有较高的还原活性,可迅速将水相中的溴酸根还原至溴离子.     

脯氨酸掺杂g-C3N4纳米片的制备及其对RhB的降解

通过简单的水热及煅烧方法制备了脯氨酸掺杂的g-C₃N₄纳米片,借助FTIR、XRD、SEM、BET、XPS、UV-vis DRS、PL、电化学工作站等手段对所制备的光催化剂进行结构、形貌、组成及光电性能表征分析.结果表明,脯氨酸的加入可以自主剥离前驱体,制成纳米片状的g-C₃N₄,增加催化剂的比表面积.此外脯氨酸的引入可以调节催化剂的能带结构,增加可见光吸收,提高光生载流子分离率.在模拟可见光照射下,考察其对罗丹明B (RhB)的光催化降解性能获得了最优掺杂条件.1%脯氨酸掺杂(PCN-1%)的催化剂经过60min可见光照射即可降解99%以上的污染物.降解速率得到显著提升,PCN-1%对RhB的降解速度(0.0271min^-1)达到传统体相氮化碳(BCN)降解速率(0.0027min^-1)的10.04倍,显著提高了g-C₃N₄的光催化能力.     

Strategies for improving the photocatalytic performance of metal-organic frameworks for CO2 reduction: A review

Photocatalytic CO₂ reduction is an appealing strategy for mitigating the environmental effects of greenhouse gases while simultaneously producing valuable carbon-neutral fuels. Numerous attempts have been made to produce effective and efficient photocatalysts for CO₂ reduction. In contrast, the selection of competitive catalysts continues to be a substantial hindrance and a considerable difficulty in the development of photocatalytic CO₂ reduction. It is vital to emphasize different techniques for building effective photocatalysts to improve CO₂ reduction performance in order to achieve a long-term sustainability. Metal-organic frameworks (MOFs) are recently emerging as a new type of photocatalysts for CO₂ reduction due to their excellent CO₂ adsorption capability and unique structural characteristics. This review examines the most recent breakthroughs in various techniques for modifying MOFs in order to improve their efficiency of photocatalytic CO₂ reduction. The advantages of MOFs using as photocatalysts are summarized, followed by different methods for enhancing their effectiveness for photocatalytic CO₂ reduction via partial ion exchange of metal clusters, design of bimetal clusters, the modification of organic linkers, and the embedding of metal complexes. For integrating MOFs with semiconductors, metallic nanoparticles (NPs), and other materials, a number of different approaches have been also reviewed. The final section of this review discusses the existing challenges and future prospects of MOFs as photocatalysts for CO₂ reduction. Hopefully, this review can stimulate intensive research on the rational design and development of more effective MOF-based photocatalysts for visible-light driven CO₂ conversion.     

AgInS2/g-C3N4复合材料光催化降解邻二氯苯性能

以g-C₃N₄纳米片为模板,通过水热法原位合成高催化活性的AgInS₂/g-C₃N₄复合光催化材料,采用扫描电子显微镜（SEM）、X射线衍射（XRD）,X射线光电子能谱（XPS）,荧光光谱（PL）和表面光电压（SPV）等表征手段对材料物理、化学性能进行表征,并以邻二氯苯（o-DCB）为目标污染物研究其光催化性能.结果表明：AgInS₂成功负载到g-C₃N₄纳米片上,其组成的复合材料拓宽了光吸收范围,提高了光生电子-空穴迁移效率且降低了复合率;在可见光照射8h后气相o-DCB的光催化降解效率达到62.7%,动力学参数分别是g-C₃N₄纳米片和AgInS₂的2.13倍和1.76倍.利用原位红外光谱技术和ESR技术推导其反应机理,发现降解过程中产生了超氧自由基活性氧物种,降解的最终产物是二氧化碳、水等.     

Photocatalytic activity of Fe-doped CaTiO3 under UV-visible light

The photocatalytic degradation of methylene blue（MB） over Fe-doped CaTiO3 under UV-visible light was investigated. The as-prepared samples were characterized using X-ray diffraction（XRD）, scanning electron microscope（SEM） equipped with an energy dispersive spectrometer（EDS） system, Fourier transform infrared spectra（FT-IR）, and UV-visible diffuse reflectance spectroscopy（DRS）. The results show that the doping with Fe significantly promoted the light absorption ability of CaTiO3 in the visible light region. The Fe-doped CaTiO3 exhibited higher photocatalytic activity than CaTiO3 for the degradation of MB.However, the photocatalytic activity of the Fe-doped CaTiO3 was greatly influenced by the calcination temperature during the preparation process. The Fe-doped CaTiO3 prepared at500°C exhibited the best photocatalytic activity, with degradation of almost 100% MB（10 ppm）under UV-visible light for 180 min.     

Ag/P-g-C3N4复合材料可见光催化降解双酚AF的机理研究

利用简单的热聚合及原位沉淀法制备了一系列不同质量比(1%～10%)的Ag/P-g-C_3N_4复合材料,采用XRD、SEM、TEM、UV-Vis DRS、FTIR、BET和XPS等表征手段对复合材料的形貌结构、光学特性和化学组成进行了表征.利用合成材料光催化降解双酚AF(BPAF),研究了溶液初始pH、溶解性有机质(DOM)对BPAF降解的影响,并对光催化降解机理进行了探讨.结果表明,在pH=7时,5%Ag/P-g-C_3N_4表现出最强的光催化性能,其在90 min内对BPAF的降解率达到100%.DOM在低浓度(0.5 mg·L~(-1))时促进了BPAF的光降解,而在高浓度时(2～10 mg·L~(-1))抑制了BPAF的光降解.活性基团捕获实验结果表明,在Ag/P-g-C_3N_4降解BPAF过程中,h~+和·OH起主要的作用,直接参与了BPAF的降解.相对于P-g-C_3N_4,Ag/P-g-C_3N_4光催化性能的增强主要是因为Ag的负载促进了e~-和h~+的分离,同时Ag单质的SPR效应提高了复合材料对可见光的吸收率,延长了光生载流子的寿命.     

Visible light driven mineralization of spiramycin over photostructured N-doped TiO2 on up conversion phosphors

A novel visible light-active photocatalyst formulation(NdT/OP) was obtained by supporting N-doped TiO_2(NdT) particles on up-conversion luminescent organic phosphors(OP). The photocatalytic activity of such catalysts was evaluated for the mineralization process of spiramycin in aqueous solution. The effect of NdT loading in the range 15–60 wt.% on bulk and surface characteristics of NdT/OP catalysts was investigated by several chemicophysical characterization techniques. The photocatalytic performance of NdT/OP catalysts in the removal of spyramicin from aqueous solution was assessed through photocatalytic tests under visible light irradiation. Total organic carbon(TOC) of aqueous solution,and CO and CO_2 gas concentrations evolved during the photodegradation were analyzed. A dramatic enhancement of photocatalytic activity of the photostructured visible active NdT/OP catalysts,compared to NdT catalyst,was observed. Only CO_2 was detected in gas-phase during visible light irradiation,proving that the photocatalytic process is effective in the mineralization of spiramycin,reaching very high values of TOC removal. The photocatalyst NdT/OP at 30 wt.% of NdT loading showed the highest photocatalytic activity(58%of TOC removed after 180 min irradiation against only 31% removal after 300 min of irradiation of NdT). We attribute this enhanced activity to the high effectiveness in the utilization of visible light through improved light harvesting and exploiting. OP particles act as "photoactive support",able to be excited by the external visible light irradiation,and reissue luminescence of wavelength suitable to promote NdT photomineralization activity.     

Visible light responsive N-F-codoped TiO2 photocatalysts for the degradation of 4-chlorophenol

Visible light responsive N-F-codoped TiO₂ photocatalysts exhibit a higher catalytic activity than N-doped TiO₂ for the degradation of 4-chlorophenol due to the synergistic effect of nonmetal elements.     

Bi2MoO6/Bi2S3异质结光催化降解四环素-铜复合物

利用溶剂热法制备了Bi₂MoO₆/Bi₂S₃异质结材料,采用XRD、TEM、UV-Vis、XPS和光电流响应等表征手段对异质结材料的形貌结构、化学组成和光电性能进行了表征.利用所合成的Bi₂MoO₆/Bi₂S₃对四环素（TC）及四环素-铜（TC-Cu）复合物进行光催化降解.考察了溶液的初始pH,TC初始浓度及TC与Cu²⁺复合量比对TC降解效果的影响.通过自由基捕获实验及中间产物的鉴定探讨了Bi₂MoO₆/Bi₂S₃光催化降解TC和TC-Cu过程的主要活性自由基、中间产物及降解机制;并利用小球藻生长抑制率实验评估了光催化降解过程的毒性.结果表明所制备的Bi₂MoO₆/Bi₂S₃异质结是均匀的纳米片,带隙能为1.76 eV.Bi₂MoO₆与Bi₂S₃质量比为3：1（MS-0.3）异质结对TC浓度为10 mg·L^-1和量比为2：1的TC与Cu²⁺的中性溶液表现出最强的光催化性能,反应60 min后,TC-Cu中TC的去除率和溶液的矿化率分别为85.63%和52.94%.活性基团捕获实验的结果表明,该异质结在可见光下主要的活性物种是·O₂^-.生长抑制率实验结果表明,Cu²⁺的存在降低了复合物中TC光催化降解产物的毒性,光催化氧化可以有效去除复合物中的抗生素.     

Synergistic effect of N- and F-codoping on the structure and photocatalytic performance of TiO2

Three types of TiO₂ nanostructures were synthesized via a facile hydrolysis method at 195 °C. Effects of the preparation method and doping with N and F on the crystal structure and photocatalytic performance of TiO₂ were investigated. The nanomaterials were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, Brunauer–Emmett–Teller porosimetry, ultraviolet–visible diffuse reflectance spectroscopy and fluorescent emission spectra. Their photo-catalytic activity was examined by the photodegradation of methylene blue in aqueous solution under both ultra-violet and visible light irradiation. The results show that nitrogen and fluorine co-doped anatase TiO₂ had the characteristics of a smaller crystalline size, broader light absorption spectrum and lower charge recombination than pure TiO₂. Most importantly, more efficient photocatalytic activity under both ultra-violet and visible light was observed. The obtained N–F-TiO₂ nanomaterial shows considerable potential for water treatment under sunlight irradiation.