CNs−Bi12O17Cl2复合体系制备及光催化降解性能研究

采用简易水解法制备了一系列CNs−Bi₁₂O₁₇Cl₂复合半导体材料并对其物相、光学性质和光催化降解性能进行了分析表征。X射线衍射光谱表明复合体系衍射峰与四方晶相Bi₁₂O₁₇Cl₂一致,紫外可见漫反射光谱证明复合材料在可见区域具有较强的光吸收能力,由此可提高光催化活性。在可见光照射下,复合体系相对于纯Bi₁₂O₁₇Cl₂对亚甲基蓝具有更高的降解效率,特别是具有合适组分的样品CB50可以在180 min后完全去除20 mg·L⁻¹的亚甲基蓝分子,这主要是由于CNs的引入抑制了光生载流子的复合,使复合体系表现出更高的光催化降解性能。最后,提出了可能的光催化机理。     

g-C3N4/TiO2可见光催化降解磺胺甲恶唑的研究

以TiO₂颗粒和三聚氰胺为原料,采用高温煅烧法制备g-C₃N₄/TiO₂复合光催化材料,研究其对仿生生态系统中磺胺类抗生素的去除效果。利用扫描电子显微镜（SEM）、X射线衍射仪(XRD)、傅里叶变换红外光谱仪（FTIR）、紫外可见分光光度计（UV-vis DRS）对g-C₃N₄/TiO₂进行表征,并研究在可见光条件下g-C₃N₄/TiO₂对溶液中磺胺甲恶唑（SMX）的光催化降解效果。结果表明,g-C₃N₄/TiO₂具有良好的光催化活性,在可见光照射下,当g-C₃N₄/TiO₂投加量为0.2 g·L^-1时,对初始质量浓度为200 μg·L^-1的SMX的去除率可达84.3%。在相同条件下,而g-C₃N₄和TiO₂只能分别去除21.0%和16.0%的SMX,同时在仿生系统中12.37 g·m^-2 g-C₃N₄/TiO₂可以去除95.35%的SMX。通过质谱分析推测,SMX可能的降解路径分别为S—N键断裂、C—N键断裂、S—C键断裂、SMX的羟基化和SMX上氨基的硝化反应,两种可能的中间产物分别为对氨基苯磺酰胺和3-氨基-5-甲基异恶唑。     

伊红-Y敏化TiO2的制备及其可见光下光催化制氢性能

采用溶胶-凝胶法在不同温度煅烧制得TiO_2,光还原沉积法进行载铂,浸渍法使伊红-Y负载在Pt-TiO_2表面,制得系列染料敏化的Eosin Y-Pt-TiO_2可见光光催化剂。以可见光光催化制氢为探针反应考察了制备的催化剂的活性,发现350℃煅烧的Eosin Y-Pt-TiO_2可见光光催化活性最好。通过XRD、BET、FT-IR、UV-Vis漫反射等手段对样品进行了表征,发现伊红-Y的敏化扩展了TiO_2的可见光响应范围,使其在400～600nm有很强的吸收峰;随着TiO_2煅烧温度的降低,比表面积不断增大,表面羟基的数量也增加,吸附伊红-Y的量也不断增加,因此Eosin Y-Pt- TiO_2可见光光催化活性也相应提高。     

溶胶凝胶法制备氮掺杂二氧化钛及其可见光活性的研究

室温下采用溶胶凝胶法,以氨水为氮源制备出淡黄色氮掺杂二氧化钛粉末。以TG-DSC、XRD、UV-Vis漫反射吸收光谱以及XPS等手段对二氧化钛进行了表征。结果显示,所制备氮掺杂二氧化钛均为锐钛矿相,且掺杂引起光催化剂在可见光区的光吸收。以甲基橙水溶液在紫外及可见光下的脱色率为光催化活性评价依据,结果显示纯二氧化钛无可见光活性,而氮掺杂二氧化钛360 min的最大脱色率可达65.3%,说明氮掺杂有效改变了二氧化钛的可见光活性,但其紫外活性逊于纯二氧化钛。另外,在实验范围内所做的N/Ti配比与光活性的关系研究中发现,可见光活性随N/Ti配比的增大有一最佳值,而紫外光活性顺序与可见光活性不同。     

可见光激发高光催化活性的纳米TiO2光催化剂——丙酮溶剂水热合成、特性表征与光催化活性起因

通过XRD、TEM、TG-DTA和漫反射谱(DRS)等手段,分析了采用丙酮溶剂水热法合成的在可见光波段对甲基橙具有高光催化降解率的纳米TiO2粉体的材料特性与光催化活性的起因。结果表明,经不同温度热处理得到的样品均为锐钛矿晶型、粒径基本相同,但在表面剩余吸附物含量以及可见光波段的光吸收率等方面差异明显,且样品表面剩余吸附物含量、可见光波段的光吸收率与其可见光催化活性之间存在直接关联。分析认为,TiO2表面剩余吸附有机物导致的对可见光的强烈吸收是其可见光波段高光催化活性的重要起因。     

可见光激发高光催化活性的纳米Ti02光催化剂--丙酮溶剂水热合成、特性表征与光催化活性起因

通过XRD、TEM、TG-DTA和漫反射谱(DRS)等手段,分析了采用丙酮溶剂水热法合成的在可见光波段对甲基橙具有高光催化降解率的纳米TiO2粉体的材料特性与光催化活性的起因.结果表明,经不同温度热处理得到的样品均为锐钛矿晶型、粒径基本相同,但在表面剩余吸附物含量以及可见光波段的光吸收率等方面差异明显,且样品表面剩余吸附物含量、可见光波段的光吸收率与其可见光催化活性之间存在直接关联.分析认为,TiO2表面剩余吸附有机物导致的对可见光的强烈吸收是其可见光波段高光催化活性的重要起因.     

Ho掺杂纳米TiO2光催化性能研究

以钛酸四正丁酯为原料,采用溶胶-凝胶法制备了纯的和Ho掺杂的TiO_2纳米粒子,对样品进行了TG- DTA、XRD和UV-Vis吸收光谱分析,并以甲基橙的光脱色反应考察了样品的光催化性能。发现Ho的掺杂抑制了TiO_2粒径的长大,细化了晶粒;Ho掺入到TiO_2的晶格中,引起了晶格的畸变和膨胀;Ho的掺杂使TiO_2的吸收带边发生微小的蓝移,且在450nm和540nm光区附近产生吸收;适量Ho的掺杂可提高TiO_2的光催化性能,紫外光照下,Ho的掺杂量为0.3%时,光催化性能最佳;可见光下(波长>420nm),Ho掺杂的TiO_2呈现光催化活性,210min内甲基橙的脱色率可达21.6%。     

S掺杂ZnS纳米晶的水热合成及其可见光光催化活性

以硫代乙酰胺(TAA)和硝酸锌(Zn(NO_3)_2·6H_2O)为原料,通过简单的控制TAA的投量,利用水热法制备了不同S量掺杂的ZnS纳米晶粒.XRD分析表明所合成样品均为六方相的ZnS,通过Scherrer公式计算出其晶粒大小约为21nm,紫外-可见漫反射吸收光谱显示所合成样品在400～600nm范围内有部分吸收,可见光降解罗丹明B的光催化反应表明S掺杂ZnS样品对罗丹明B有一定的可见光光催化活性.笔者认为,S以填隙掺杂方式进入ZnS,在其中产生杂质能级,改善了样品可见光吸收特性,并最终产生可见光光催化活性.     

TiO2/沸石光催化性能的研究

以钛酸丁酯为原料,用溶胶-凝胶法制备了TiO2并将之负载到天然沸石上。使用XRD、SEM及比表面积分析仪对样品进行了表征;以甲基橙为光催化降解模型,紫外灯为光源,用褪色率等对光催化剂性能进行了评价;对天然沸石负载TiO2的光催化性能及影响因素进行了探讨。实验表明:300℃焙烧后、含有少量金红石相混晶的锐钛矿TiO2光催化能力最好。甲基橙的初始浓度及光强越大,光解率也越大,在pH约等于6时,光解率达到最大。     

ZnxCd1-xS的共沉淀法制备及其光催化活性研究

利用共沉淀一步法在常温下合成具有高光催化活性的Zn_xCd_1-xS固溶体光催化剂,用XRD、SEM、XPS、BET、UV-VIS DRS和PL对制备出的Zn_xCd_1-xS样品进行结构和光学性能的表征,并在模拟太阳光照射下对罗丹明B（RhB）溶液进行降解,评价其光催化活性。结果表明,Zn_xCd_1-xS对可见光的吸收阀值随Zn含量增加而减少,禁带宽度随之增大;颗粒状Zn_xCd_1-xS固溶体对罗丹明B具有较高的光催化活性,其中Zn_0.8Cd_0.2S的光催化性能最优,在90 min内对RhB的降解率达到98.5%,远高于CdS和ZnS光催化剂;经过4次重复使用后,Zn_0.8Cd_0.2S对RhB的降解率维持在75%以上。Zn_0.8Cd_0.2S的比表面积和孔隙体积相对于CdS分别增至154.6 m²/g和0.40 cm³/g,其光催化活性显著增强的主要原因是由于其较高的光生电子空穴对的分离效率及较低的复合率。     

Sonochemistry synthesis of Bi2S3/CdS heterostructure with enhanced performance for photocatalytic hydrogen evolution

Photocatalytic hydrogen evolution from water splitting is an efficient, eco-friendly method for the conversion of solar energy to chemical energy. A great number of photocatalysts have been reported but only a few of them can respond to visible-light. Metal sulfides, a class of visible-light response semiconductor photocatalysts for hydrogen evolution and organic pollutant degradation, receive a lot of attention due to their narrow band gaps. Herein, we report the sonochemical synthesis of Bi₂S₃/CdS nanocrystal composites with microsphere structure at mild temperature. The phases of Bi₂S₃ and CdS can be observed obviously in HRTEM image. The heterostructure consisting of the two species of nanocrystals plays a key role in separating photo-generated charge carriers. Photocatalytic activities for water splitting are investigated under visible-light irradiation (λ > 400 nm) and an enhanced photocatalytic activity is achieved. The initial rate of H₂ evolution is up to 5.5 mmol h⁻¹ g⁻¹ without resorting to any cocatalysts.     

Cetyltrimethylammoniumbromide (CTAB)-assisted hydrothermal synthesis of ZnIn2S4 as an efficient visible-light-driven photocatalyst for hydrogen production

A series of ZnIn₂S₄ photocatalysts was synthesized via a cetyltrimethylammoniumbromide (CTAB)-assisted hydrothermal method. These ZnIn₂S₄ products were characterized by X-ray diffraction (XRD), UV–visible absorption spectra (UV–vis) and scanning electron microscopy (FESEM). The effects of hydrothermal time and CTAB on the crystal structures, morphologies and optical properties of ZnIn₂S₄ products were discussed in detail. The photocatalytic activities of the as-prepared samples were evaluated by photocatalytic hydrogen production from water under visible-light irradiation. It was found that the photocatalytic activities of these ZnIn₂S₄ products decreased with the hydrothermal time prolonging while increased with the amount of CTAB increasing. The highest quantum yield at 420 nm of ZnIn₂S₄ photocatalyst, which was prepared through the CTAB (9.6 mmol)-assisted hydrothermal procedure for 1 h, was determined to be 18.4%. The optimum amount of Pt loaded for the ZnIn₂S₄ photocatalyst was about 1.0 wt%, under the present photocatalytic system.     

Photocatalytic hydrogen production from aqueous solutions over novel Bi0.5Na0.5TiO3 microspheres

Metal oxide compounds containing bismuth are considered as potential candidates for photocatalysis in both contaminant degradation and H₂ generation, due to the interesting lone electron pairs and the band gap narrowing effect of Bi³⁺. Quaternary perovskite oxide Bi_0.5Na_0.5TiO₃ was thus synthesized at low temperature via a soft chemical route. The influence of alkaline concentrations on the structure, morphology, and optical properties of the samples has been systematically investigated. All samples existed as hierarchical microspheres, which are consisted of cubic nanocrystallines. For the first time, the photocatalytic water splitting for H₂ evolution over Bi_0.5Na_0.5TiO₃ has been studied. A high H₂ evolution rate of 325.4 μmol h⁻¹ g cat⁻¹ under the irradiation of a 500 W xenon lamp was obtained. More importantly, no decrease in the catalytic performance was observed after three consecutive runs of 15 h, suggesting new possibility in designing multi-component photocatalysts for future applications.     

Synergetic catalysis of CuO and graphene additives on TiO2 for photocatalytic water splitting

A highly efficient and visible-light-responsive CuO/TiO₂-GR photocatalyst had been synthesized by a two-step process. The as-prepared CuO/TiO₂-GR composites were characterized by X-ray diffraction, N₂-physisorption, transmission electron microscope, X-ray photoelectron spectroscopy, Raman spectra, UV–vis diffuse reflectance spectra and Photoluminescence spectra. The results indicated that a chemical bond formed between GR and TiO₂ in CuO/TiO₂-GR composites. CuO/TiO₂-GR composites had a higher photocatalytic activity for hydrogen production due to a synergistic effect between CuO and GR. The synergistic effect could efficiently suppress charge recombination, improve interfacial charge transfer, enhance visible-light adsorption and provide plentiful phtotocatalytic reaction active sites. The maximum hydrogen evolution rate of CuO/TiO₂-GR-0.5 was 2905.60 μmol/(h·g), which was 20.20 times larger than pure P25.     

Synthesis of (CuIn)xCd2(1−x)S2 photocatalysts for H2 evolution under visible light by using a low-temperature hydrothermal method

A new series visible-light driven photocatalysts (CuIn)_xCd_2(1−x)S₂ was successfully synthesized by a simple and facile, low-temperature hydrothermal method. The synthesized materials were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) surface area measurement, X-ray photoelectron spectroscopy (XPS) and ultraviolet-visible spectroscopy (UV–Vis DRS). The results show that the morphology of the photocatalysts changes with the increase of x from 0.01 to 0.3 and their band gap can be correspondingly tuned from 2.37 eV to 2.30 eV. The (CuIn)_xCd_2(1−x)S₂ nanocomposite show highly photocatalytic activities for H₂ evolution from aqueous solutions containing sacrificial reagents, SO₃²⁻ and S²⁻ under visible light. Substantially, (CuIn)_0.05Cd_1.9S₂ with the band gap of 2.36 eV exhibits the highest photocatalytic activity even without a Pt cocatalyst (649.9 μmol/(g h)). Theoretical calculations about electronic property of the (CuIn)_xCd_2(1−x)S₂ indicate that Cu 3d and In 5s5p states should be responsible for the photocatalytic activity. Moreover, the deposition of Pt on the doping sample results in a substantial improvement in H₂ evolution than the Pt-loaded pure CdS and the amount of H₂ produced (2456 μmol/(g h)) in the Pt-loaded doping system is much higher than that of the latter (40.2 μmol/(g h)). The (CuIn)_0.05Cd_1.9S₂ nanocomposite can keep the activity for a long time due to its stability in the photocatalytic process. Therefore, the doping of CuInS₂ not only facilitates the photocatalytic activity of CdS for H₂ evolution, but also improves its stability in photocatalytic process.     

Morphological, optical and photocatalytic properties of TiO2–Fe2O3 multilayers

Morphological, optical and photocatalytic properties of TiO₂, Fe₂O₃ and TiO₂–Fe₂O₃ samples (formed by 1, 3 and 5 coatings) were studied. The layers were deposited on glass substrate by the sol–gel method. The catalytic activity of the samples was studied by the photodecomposition of methylene blue (MB) under visible light illumination. The FTIR results indicate that all samples present surface OH radicals that are bound either to the Ti or Fe atoms. This effect is better visualized at larger number of coatings in the TiO₂–Fe₂O₃/glass systems. Also, two mechanisms are observed during the photodecomposition of the MB.     

Fabrication of graphene/CaIn2O4 composites with enhanced photocatalytic activity from water under visible light irradiation

A series of graphene/CaIn₂O₄ composites were synthesized using a facile solvothermal method to improve the photocatalytic performance of CaIn₂O₄. The reduction of graphene oxide to graphene and the deposition of CaIn₂O₄ nanoparticles on the graphene sheets can be achieved simultaneously during the solvothermal process. The photocatalytic activities of as-prepared graphene/CaIn₂O₄ composites for hydrogen evolution from CH₃OH/H₂O solution were investigated under visible light irradiation. It was found that graphene exhibited an obvious influence on the photocatalytic activity of CaIn₂O₄. The graphene/CaIn₂O₄ composite reached a high H₂ evolution rate of 62.5 μmol h⁻¹ from CH₃OH/H₂O solution when the content of graphene was 1 wt%. Furthermore, the 1 wt% graphene/CaIn₂O₄ composite did not show deactivation for H₂ evolution for longer than 32 h. This work could provide a new insight into the fabrication of visible light driven photocatalysts with efficient and stable performance.     

Improving photocatalytic activity for hydrogen evolution over ZnIn2S4 under visible-light: A case study of rare earth modification

A series of rare earth (RE) ions (La³⁺, Ce³⁺, Gd³⁺, Er³⁺ or Y³⁺) modified ZnIn₂S₄ photocatalysts (RE-ZnIn₂S₄) were prepared using the hydrothermal method and characterized by various analysis techniques, such as UV–Vis diffusive reflectance spectroscopy, X-ray diffraction, scanning electron microscopy, Brunauer–Emmett–Teller surface analyzer, photoluminescence spectroscopy and X-ray photoelectron spectroscopy. The results indicated that the RE element exists as the oxide RE₂O₃ and their modification can reduce ZnIn₂S₄ crystallite size, inhibit ZnIn₂S₄ grain growth, promote ZnIn₂S₄ crystallite self-organization into a micro-sphere flower-like morphology, increase ZnIn₂S₄ surface area and total pore volume, and bring rich defects to ZnIn₂S₄. The photocatalytic activities of RE-ZnIn₂S₄ were evaluated based on photocatalytic hydrogen production from water under visible-light irradiation and the hydrogen production efficiency increased by 46%, 53%, 61%, 69%, and 106% after adding 2.0 wt% of Y, Gd, Er, Ce and La, respectively. The relationship between the photocatalytic activity of RE-ZnIn₂S₄ and the RE properties was discussed.     

Preparation of multiwalled carbon nanotubes/Cd0.8Zn0.2S nanocomposite and its photocatalytic hydrogen production under visible-light

Multiwalled carbon nanotubes (MWCNTs)/Cd_0.8Zn_0.2S nanocomposites were synthesized via the simple co-precipitation of pretreated MWCNTs, acetates and sodium sulfide. The photocatalytic activities for hydrogen production of the produced MWCNTs/Cd_0.8Zn_0.2S with different amount of MWCNTs were systematically investigated under visible-light (λ ≥ 420 nm) irradiation. Enhanced photoactivity of the nanocomposite was observed and can be attributed to the synergetic effect of its components’ intrinsic properties, such as excellent light absorption and charge separation on the interfaces between the modified MWCNTs and Cd_0.8Zn_0.2S. It is also found that the nanocomposite with 15 wt% MWCNTs shows a higher photocatalytic hydrogen production efficiency and photostability than the pristine CdS and Cd_0.8Zn_0.2S nanoparticles. The MWCNTs/Cd_0.8Zn_0.2S nanocomposite holds promise for hydrogen production by improving the visible-light-driven photoactivity and photostability of Cd_0.8Zn_0.2S.