溴化银/二氧化钛复合材料的可见光催化性能

将硝酸银的乙醇溶液与溶胶凝胶TiO2混合得到前驱体,随后经共沉淀-煅烧制备得到AgBr/TiO2复合材料;采用扫描电镜、X射线衍射仪、X射线光电子能谱仪分析了复合材料的形貌、晶体结构、Ag元素的价态,采用紫外-可见漫反射光谱仪测定了其光吸收性能;进而以甲基橙(MO)的可见光降解为探针反应测定了AgBr/TiO2复合材料的可见光催化性能.结果表明,当前驱体在不同温度下煅烧后,无定形TiO2颗粒逐渐增大,并逐渐转变为锐钛矿结构;担载的AgBr可明显拓展TiO2的可见光吸收范围;Ag物种主要以Ag+形式存在.当煅烧温度为300℃时,复合材料的光催化活性最高,MO的降解率在60min内达到90%以上;随着煅烧温度的增加,催化活性逐渐降低.     

Facile synthesis of phenacyl iodides from styrenes under visible light irradiation with fluorescent lamps

Phenacyl iodides were easily synthesized from styrenes with iodine under irradiation of visible light from a fluorescent lamp.     

Aerobic oxidative esterification of benzyl alcohols with catalytic tetrabromomethane under visible light irradiation

We report a useful method for the facile synthesis of aromatic esters from benzyl alcohols with molecular oxygen and catalytic tetrabromomethane in alcohol under visible light irradiation with a fluorescent lamp. This is the first metal-free reaction using molecular oxygen as the terminal oxidant.     

Photocatalytic degradation of methylene blue over N-doped MnWO4 under visible light irradiation

In recent years, the transition-metal tungstate materials with formula MWO₄ have attracted much attention in photocatalytic environmental purification due to their interesting structural and optical properties. Among the others, manganese tungstate (MnWO₄) has attracted particular attention because of its appropriate bandgap energy (2.67 ​eV) with tunable optical and electrical properties, chemical stability, and low cost which makes a suitable photocatalyst. Nevertheless, the manganese tungstate (MnWO₄) based materials are less explored as visible light responsive photocatalysts for wastewater purification. Hence, both parent and N-doped MnWO₄ are synthesized by a hydrothermal method with different nitrogen contents (5, 10, and 15 ​mol%). The as-prepared photocatalysts were characterized by XRD, SEM-EDS, TEM-SAED, FT-IR, UV–Vis DRS, XPS and PL techniques. The photocatalytic activities of the synthesized samples were evaluated by degradation of methylene blue (MB) dye under the visible light irradiation. All the N-doped MnWO₄ samples exhibited enhanced visible-light photocatalytic activity compared to the parent MnWO₄, and the optimal dopant amount of nitrogen was 15 mol% for the best photocatalytic activity. The active species generated during the process of MB degradation are investigated by scavenging experiments. Further, the reusability of the 15 ​mol% N-doped MnWO₄ photocatalyst was examined in three consecutive catalytic runs.     

Photocatalytic activities of various pentavalent bismuthates under visible light irradiation

LiBiO₃, NaBiO₃, MgBi₂O₆, KBiO₃, ZnBi₂O₆, SrBi₂O₆, AgBiO₃, BaBi₂O₆ and PbBi₂O₆ were synthesized by various processes such as hydrothermal treatment, heating and so on. These materials were examined for their photocatalytic activities in the decolorization of methylene blue and decomposition of phenol under visible light irradiation. For methylene blue decolorization, the presence of KBiO₃ resulted in complete decoloration within 5 min. For phenol decomposition, NaBiO₃ showed the highest activity, while LiBiO₃, SrBi₂O₆ and BaBi₂O₆ possessed almost comparable decomposition rates. Their decomposition rates were apparently higher than that by anatase (P25) under UV irradiation.     

Aerobic oxidation under visible light irradiation of a fluorescent lamp with a combination of carbon tetrabromide and triphenyl phosphine

A combination of CBr₄–Ph₃P, a non-metal method, enables us to carry out aerobic photo-oxidation of alcohols and aromatic methyl groups to the corresponding carboxylic acids under irradiation of vis from a general-purpose fluorescent lamp. Aliphatic primary- and secondary alcohols, benzyl alcohols, and methyl groups at the aromatic nucleus generally afforded the carboxylic acids directly in good to high yield.     

银-溴化银/麦羟硅钠石可见光催化剂的制备及其光催化性能

利用离子交换法将AgBr负载到水热合成的麦羟硅钠石(magadiite,MD)载体上,通过光照还原生成新型Ag-AgBr/MD复合光催化剂;采用X射线衍射仪、扫描电镜、透射电镜分析了复合催化剂的结构,采用紫外-可见分光光度计评价了AgBr负载量和pH对复合催化剂可见光催化降解罗丹明(RhB)水溶液活性的影响.结果表明,随着AgBr负载量的增加,RhB的降解率先增大后减小,随pH的增大RhB的降解率减小.当n(AgNO3)∶n(MD)=2∶1,pH=9时,复合光催化剂具有较强的光吸收性能,且AgBr高度分散在载体MD表面,因而对RhB的光催化降解性能最高.     

可见光诱导下磺酰氯参与的C-磺酰基化合物的合成研究进展

C-磺酰基化合物在医药、材料、合成化学等领域具有广泛的应用,其合成方法一直是有机化学工作者们的研究热点。可见光催化具有成本低、易获得和环境友好等特点,其诱导的磺酰基自由基反应已成为合成砜类化合物的重要手段。磺酰氯廉价、易获得、种类多,是一类重要的磺酰基自由基前体。本文介绍了近年来在可见光催化下,磺酰氯参与的C-磺酰基化合物的合成研究进展。按照可见光催化剂种类如Ir配合物、Ru配合物、无外加光敏剂以及其他类型光催化剂等进行分类归纳讨论,并对相应的反应机理进行了阐述,为今后此类反应在有机合成中的应用提供参考,并指出该领域研究面临的挑战及发展方向。     

CuAl2O4 powder synthesis by sol-gel method and its photodegradation property under visible light irradiation

Nanocrystalline spinel CuAl₂O₄ powders were prepared by sol-gel method from nitrate Cu(NO₃)₂·3H₂O, Al(NO₃)₃·9H₂O and complex C₆H₈O₇·H₂O. Sintering was carried out at 400, 500, 600, 700, 800°C respectively for 2 h in air. The XRD patterns started to appear CuAl₂O₄ peaks after sintering of 500°C and consist of only CuAl₂O₄ peaks as spinel crystal after sintering of 700°C. The powders were analyzed by TEM and UV-vis diffuse reflectance spectrum to be round, about 10–30 nm in size and Eg=1.77 eV. Photodegradation property of nanocrystalline CuAl₂O₄ powders was investigated by using methyl orange as model pollutant and mercury lamp (λ>400 nm) as energy source. The results indicated that CuAl₂O₄ powders sintered at 700°C had the excellent visible photocatalytic property. Under the irradiation of visible light, methyl orange could be degraded 97% in 120 min.     

可见光驱动Ag3PO4催化降解罗丹明B和甲基橙

采用简易离子交换法制备可见光驱动Ag3PO4光催化剂.通过X射线衍射、场发射扫描电子显微镜、N2吸附-脱附、紫外-可见漫反射光谱及傅里叶变换红外光谱对所制备的Ag3PO4催化剂进行表征.结果表明,在可见光照射下,Ag3PO4催化剂对罗丹明B降解表现出优越的光催化活性,但对甲基橙的降解活性低,这归因于Ag3PO4催化剂对甲基橙分子吸附量低.可见光照Ag3PO4反应体系中,空穴和超氧自由基共同发挥作用导致罗丹明B和甲基橙光催化降解.在罗丹明B的协助作用下,Ag3PO4催化剂对甲基橙的可见光催化降解活性大大增强,这是由于罗丹明B的存在可产生更多的超氧自由基,从而使甲基橙进一步降解.     

One-pot hydrothermal synthesis of willow branch-shaped MoS2/CdS heterojunctions for photocatalytic H2 production under visible light irradiation

Willow branch-shaped MoS₂/CdS heterojunctions are successfully synthesized for the first time by a facile one-pot hydrothermal method. The as-prepared samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, nitrogen adsorption-desorption measurements, diffuse reflectance spectroscopy, and photoelectrochemical and photoluminescence spectroscopy tests. The photocatalytic hydrogen evolution activities of the samples were evaluated under visible light irradiation. The resulting MoS₂/CdS heterojunctions exhibit a much improved photocatalytic hydrogen evolution activity than that obtained with CdS and MoS₂. In particular, the optimized MC-5 (5 at.% MoS₂/CdS) photocatalyst achieved the highest hydrogen production rate of 250.8 μmol h^-1, which is 28 times higher than that of pristine CdS. The apparent quantum efficiency (AQE) at 420 nm was 3.66%. Further detailed characterizations revealed that the enhanced photocatalytic activity of the MoS₂/CdS heterojunctions could be attributed to the efficient transfer and separation of photogenerated charge carriers resulting from the core-shell structure and the close contact between MoS₂ nanosheets and CdS single-crystal nanorods, as well as to increased visible light absorption. A tentative mechanism for photocatalytic H₂ evolution by MoS₂/CdS heterojunctions was proposed. This work will open up new opportunities for developing more efficient photocatalysts for water splitting.     

Synthesis,characterization and photocatalytic performance of W,N, S-tri-doped TiO2 under visible light irradiation

W–S–N-tri-doped TiO₂ photocatalysts (WSNTiO₂) were prepared by a simple sol–gel method. Tungstic acid, sodium sulfate and urea were used as tungsten, sulfur and nitrogen sources, respectively. The morphology and microstructure characteristics of the photocatalysts were evidenced by means of XRD, BET, TEM, SEM and UV–vis DRS techniques. The XRD results show that the main crystal phase of samples is anatase. It was also found that the tri-doping of TiO₂ increases its BET specific surface area from 95 to 121 m²·g⁻¹. Besides, it was shown that tri-doping narrows the band gap of TiO₂ effectively, which has greatly improved the photocatalytic activity in the visible light region. The photocatalytic activity of tri-doped TiO₂ powders was compared to that of bi-doped ones through the degradation of Congo Red (CR) under visible irradiation. Thus, the prepared 0.5% W–N–S–TiO₂ heat treated at 450 °C showed the best photocatalytic activity compared to the prepared pure TiO₂, Degussa P25, and co-doped samples (WNTiO₂ and WSTiO₂). In particular, a Congo Red degradation rate of approximately 99% was reached after only 35 min of visible light irradiation in the presence of 0.5% of WNSTiO₂. Total organic carbon (TOC) removal of CR was up to 72% and confirmed its significant mineralization in the presence of 0.5% of WNSTiO₂ photocatalyst.     

Ag/AgCl/铁-海泡石异相可见光Fenton催化降解双酚A

光-Fenton技术是高级氧化技术中的一种,常用于难降解废水处理,由于其反应速度快、毒性低、反应条件温和而受到广泛关注.然而,传统的光-Fenton体系具有可见光利用率低、回收困难等缺点.为了解决这些问题,本文采用廉价易得、无污染、吸附能力强的天然矿物海泡石作为催化剂载体,并利用Ag/AgCl能够吸收可见光的表面等离子响应这一光学性质,合成了一种有潜力的非均相等离子体光催化剂Ag/AgCl/铁-海泡石催化剂(Ag/AgCl/Fe-S),并对该催化剂的形貌结构、性能和机理等进行了系统研究.通过XRD,SEM,XPS,BET,UV-vis等表征手段对催化剂形貌、结构和可见光性能进行了分析.其中,XRD和SEM结果显示,Ag/AgCl粒子已经成功负载在Fe-海泡石上;XPS结果显示,铁氧化物的组成主要为FeOOH和Fe2O3;UV-vis结果显示,催化剂有较好的可见光吸收性能.以双酚A为目标污染物,分别考察了Ag/AgCl/Fe-S,Ag/AgCl和Fe-海泡石的光-Fenton催化性能.结果显示,Ag/AgCl/Fe-S降解双酚A的效果明显优于另外两种催化剂,在H2O2浓度为6mmol/L,pH为4,光照强度500W,Ag/AgCl/Fe-S催化剂量为1.0 g/L,双酚A初始浓度为10 mg/L的条件下,1 h时,双酚A基本被完全降解,且3 h时,其矿化率达到61.2%;而Ag/AgCl和Fe-海泡石催化剂在同样的条件下完全降解双酚A至少要3 h,且其矿化率分别只有46.61%和28.85%.另外,还分别探讨了H2O2浓度、pH值、光照强度和催化剂剂量对双酚A降解的影响.最后,通过活性物种捕获、ESR、电化学和PL实验对该体系的反应机理进行了探讨.活性物种捕获实验和ESR实验结果表明,羟基自由基(?OH)和空穴(h+)是该体系中的主要活性物种,且Ag/AgCl/Fe-S+H2O2+vis体系产生的?OH明显多于Fe-S+H2O2+vis体系.为了探讨?OH增多的原因,我们进行了电化学实验和PL实验.电化学实验结果显示,Ag/AgCl/Fe-S催化剂具有更低的阻抗,因此有利于电子-空穴分离.PL结果显示,Ag/AgCl/Fe-S催化剂的电子-空穴复合率更低.结合以上实验,我们提出了Ag/AgCl/Fe-S+H2O2+vis体系对双酚A的降解机理,即一方面催化剂能够发生Fenton反应而产生?OH,另一方面,催化剂中的Ag/AgCl在可见光下由于表面等离子响应而产生电子-空穴,空穴本身可作为活性物种降解双酚A.同时,产生的电子被体系中的Fe3+捕获生成Fe2+,从而促进了铁循环,有利于体系中产生更多的?OH.最后,空穴和羟基自由基发生协同作用共同促进污染物降解.     

Selective α-monoallylation of phenyl ketones and benzocycloalkanones under microwave irradiation

A method for the selective α-monoallylation of phenyl ketones and benzocycloalkanones with allyl alcohol under microwave irradation is described. The corresponding α-allyl ketones are obtained in moderate to good yields with only minor quantities of diallylation by-products.     

Photocatalytic hydrogen evolution from water on SiC under visible light irradiation

A kind of green SiC fine powder was characterized by XRD and UV-Vis diffuse reflectance, and studied in the photocatalytic splitting of water. The results showed that the green SiC fine powder can absorb visible light and split water with the formation of hydrogen under visible light irradiation. The activity is affected significantly by the initial pH of solutions and the types of cheap reagents, where the addition of OH⁻ or S²⁻ leads to a remarkable increase in the activity.     

Comparison of catalytic activity of carbon-based AgBr nanocomposites for conversion of CO2 under visible light

The catalytic activities of carbon-based AgBr nanocomposites (AgBr/CNT, AgBr/GP, AgBr/EG, and AgBr/AC) for CO₂ reduction to hydrocarbons under visible light were investigated in this study. The carbon-based AgBr nanocomposites were prepared on carbon-based supporting materials (CNT, GP, EG, and AC) by the deposition–precipitation method in the presence of cetyltrimethylammonium bromide (CTAB). The photocatalytic activities of AgBr nanocomposites on different supporting materials (CNT, GP, EG, and AC) were investigated by CO₂ reduction yield in the presence of water under visible light (λ > 420 nm). The results of X-ray diffraction (XRD) and transmission electron microscopy (TEM) showed that AgBr nanoparticles were well dispersed on the surface of supporting materials. AgBr/CNT and AgBr/GP had a relatively higher reduction yield under visible light due to the transfer of photoexcited electrons from the conduction band of well-dispersed AgBr to carbon supporting materials. In addition, the carbon-based AgBr nanocomposites were stable in the repeated uses under visible light. The total product yields of carbon-based AgBr nanocomposites after the 5 repeated uses almost remained about 83% of the first run. Therefore, carbon-based AgBr nanocomposite is an effective and stable visible-light-driven photocatalyst for CO₂ photoreduction.     

Research on photodegradation of formaldehyde by nanocrystalline N-TiO<Subscript>2</Subscript> powders under visible light irradiation

The photo-degradation of formaldehyde (HCHO) by nitrogen-doped nanocrystalline TiO₂ (N-TiO₂) powders under visible light irradiation has been systematically investigated. Experimental results show that the degradation ratio reached up to 42.6% after 2 h visible light irradiation when the amounts of N-TiO₂ powders were 0.5 g, the initial concentration of the HCHO was set at 0.98 mg/m³, the illumination intensity was fixed at 10,000 lux, the ambient temperature was set at 26 °C, and the relative humidity was maintained at 33 ± 5%. Further research shows that the degradation ratios were all larger than 40% in ten repeated cycles of photodegradation of HCHO by N-TiO₂ powders. The degradation ratio was as high as 82.9% after 2 h visible light irradiation when the amount of N-TiO₂ was 5 g. The degradation ratio was increased from 25.5 to 59.6% when the illumination intensity of the visible light was increased from 0 to 30,000 lux. However, the degradation ratio could not be further increased by further increasing the illumination intensity.     

Aerobic oxidation of aldehydes by visible light photocatalysis

An efficient and environmentally benign method for the oxidation of aldehydes to carboxylic acids has been developed. Singlet oxygen, generated by visible light in the presence of a Ru or Ir photocatalyst, reacted with aldehydes to give the corresponding carboxylic acids in excellent yields. The reaction is highly chemo-selective, in which only an aldehyde moiety is reactive even in the presence of other photo-oxidation active sites. This method is an example of an ideal green chemical reaction in the sense that molecular oxygen and visible light are key sources for the transformation.     

可见光辐射下新型可循环石墨烯-铁酸铋杂化催化剂高效光催化降解氨氮

近年来,本课题组利用简单的一步水热法,将石墨烯和铁酸锰、铁酸镍进行掺杂,先后制备出石墨烯铁酸锰和活性炭铁酸镍纳米光催化材料,并发现在可见光辐射作用下,这两种光催化剂均能利用可见光能量催化分解过氧化氢产生活性因子,从而有效地降解氨.基于此,本文采用简单的水热法成功制备出新型的高效多相石墨烯铁酸铋(rG-BiFeO3)催化剂,并尝试在不添加H2O2的条件下进行光降解氨氮实验.结果表明,该复合光催化剂仍可接受可见光辐射,在rG和BiFeO3的协同作用下高效地光分解氨氮.由X射线衍射结果计算出rG-BiFeO3的平均粒径约为18.5 nm.通过清晰的rG-BiFeO3的透射电镜图可以观察到,BiFeO3纳米颗粒物较均匀地分散在rG的二维表面上.对比BiFeO3和rG-BiFeO3的傅里叶变换红外光谱可以发现,rG和BiFeO3之间可能形成了化学键.拉曼光谱结果表明,相对于纯的GO,rG-BiFeO3拉曼谱线的D带和G带发生了蓝移,表明石墨烯铁酸铋复合材料中的GO被充分还原成石墨烯.对比BiFeO3和rG-BiFeO3的紫外-可见漫反射光谱发现,rG-BiFeO3的漫反射光谱发生了红移,表明rG-BiFeO3光催化材料对可见光的响应程度进一步提高.比表面积测定表明,BiFeO3的比表面积为21.0 m2/g,而rG-BiFeO3催化剂的比表面积则增加到48.6 m2/g,说明rG-BiFeO3的吸附性能将得到很大提高.可见光催化反应结果表明,在不添加H2O2,pH=11的条件下,0.2 g rG-BiFeO3对50 mg/L NH3-N的降解率达到91.2%.动力学研究表明,BiFeO3光催化剂氧化氨氮反应遵循一级反应动力学规律.另外,由于BiFeO3纳米材料本身具有一定的弱磁性,所以BiFeO3和rG的复合材料也具有一定的磁性,较易回收.催化剂经过7次循环使用后,仍然具有很高的光催化活性.根据已有文献报道,吸附在催化剂表面的氨氮被氧化的路径有两条:(1)氨在被氧化为NH2,NH和N2Hx+y(x+y=0,1,2)等一系列中间产物后,最终被分解为氮气;(2)氨被氧化为中间产物HONH2,最终分解为硝酸盐和亚硝酸盐.本文利用紫外-可见分光光度计对rG-BiFeO3光降解体系下的氨溶液进行了全波长扫描,在206和211 nm处未检测到任何吸光度,从而排除了氨氮最终分解产物为硝酸盐和亚硝酸盐的可能性.这意味着rG-BiFeO3可见光降解氨体系符合第一种氧化路径.进一步的机理研究表明,反应过程中石墨烯与铁酸铋之间的协同作用所产生的空穴、超氧阴离子自由基和羟自由基共同将NH3直接氧化成N2,其中羟基自由基在整个氧化分解过程中起着最主要的作用.