Preparation of Calcium Cross-linked Nano-Fe3O4 Modified Zeolite Microspheres for Cu^2+ Adsorption from Wastewater

Artificial zeolite was modified by nano-Fe3O4 for development of functional adsorbents.Subsequently,adsorbents such as calcium cross-linked nano-Fe3O4 microspheres (Ca-MS),calcium cross-linked nano-Fe3O4 modified zeolite microspheres (Ca-MZS) and iron cross-linked nano-Fe3O4 modified zeolite microspheres (Fe-MZS) were prepared and compared for their adsorption performance.The effects of adsorbent dosage,solution pH,initial concentration and ion content on the removal of Cu^2+ from wastewater are investigated,and the adsorption kinetics and isotherms for the adsorbent materials were analyzed.The experimental results indicate that for the initial concentration of Cu^2+ of 30 mg/L,the adsorption is noted to be most stable.The optimal initial pH for adsorbing Cu^2+ is observed to be 5.5.At an optimal dosage of Ca-MZS of 900 mg/L,the adsorption capacity is measured to be 28.25 mg/g,along with the removal rate of 72.49%.The addition of Na+ and K+ affects the adsorption of Cu^2+.For the Na^+ and K^+ concentration of 0.2 mmol/L,the Cu^2+ removal rate by Ca-MZS drops to 11.94% and 22.12%,respectively.As compared with the adsorbents such as Natural Zeolite (NZ),Ca-MS and Fe-MZS,Ca-MZS demonstrates the best removal effect in solution,where the removal rate reaches 84.27%,with the maximum adsorption capacity of 28.09 mg/g.The Cu^2+ adsorption kinetics of Ca-MZS is observed to follow the Elovich kinetic model,with the adsorption isotherm data fitting the Freundlich isotherm model by using the non-linear method.

3D flower-like heterostructured TiO_2@Ni(OH)_2 microspheres for solar photocatalytic hydrogen production

TiO2@Ni(OH)2 core-shell microspheres were synthesized by a facile strategy to obtain a perfect 3D flower-like nanostructure with well-arranged Ni(OH)2 nanoflakes on the surfaces of TiO2 microspheres;this arrangement led to a six-fold enhancement in photocatalytic hydrogen evolution. The unique p-n type heterostructure not only promotes the separation and transfer of photogenerated charge carriers significantly, but also offers more active sites for photocatalytic hydrogen production. A photocatalytic mechanism is proposed based on the results of electrochemical measurements and X-ray photoelectron spectroscopy.

Highly photoreactive TiO_2 hollow microspheres with super thermal stability for acetone oxidation

TiO2hollow microspheres(TiO2‐HMSs)have attracted much attention because of their high photoreactivity,low density,and good permeability.However,anatase TiO2‐HMSs have poor thermal stability.In this study,surface‐fluorinated TiO2‐HMSs were assembled from hollow nanoparticles by the hydrothermal reaction of the mixed Ti(SO4)2–NH4HF–H2O2solution at180°C.The effect of the calcination temperature on the structure and photoreactivity of the TiO2‐HMSs was systematically investigated,which was evaluated by photocatalytic oxidation of acetone in air under ultraviolet irradiation.We found that after calcination at300°C,the photoreactivity of the TiO2‐HMSs decreases from1.39×10?3min?1(TiO2‐HMS precursor)to0.82×10?3min?1because of removal of surface‐adsorbed fluoride ions.With increasing calcination temperature from300to900°C,the building blocks of the TiO2‐HMSs evolve from truncated bipyramidal shaped hollow nanoparticles to round solid nanoparticles,and the photoreactivity of the TiO2‐HMSs steady increases from0.82×10?3to2.09×10?3min?1because of enhanced crystallization.Further increasing the calcination temperature to1000and1100°C results in a decrease of the photoreactivity,which is ascribed to a sharp decrease of the Brunauer–Emmett–Teller surface area and the beginning of the anatase–rutile phase transformation at1100°C.The effect of surface‐adsorbed fluoride ions on the thermal stability of the TiO2‐HMSs is also discussed.

Photocatalytic Activity of TiO_2 Coating on Natural Feather Zeolite in Degradation of Orthomonochlorphenol

Ti02 coatings on natural feather zeolite are respectively prepared by a collosol （Sol-gel） method and two powder coating methods with deionizod water or dehydrated ethanol as a dispersant. During degradation of orthomono- chlorphenol solutions by ultraviolet, the strong adsorption capability of the zeolite results in increased concentration of substrate on its surface. The Ti（h film coated on feather zeolite further enhances the photocatalytic activity. The TiO~ film on the zeolite prepared by the Sol-gel method is found more effective as a catalyst than that by two powder coating methods.

Preparation and Properties of TiO2-Coated Hollow Glass Microspheres as Thermal Insulation Materials for Energy-Saving Buildings

A hollow glass microsphere(HGM)/TiO2 composite hollow sphere was successfully prepared via a simple precipitation method.The TiO2 coating layers grew on the surface of the HGMs that range from 20 to 50μm in diameter as nanoparticles with the formation of the SiO Ti bonds.The growth mechanism accounting for the formation of the TiO2 nanolayers was proposed.The morphology,composition,thermal insulation properties,and visible-near infrared(VIS-NIR)refl ectance of the HGMs/TiO2 composite hollow spheres were characterized.The VIS-NIR reflectance of the HGMs/TiO2 composite hollow spheres increased by more than 30%compared to raw HGMs.The thermal conductivity of the particles is 0.058 W/(m K).The result indicates that the VIS-NIR reflectance of the composite hollow spheres is strongly influenced by the coating of TiO2.The composite hollow spheres were used as the main functional filler to prepare the organic-inorganic composite coatings.The glass substrates coated by the organic-inorganic coatings had lower thermal conductivity and higher near infrared reflectivity.Therefore,the HGMs/TiO2 composite hollow spheres can reflect most of the solar energy and effectively keep out the heat as a thermal insulation coating for energy-saving constructions.

利用天然矿物承载TiO_2制备光催化功能材料的研究

利用天然沸石、膨润土作载体制备的TiO2 /矿物复合体光催化材料 ,在阳光照射下对有机染料罗丹明 -B具分解脱色性能。实验证实未经高温处理的样品光催化性能优于经高温处理的 ,沸石的脱色率 6小时达 10 0 %,膨润土的脱色率达 94 %。晶相分析和热分析证实锐钛矿在有沸石、膨润土存在的水相体系中可直接在矿物表面生成 ,结合牢固 ,同时引起矿物结构的调整。

TiO2/沸石复合光催化剂的制备及其对盐酸四环素的光降解

用溶胶-凝胶法制备TiO 2/沸石复合光催化剂,采用X射线衍射仪、拉曼光谱等分析手段对其进行了表征,通过试验探究复合光催化剂降解水中盐酸四环素的影响因素及其规律,同时对催化剂稳定性作评价。结果表明,当复合光催化剂投加量为4 g/L,盐酸四环素初始质量浓度为20 mg/L,pH值为4.47,暗反应30 min,紫外光照120 min时,盐酸四环素去除率可达91.7%。催化剂的稳定性试验表明,复合光催化剂在重复使用4次以内时去除率可保持在80%左右。

FTIR与XRD的均匀粒度分布Ce-Cu/TiO2空心微球制备机理研究

随着社会经济的发展,环境空气品质已经成为研究热点。 TiO 2是一种化学稳定性高,耐腐蚀性强,对人体无毒无害的N型半导体材料。利用TiO 2的光催化性能提高室内环境空气品质已经成为研究焦点,但是由于TiO 2只能在紫外光源下才具有较高的光催化效率,而在可见光源下的光催化效率较低,从而极大的限制了TiO 2在室内环境领域的发展。因此,研发在可见光源下具有良好光催化性能的TiO 2复合材料势在必行。利用元素掺杂改性技术与提高比表面积方法可以改善光催化反应过程中量子效率和对光能的利用率,以加快电子和空穴向表面迁移的速率同时降低光生载流子的复合机率。以二氧化硅SiO 2为模板、聚乙烯吡咯烷酮为成膜剂、硝酸铈Ce(NO 3) 3·6H 2O和硝酸铜Cu(NO 3) 2·3H 2O为改性剂采用溶胶-凝胶法制备均匀粒度分布的Ce-Cu/TiO 2空心微球,并将制备过程分为四个阶段,即纳米SiO 2球模板的制备、 Ce-Cu/TiO 2-SiO 2复合微球凝胶的制备、 Ce-Cu/TiO 2-SiO 2复合微球的制备和Ce-Cu/TiO 2空心微球的制备。利用傅里叶变换红外光谱仪(FTIR)与X射线衍射仪(XRD)对Ce-Cu/TiO 2空心微球的制备过程各阶段生成物进行测试与分析,即在纳米SiO 2球模板的制备阶段从微观角度研究纳米SiO 2球模板的搭建过程,在Ce-Cu/TiO 2-SiO 2复合微球凝胶的制备阶段研究TiO 2附着于纳米SiO 2球模板的过程,在Ce-Cu/TiO 2-SiO 2复合微球的制备阶段研究煅烧工艺对Ce-Cu/TiO 2-SiO 2复合微球中晶相与结构的影响,在Ce-Cu/TiO 2空心微球的制备阶段研究氢氧化钠溶液对Ce-Cu/TiO 2-SiO 2复合微球中纳米SiO 2球模板洗涤效果的影响。利用紫外-可见分光光度计(UV-Vis)对Ce-Cu/TiO 2空心微球的光响应性能进行测试与分析,以研究Ce-Cu/TiO 2空心微球对可见光源的利用效率。利用激光粒度分析仪(LPSA)与扫描电子显微镜(SEM)对Ce-Cu/TiO 2空心微球的粒度分布与微观形貌进行测试与分析,以研究Ce-Cu/TiO 2空心微球的均匀粒度分布效果。结果表明:以Si—O—Si基团构建非晶体结构的无定形态纳米SiO 2球模板,有利于聚乙烯吡咯烷酮在纳米SiO 2球模板表面附着,从而控制Ce-Cu/TiO 2空心微球的空腔结构。 Ce-Cu掺杂基本进入TiO 2晶体,极少进入纳米SiO 2球模板晶体,从而抑制了Ce-Cu/TiO 2-SiO 2复合微球中TiO 2由锐钛矿相向金红石相的转变。 Ce-Cu掺杂TiO 2可以促使TiO 2内部形成新的能级,实现能量较小的光子捕获e -和h +,从而提高Ce-Cu/TiO 2空心微球对可见光源的利用效率。 Ce-Cu/TiO 2空心微球的表面光滑且不存在明显的缺陷,其形貌呈现良好的球体且粒径分布均匀,即 d 90 为219.54 nm, d 50 为151.60 nm、 d 10 为103.84 nm,以及 d 90 -d 10 为115.70 nm。研究结果为进一步获得可见光源下具有良好光催化性能的均匀粒度分布Ce-Cu/TiO 2空心微球提供理论依据和研究基础。

TiO_2/沸石负载型催化剂的催化性能研究

以钛液 (TiOSO4)为原料 ,尿素为沉淀剂 ,10 0目沸石为载体 ,制备了负载型TiO2 /沸石催化剂 ,并探讨了TiOSO4的浓度、反应温度、反应时间及负载TiO2 /沸石催化剂的焙烧温度和降解时辅助氧化剂H2 O2 的用量对TiO2 /沸石负载型催化剂催化降解

沸石及水泥基材料二次负载TiO2的光催化性能

以天然沸石为原料,通过6 h碱处理及400℃热处理对沸石进行改性,以改性沸石为载体来分散负载光催化剂纳米TiO2,制备出了改性沸石负载光催化剂.通过内掺法、喷涂法和露骨料法将改性沸石负载光催化剂二次负载于水泥基材料,研究负载纳米TiO2水泥基材料的光催化性能.结果表明:碱热处理增加了改性沸石对纳米TiO2的负载量,光催化剂的吸附水平与降解水平均明显提升;改性沸石与纳米TiO2形成了新的Ti—O—Si化学键,结合牢固;喷涂法二次负载制备的光催化水泥基材料具有较高的降解率.

Porous TiO2-coated Magnetic Core-Shell Nanocomposites：Preparation and Enhanced Photocatalytic Activity

The core-shell structured TiO2/SiO2 @Fe3O4 photocatalysts were prepared using Fe3O4 as magnetic core,tetraethoxysilane（TEOS） as silica source and tetrabutyl titanate（TBOT） as titanium sources.The as-obtained structure was composed of a SiO2@Fe3O4 core and a porous TiO2 shell.The diameter of SiO2@Fe3O4 core was about 205 nm with thickness of porous TiO2 of about 5-6 nm.The 9%TiO2/6%SiO2@Fe3O4 microspheres possess the highest BET surface area and the BJH pore volume,which are 373.5 m2.g-1 and 0.28 cm3.g-1,respectively.The 9%TiO2/6%SiO2@Fe3O4 photocatalyst exhibited an excellent performance for the degradation of methyl orange and methylene blue dyes.Two different dyes were completely decolorized in 60 min under UV irradiation.The photocatalytic activity and the amount of catalyst were almost not decrease after recycling for 6 times by using external magnetic field.

TiO_2/NaY Composite as Photocatalyst for Degradation of Omethoate

Photocatalytic activities of TiO2 and NaY zeolites-supported TiO2 were investigated with omethoate as a model pollutant.The physical and chemical states of NaY zeolite-supported TiO2 were evaluated via XRD,FTIR,BET and SEM.Photodegradation of omethoate was studied with H2O2 as oxidant and TiO2 supported on NaY zeolite as photocatalyst.Parameters involved in the photo-catalysis of omethoate,i.e.,the calcination temperature of the photocatalyst,initial omethoate concentration,the amount of TiO2 loaded on NaY zeolite,photocatalyst dosage and H2O2 concentration were investigated in detail.The results show that TiO2/NaY zeolite prepared by means of sol-gel method exhibited a good photocatalytic activity for the degradation of omethoate.Optimum conditions included the calcination temperature of photocatalyst 550℃,initial omethoate concentration 500 mg/L,the amount of TiO2 loaded on NaY zeolite 35%（mass fraction）,the amount of photocatalyst 5 g/L,H2O2 concentration 30 mL/L and an irradiation time of 180 min.The removal of omethoate was up to 93%.Kinetics parameters of the photocatalytic degradation of omethoate were measured and calculated.The result shows the kinetics of photocatalytic degradation of omethoate is first-order.

改性沸石/TiO_2的制备及光催化降解亚甲基蓝

使用碱液侵蚀加煅烧的方法对天然沸石改性,获得改性沸石。以改性沸石为载体,钛酸丁酯为前驱体,使用溶胶-凝胶法制备了改性沸石/TiO_2催化剂。使用亚甲基蓝作为目标污染物,测试改性沸石/TiO_2催化剂的降解性能。结果表明,采用改性沸石负载TiO_2的方法有助于提高光催化剂的利用效率,当TiO_2的负载率为6. 08%时,对亚甲基蓝的降解效率高达0. 935。XRD、SEM-EDS、BET、FTIR测试结果表明,TiO_2以纳米尺度在改性沸石表面均匀分布,并且与改性沸石建立了较强的化学键连接,有利于改性沸石/TiO_2催化剂的长期性能。

Synergic effects of Cu_xO electron transfer co-catalyst and valence band edge control over TiO_2 for efficient visible-light photocatalysis

Bandgap engineering by doping and co‐catalyst loading are two primary approaches to designing efficient photocatalysts by promoting visible‐light absorption and charge separation,respectively.Shifting of the TiO2conduction band edge is frequently applied to increase visible‐light absorption but also lowers the reductive properties of photo‐excited electrons.Herein,we report a visible‐light‐driven photocatalyst based on valance band edge control induced by oxygen excess defects and modification with a CuxO electron transfer co‐catalyst.The CuxO grafted oxygen‐rich TiO2microspheres were prepared by ultrasonic spray pyrolysis of the peroxotitanate precursor followed by a wet chemical impregnated treatment.We found that oxygen excess defects in TiO2shifted the valence band maximum upward and improved the visible‐light absorption.The CuxO grafted onto the surface acted as a co‐catalyst that efficiently reduced oxygen molecules to active intermediates(i.e.,O2??radial and H2O2),thus consuming the photo‐generated electrons.Consequently,the CuxO grafted oxygen‐rich TiO2microspheres achieved a photocatalytic activity respectively8.6,13.0and11.0as times high as those of oxygen‐rich TiO2,normal TiO2and CuxO grafted TiO2,for degradation of gaseous acetaldehyde under visible‐light irradiation.Our results suggest that high visible‐light photocatalytic efficiency can be achieved by combining oxygen excess defects to improve visible‐light absorption together with a CuxO electron transfer co‐catalyst.These findings provide a new approach to developing efficient heterojunction photocatalysts.

The removal of arsenic from (ground)-water by adsorbent loaded in polymeric microspheres

Arsenic is a natural tasteless and odourless element,existing in the earth's crust at average levels of between two and five thousands micrograms per liter (parts per million) . Arsenic is highly toxic to humans, who are exposed to it primarily from air,food and water. The occurrence of arsenic in groundwater is due to geological composition of soil. High concentrations of arsenic in water are the result of dissolution or desorption of ferric oxides and the oxidation of mineral arsenopyrites. Arsenic in drinking water has an important impact on the human health,especially in the less developed countries. Different methods exist to remove arsenic from aquatic media,and one of them is by adsorption. In this work,the adsorption of both As(III) and As(V) by means of novel microspheres has been investigated. In particular,TiO2 has been embedded into polymeric microspheres PES (PolyEtherSulphone) and PEEK-WC (PolyEtherEther-Ketone) . The main advantages of this encapsulation adsorption material are: no loss of adsorbents into the water stream,easy to be used and scaled-up.

Controlled TiO2 coating on hollow glass microspheres and their reflective thermal insulation properties

Hollow glass microspheres(HGMs)have great potential in building energy-saving and industrial insulation.Anatase TiO2-modified HGMs were prepared by a sol-gel method in acetic acid-ethanol solution.Scanning electron microscopy,X-ray diffraction,zeta-potential measurements,nitrogen-sorption measurements,and Fourier-transform infrared and ultraviolet-visible-near-infrared diffuse reflectance spectroscopies showed that the alkali modification of the HGMs greatly influenced the loading and microstructure of the TiO2 film.The TiO2 loading could be accurately controlled by ethanol addition and the TiO2 coating time.A mechanism for the TiO2 coating of the HGM surface is proposed.The synergistic action of hydrogen bonding and electrostatic forces resulted in close contact between the HGMs and TiO2 sol at pH 3.5.The effects of different TiO2 loading rates on the reflective and thermal insulation properties were studied.The near-infrared reflectance of 15.9%TiO2 coated on HGMs was 96.27%,and the inner surface temperature of the composite pigment coated on aluminum board was reduced by 22.4℃.The TiO2/HGM composite pigments exhibited excellent solar reflective and thermal insulation properties,so have potential in the construction of exterior walls and roofs.

Inside-out Ostwald ripening： A facile process towards synthesizing anatase TiO2 microspheres for high- efficiency dye-sensitized solar cells

A facile inside-out Ostwald ripening route to the morphology-controlled preparation of TiO2 microspheres is developed. Here, TiO2 hollow microspheres （HM） and solid microspheres （SM） are prepared by adjusting the volume ratio of isopropanol （IPA） to acetylacetone （Acac） in the solvothermal process. During the formation process of HM, precipitation of solid cores, subsequent deposition of outer shells on the surface of cores, and simultaneous core dissolution and shell recrystallizafion are observed, which validate the inside-out Ostwald ripening mechanism. Design and optimization of the properties （pore size, surface area, and trap state） of TiO2 microspheres are vital to the high performance of dye- sensitized solar cells （DSSCs）. The optimized TiO2 rnicrospheres （rHM and rSM） obtained by post-processing on recrystallization, possess large pore sizes, high surface areas and reduced trap states （Ti3~ and oxygen vacancy）, and are thus ideal materials for photovoltaic devices. The power conversion efficiency of DSSCs fabricated using rHM photoanode is 11.22%, which is significantly improved compared with the 10.54% efficiency of the rSM-based DSSC. Our work provides a strategy for synthesizing TiO2 microspheres that simultaneously accommodate different physical properties, in terms of surface area, crystallinity, morphology, and mesoporosity.

Carbon coated Au/TiO_2 mesoporous microspheres: a novel selective photocatalyst

Photocatalysts with desirable selectivity to transformation and purification of targeted pollutants are of great importance in water purification. Here, we demonstrate that selective photocatalysis can be realized by the assistance of gold-enhanced selective adsorption onto carbon-coated Au/TiO2 mesoporous microspheres （Au/TiO2@C-MM）, which were prepared via a surfactant-assisted two-step method that involved the assembly of oleic acid-stabilized titania and gold nanoparticles into colloidal spheres in an emulsion using sodium dodecyl sulfate as a surfactant and the conversion of the surfactants into carbon under annealing in Ar. Due to the negatively charged amorphous carbon, the mesoporous structure, and the surface plasmon resonance absorption of the Au components, the Au/TiO2@C-MM shows enhanced charge- and size-selective adsorption prop- erties, which enables the materials to have high selectivity in the photocatalytic process.

Rutile TiO2 Microspheres with Exposed Nano-Acicular Single Crystals for Dye-Sensitized Solar Cells

Uniquely structured rutile TiO2 microspheres with exposed nano-acicular single crystals have been successfully synthesized via a facile hydrothermal method. After calcination at 450 ℃ for 2 h, the futile TiO2 microspheres with a high surface area of 132 m2/g have been utilized as a light harvesting enhancement material for dye-sensitized solar cells （DSSCs）. The resultant DSSCs exhibit an overall light conversion efficiency of 8.41% for TiO2 photoanodes made of futile TiO2 microspheres and anatase TiO, nanoparticles （mass ratio of 1：1）, significantly higher than that of pure anatase TiO2 nanoparticle photoanodes of similar thickness （6.74%）. Such a significant improvement in performance can be attributed to the enhanced light harvesting capability and synergetic electron transfer effect. This is because the photoanodes made of futile TiO2 microsphere possess high refractive index which improves the light utilisation efficiency, suitable microsphere core sizes （450-800 nm） to effectively scatter visible light, high surface area for dye loading, and synergetic electron transfer effects between nanoparticulate anatase and nano-acicular futile single crystals phases giving high electron collection efficiency.

Synthesize TiO_2 microspheres self-assembled from nanorods via hydrothermal treatment

The TiO2 microspheres were deposited on the glass substrates under certain conditions via hydro-thermal reaction using 0.15 mol·L?1 TiCl3 saturated NaCl aqueous solution adding urea as an additive. The TiO2 is characterized rutile by results of SEM,TEM and XRD techniques,the TiO2 microspheres are large scale assembled from TiO2 nanorods. The affections on the products by the factors of the con-tents of urea being an additive(the key techniques) ,the reaction temperature,the reaction time and the concentration of TiCl3 were studied. The optimum condition was found,and the mechanism of reac-tions was discussed also.