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.

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.

复合空心TiO_2@SiO_2纳米微球光催化性能研究

通过聚乙烯吡咯烷酮(PVP)功能化的聚苯乙烯(PS)粒子在SiO2包覆的同时被乙醇/氨水介质溶解,得到了单分散空心SiO2纳米微球,经溶胶-凝胶法与纳米TiO2复合制备得到了TiO2@SiO2纳米球.利用透射电子显微镜(TEM)和X射线衍射仪(XRD)对制备的TiO2@SiO2纳米球进行了物理特性及光化学性质的初步表征,探讨了SiO2纳米微球的复合对TiO2粒径大小、比表面积、形貌、晶型转变以及光催化活性的影响.在可见光照射下,利用有机染料罗丹明B(Rhodamine B,RhB)的光催化降解为探针反应,研究了TiO2@SiO2纳米球的光催化活性及适应的pH范围.结果表明,SiO2纳米球的复合能明显提高光催化剂的比表面积及其对RhB的吸附量.同时能明显提高TiO2在可见光下的光催化活性,可见光下照射120min后RhB完全褪色,同时16h后的矿化率达到60%.TiO2@SiO2纳米球在pH 3～9范围内均表现出较高的催化性能.

TiO_2@SiO_2微球的制备及其光催化性能研究

采用模板法以钛酸丁酯为钛源,SiO2为模板球,制备出了TiO2包覆SiO2微球。利用SEM、TEM、XRD、EDS对样品形貌、结构和成分进行了表征分析,并测试了样品的光催化性能。结果表明TiO2@SiO2微球的光催化性能优于用相同方法制得的TiO2的光催化性能,当使用TiO2@SiO2微球为光催化剂时,在光照180min后甲基橙的降解率达到82%,而相同方法制得的TiO2为56%,较后者提高了26%,具有良好的光催化活性。

TiO2@SiO2复合材料的制备及其光催化与抗菌性能的研究

采用溶胶凝胶法制备载体SiO2,并通过水解法制备出负载型TiO2@SiO2复合光催化抗菌材料,采用SEM、XRD、BET、FT-IR、XPS和粒度仪对材料进行表征和分析。在UVA紫外光照下,通过降解甲基橙溶液考察了复合材料的光催化性能,在照射3 h后,不同钛掺杂量复合材料的光催化降解率均能达到99.9%,钛掺比为0.58时催化效率最高。通过平板涂布法检测了复合材料对大肠杆菌的抗菌效果,发现抗菌性能随着钛含量的增加而提高,在紫外照射条件下最高可达92%以上,同时在可见光照射下也能表现出良好的抗菌性能。通过细菌荧光检测,可以有效证明复合材料所产生的活性氧迁移到了细胞内部,造成细胞体氧化损伤,这是光催化材料抗菌机理研究的重要依据。

响应面优化核-壳结构TiO2@SiO2的制备工艺

以金红石二氧化钛为核、硅酸钠作为包覆剂,并流法制备核-壳结构TiO2@SiO2。采用单因素实验探究pH、温度、搅拌速率、包覆时间、二氧化钛初始浓度、包覆剂用量及陈化时间7个因素对产品酸溶率的影响,响应面实验优化制备工艺,用TEM、XPS、SEM、XRD、FT-IR、UV-vis等手段对产物进行表征。结果表明,固定搅拌速率为300 r/min、包覆时间为60 min、二氧化钛初始质量浓度为200 g/L,各因素对酸溶率的影响次序由大到小为:包覆剂用量、温度、pH、陈化时间,在较优工艺条件包覆剂用量为4.41%、温度为83.65℃、pH为9.59、陈化时间为25.62 h下,产物的酸溶率为3.43%。壳层为无定形二氧化硅、厚度约为5 nm左右的致密膜,以Ti—O—Si化学键合在二氧化钛核的表面,核-壳结构的TiO2@SiO2具有更高的紫外屏蔽能力。

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。

磁性TiO_2纤维的制备及光催化性能研究

以聚乙烯吡咯烷酮、钛酸丁酯和Fe3O4@SiO2为前驱物,将静电纺丝技术和高温煅烧法相结合,成功地制备出内含Fe3O4@SiO2纳米粒子的磁性TiO2纳米纤维.利用XRD、SEM、TEM、UV-Vis光谱及Shole7304型振动样品磁强计等测试手段对样品的结构和形貌及磁性进行表征,在光催化实验中选罗丹明B为降解模拟污染物测试了太阳光照射下的光催化活性.实验结果表明:所制备的磁性TiO2纳米纤维在模拟太阳光光照下表现出较好的光催化活性.另外,该纤维在外加磁场下能够简单有效地分离回收.

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.

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.

A Facile Synthesis of Hierarchically Porous TiO2 Microspheres with Carbonaceous Species for Visible-light Photocatalysis

Hierarchically porous anatase Ti02 microspheres composited with carbonaceous species （TCS） have been successfully fabricated by a one-step template-free solvothermal method, combined with subsequent low temperature dried process. In this configuration, the TCS microspheres are constructed by the intercon- nected porous nanosheets, which are further assembled with abundant nanoparticles and carbonaceous species. Such composite microspheres possess a large specific surface area of 337 m2 g-l, uniform mesopores of 3.37 nm and high total pore volumes of 0.275 cm3 g-1. The materials exhibit the enhanced photocatalytic properties and stability for degradation of rhodamine B （RhB） under visible-light irradiation. The enhanced photocatalytic degradation performance may be ascribed to their abundant porous structure, large specific surface area and the unique assist-function of the carbonaceous species.

Au Nanoparticles Loaded on Hollow TiO2 Microspheres with （001） Exposed Facets： a Strategy for Promoting Photocatalytic Performance

Au nanoparticles loaded TiO2 hollow microspheres with exposed （001） facets（Au-HTFs） were synthesized through template-free hydrothermal process combined with a chemical reduction role. Au-HTFs displayed excellent photocatalytic activity in catalyzing oxidization reaction in organic pollutant system, which originates from the synergistic effect of the reactive （001） facets and Au nanoparticles with a wide range of absorption in visible region based on localized surface plasmon resonance effect. The unique synergistic effect could largely increase the photocatalytic performance resulting from the improvements of both the visible light aborption and the recombination of electron-hole pairs. Our findings revealed that among Au-HTFs with different Au loading percentages, Au-HTFs with 2%（mass fraction） Au loading possessed the superior photocatalytic activity.

Plasmonic Au Decorated Single-crystal-like TiO2-NaYF4 Mesoporous Microspheres for Enhanced Broadband Photocatalysis

Single-crystal-like TiO2 mesoporous microspheres have been reported with high photocatalytic activity under ultraviolet light （UV light） because of their high specific surface areas and single-crystal-like channel walls. In this work, plasmonic gold nanoparticles （Au NPs） and fl-NaYF4： Yb3＋, Er3＋ upconversion nanoparticles （UCNPs） were composited with single-crystal-like TiO2 mesoporous microspheres through a series of facile approaches, aiming at broadening response region of solar light from UV to visible and near infrared light and enhancing the photocata- lyric activity further. The structure was rationally designed by modifying the pore size of TiO2 mesoporous micro- spheres so as to anchor plasmonic Au NPs, and covering β-NaYF4： Yb3＋, Er3＋ with SiO2 in order to embed UCNPs into TiO2 mesoporous microspheres via hydrophilic interaction. This work studied the attribution of Au NPs and UCNPs to photocatalysis and found out that combining Au NPs and certain amount of UCNPs with single-crystal- like TiO2 mesoporous microspheres in a monolithic architecture would bring enhanced broadband photocatalytic activity under simulated solar light. Consequently, the composite photocatalyts containing 150 mg UCNPs showed a significant enhancement in reaction rate, which was 36.02% higher than commercial P25 and 85.09% higher than pure TiO2 mesoporous microspheres under simulated solar light.