Preparation of hollow B-SiO2@TiO2 composites and their photocatalytic performances for degradation of ammonia-nitrogen and green algae in aqueous solution

Hollow B-SiO₂@TiO₂ composites were prepared by the wet chemical deposition method starting from TiCl₄ and hollow B-SiO₂ microspheres. TiO₂ layers composed of anatase TiO₂ nanoparticles were coated on the surfaces of the hollow B-SiO₂ microspheres probably through the formation of Ti-O-Si and Ti-O-B bonds. A great number of-OH groups were also present at the TiO₂ coating layers. The presence of Ti-O-Si bonds and Ti-O-B bonds resulted in the formation of defects in the TiO₂ coating layers, which decreased the band gap of the TiO₂ coating layers to ca. 3.0 eV and endowed the TiO₂ coating layers with visible light absorption performance. The buoyancy hollow B-SiO₂@TiO₂ composites exhibited high photocatalytic activities for the degradation of ammonia-nitrogen and green algae. The conversion of ammonia-nitrogen reached 65% when the degradation of ammonia-nitrogen (43 mg·L^-1 at pH value of 8) was catalyzed by the B-SiO₂@TiO₂(100:10) composite under the simulated solar light irradiation at 35℃ for 660 min. The green algae (5 mg·L^-1) were almost completely degraded over the B-SiO@TiO₂(100:20) photocatalyst under the visible light irradiation at 35℃ for 510 min.     

Influence of surface modified mixed metal oxide nanoparticles on the electrochemical and mechanical properties of polyurethane matrix

Newly synthesized functional nanoparticles, 3-amino-1,2,4-triazole (ATA)/SiO₂–TiO₂ were introduced to the polyurethane (PU) matrix. Electrochemical techniques were used to investigate the barrier properties of the synthesized PU–ATA/SiO₂–TiO₂ nanocomposite coated steel specimen. In natural seawater, electrochemical impedance spectroscopy experiments indicated outstanding protective behaviour for the PU–ATA/SiO₂–TiO₂ coated steel. The coating resistance (R_coat) of PU–ATA/SiO₂–TiO₂ was determined to be 2956.90 kΩ·cm^–2. The R_coat of the PU–ATA/SiO₂–TiO₂ nanocomposite coating was found to be over 50% higher than the PU coating. The current measured along the scratched surface of the PU–ATA/SiO₂–TiO₂ coating was found to be very low (1.65 nA). The enhanced ATA/SiO₂–TiO₂ nanoparticles inhibited the entry of electrolytes into the coating interface, as revealed by scanning electron microscopy/energy dispersive X-ray spectroscopy and X-ray diffraction analysis of the degradation products. Water contact angle testing validated the hydrophobic nature of the PU–ATA/SiO₂–TiO₂ coating (θ = 115.4°). When the concentration of ATA/SiO₂−TiO₂ nanoparticles was 2 wt %, dynamic mechanical analysis revealed better mechanical properties. Therefore, the newly synthesised PU–ATA/SiO₂–TiO₂ nanocomposite provided excellent barrier and mechanical properties due to the addition of ATA/SiO₂–TiO₂ nanoparticles to the polyurethane, which inhibited material degradation and aided in the prolongation of the coated steel’s life.     

Sol-enhanced electroplating of nanostructured Ni-TiO2 composite coatings—The effects of sol concentration on the mechanical and corrosion properties

Novel sol-enhanced Ni-TiO₂ nano-composite coatings were electroplated by adding a transparent TiO₂ sol into the traditional electroplating Ni solution. It was found that the structure, mechanical properties and corrosion resistance of the nano-composite coatings were largely determined by the sol concentration. The higher sol concentration in the plating electrolyte led to a higher content of TiO₂ nano-particles in the coating matrix. The coating prepared at the sol concentration of 12.5 mL/L had the best microhardness, wear resistance and corrosion resistance. Adding excessive sol to the electrolyte changed the surface microstructure, caused cracking on the coating surface and deteriorated the properties. It was demonstrated that the corrosion resistance of the composite coatings is determined by two factors: surface microstructure and incorporation of TiO₂ nano-particles.     

Preparation of TiO2 coatings on PET monoliths for the photocatalytic elimination of trichloroethylene in the gas phase

This paper presents the first data on the performance of polyethylene terephthalate (PET) monoliths as photocatalytic support. For this purpose, first a protective layer of SiO₂ was applied to the polymer to prevent oxidation of the substrate, and subsequently the photoactive layer of TiO₂ was deposited on PET monoliths using the dip-coating technique. In order to increase the adherence of inorganic coatings, two different synthesis procedures were evaluated. One approach was based on reducing the surface tension of the SiO₂ sol using a fluorinated surfactant to increment the PET wettability. The second approach consisted in modifying the PET surface with a layer of the polymer poly(diallyldimethylammonium) chloride (PDDA), which provides a positively charged surface for the fixation of the alkaline SiO₂ sol. Both TiO₂/SiO₂ coated PET monoliths were assayed in a single-pass annular reactor for the destruction of trichloroethylene (TCE). The two coating procedures were compared in terms of homogeneity, durability and photocatalytic activity.     

Interfacial potassium induced enhanced Raman spectroscopy for single-crystal TiO2 nanowhisker

Structural control and element doping are two popular strategies to produce semiconductors with surface enhanced Raman spectroscopy(SERS) properties. For TiO_2 based SERS substrates, maintaining a good crystallinity is critical to achieve excellent Raman scattering. At elevated temperatures(N600 °C), the phase transition from anatase to rutile TiO_2 could result in a poor SERS performance. In this work, we report the successful synthesis of TiO_2 nanowhiskers with excellent SERS properties. The enhancement factor, an index of SERS performance, is 4.96 × 10~6 for methylene blue molecule detecting, with a detection sensitivity around 10~(-7) mol·L~(-1).Characterizations, such as XRD, Raman, TEM, UV–vis and Zeta potential measurement, have been performed to decrypt structural and chemical characteristics of the newly synthesized TiO_2 nanowhiskers. The photo absorption onset of MB adsorbed TiO_2 nanowhiskers was similar to that of bare TiO_2 nanowhiskers. In addition, no new band was observed from the UV–vis of MB modified TiO_2 nanowhiskers. Both results suggest that the high enhancement factor cannot be explained by the charge-transfer mechanism. With the support of ab initio density functional theory calculations, we reveal that interfacial potassium is critical to maintain thermal stability of the anatase phase up to 900 °C. In addition, the deposition of potassium results in a negatively charged TiO_2 nanowhisker surface, which favors specific adsorption of methylene blue molecules and significantly improves SERS performance via the electrostatic adsorption effect.     

玉米淀粉/TiO2纳米复合薄膜制备与性能

以玉米淀粉为基质,结合纳米Ti O₂,通过超声分散采用流延法制备了可生物降解的淀粉/Ti O₂纳米复合薄膜,研究了纳米Ti O₂对薄膜拉伸性能、阻隔性能及抗菌活性的影响,采用扫描电子显微镜(SEM)、红外光谱仪(FTIR)和X射线衍射仪(XRD)对复合膜的微观形貌和结构进行了表征。结果表明,淀粉/Ti O₂纳米复合膜中Ti O₂与淀粉分子间存在缔合作用,含适量Ti O₂的复合膜组分之间有良好的相容性,与淀粉膜相比,纳米复合膜的拉伸性能和水蒸气阻隔性能得到有效改善,含0.8%Ti O₂(质量分数,下同)的纳米复合膜拉伸强度为7.54 MPa,比淀粉膜提高了53.9%,水蒸气透过系数为5.50×10^-5 g/(mm·d),较淀粉膜降低了23.5%,该复合膜同时表现出较好的紫外线隔离性能及抗菌活性。     

SBA-15/Ni/TiO2/CNTs复合材料的制备及其光催化性能

通过溶胶凝胶法,经多次涂覆在SBA-15上负载掺杂镍的纳米TiO₂,得到SBA-15/NiO/TiO₂复合物;再以TiO₂中还原态金属镍为催化剂,通过化学气相沉积法（CVD）,在SBA-15/NiO/TiO₂表面原位生长碳纳米管,制得SBA-15/Ni/TiO₂/CNTs复合材料。通过XRD、SEM、TEM、UV-Vis和Raman等方法考察了SBA-15/Ni/TiO₂/CNTs复合材料的结构和性能,并通过降解亚甲基蓝溶液评价其光催化活性。结果表明,SBA-15/Ni/TiO₂/CNTs复合光催化剂的催化活性较SBA-15/NiO/TiO₂显著提高。 二次涂覆掺杂镍的二氧化钛制得的复合光催化剂的催化活性高于一次涂覆。     

Al2O3@TiO2复合生物载体的制备及其BSA吸附特性

通过钛酸盐和氧化钛溶胶两种制备途径在氧化铝（Al₂O₃）支撑体外包覆介孔氧化钛（TiO₂）层,分析了这两种途径制备的氧化钛表面结构与性质的差异及其对于BSA蛋白吸附性能的影响。以粒径分别为0.37、10.4和21.8 mm的三种氧化铝支撑体作为基材,用XRD、Raman分析了两种路径制备的氧化钛晶型均为锐钛矿相;N₂吸脱附分析其比表面积均在（100±10）m²·g^-1,两者具有相似的介孔结构。FESEM分析发现钛酸钾溶胶制备的氧化钛的形貌受到支撑体孔径的影响。对于在牛血清蛋白（BSA）吸附实验中,钛酸钾溶胶法包覆的20 mm粒径复合载体（SP20@K-TiO₂）吸附量为22.18 mg·g^-1,高于相同条件下氧化钛溶胶制备的Al₂O₃@TiO₂复合载体。SP20@K-TiO₂ 中TiO₂吸附量为150.88 mg·g^-1,相比于TiO₂粉体,复合载体中TiO₂对BSA蛋白吸附的性能得到提升。     

Effect of external bias voltage and coating thickness on the photocatalytic activity of thermal sprayed TiO2 coating

TiO₂ coatings of different thickness were prepared by a thermal spray process. It was found that the external bias applied to the as-sprayed TiO₂ coating could significantly improve its photocatalytic performance, which was characterized by decomposition of methylene blue (MB) solution. The decomposition efficiency increased with increasing external bias voltage. However, for voltage greater than 15 V, the decomposition efficiency remained constant. The TiO₂ coating with a thickness of 6 μm showed the best photocatalytic performance under an external bias voltage of 15 V.     

Efficient synthesis of titania nanotubes and enhanced photoresponse of Pt decorated TiO2 for water splitting

We investigated the effect of HMT (hexamethylenetetraamine) on the anodic growth of TiO₂ nanotube arrays. The tube length increases to 4.3 μm with HMT concentration increasing to 0.04 mol·L^-1. Adsorption of HMT on the TiO₂ surface is shown to markedly decrease the chemical dissolution rate of tube mouth, resulting in longer nanotube length. Furthermore, Pt nanoparticles were successfully deposited on the surface of TiO₂ nanotubes by ac electrodeposition method. The TiO₂/Pt composites were characterized by field emission scanning electron microscope (FESEM), X-ray photoelectron spectra (XPS), and photoelectrochemistry. An enhancement in photocurrent density has been achieved upon modification of TiO₂ nanotubes with Pt nanoparticles.     

涂层组分对堇青石脱硝催化剂性能的影响

为了探究涂层组分对整体式低温选择性催化还原（SCR）脱硝催化剂性能的影响，本文使用锰氧化物（MnO _x ）、氧化物涂层（TiO₂、SiO₂及Al₂O₃）、堇青石（CC）基体制备整体式涂层催化剂，考察催化剂牢固度以及脱硝活性。结果表明：在200℃ 时，对于MnO _x /Al₂O₃/CC催化剂，MnO _x 负载率为6%（质量分数）时脱硝效率最高为95%；对于MnO _x /TiO₂/CC，负载率为6%~12%时脱硝效率相差不大，为75%左右；对于MnO _x /SiO₂/CC，负载率12%时脱硝效率80%。样品牢固度排列顺序如下：MnO _x /Al₂O₃/CC > MnO _x /SiO₂/CC > MnO _x / TiO₂ /CC。通过BET、SEM、TG、Raman、H₂-TPR等测试与分析方法发现：影响催化剂性能的因素主要为活性组分MnO _x 状态以及载体性能的差异。Al₂O₃涂层比表面积适中，作为载体活性好；SiO₂涂层虽然比表面积大、牢固度好，但作为载体活性差；TiO₂作为涂层比表面积较小，溶胶中溶剂挥发快使得涂层表面不均匀。     

辊式涂布法构建纸基牢固超疏水表面

采用辊式涂布的方法在纸基材料上构建超疏水表面,并对超疏水表面的牢固性、自清洁性和疏水性能进行评价。用γ-氨丙基三乙氧基硅烷和1H,1H,2H,2H-全氟辛基三乙氧基硅烷（POTS）对微米级和纳米级两种尺寸的TiO₂粒子进行疏水改性处理,然后将改性后的微/纳米TiO₂涂布在纸基材料表面。采用红外光谱（FTIR）对改性后的微/纳米TiO₂的化学组成进行了分析,采用扫描电镜（SEM）对涂布纸表面结构进行了表征,通过接触角、耐磨性和自洁净测试评价了涂层表面的超疏水性、牢固性和自清洁性。改性TiO₂的FTIR分析显示在1000～1500cm^-1之间出现多个C—F键的伸缩振动峰,表明POTS通过化学键与TiO₂表面发生了结合。涂布纸表面的SEM分析可以看出,纸基材料表面上均匀分布了微米和纳米尺寸的TiO₂颗粒,具备了类似荷叶表面微-纳结构的粗糙表面。涂层表面的水接触角为153°±1.5°,滚动角为3.5°±0.5°,水滴在涂层表面呈球形,极易滑落,涂层在水中浸泡7天后,接触角没有发生明显变化,表明纸张表面具备了优异的超疏水性能,且疏水稳定性较好。涂层表面经过10次循环磨损试验后,接触角仍能达到150°,滚动角为9°,表明机械摩擦没有对涂布纸表面的化学成分和粗糙结构造成明显的破坏,超疏水表面的牢固性较好。自洁净测试表明,涂布纸表面具有良好的自清洁和防污性能。该工艺过程操作简单,易于实现工业化生产,为在纸基表面构建综合性能优异的超疏水表面提供了一种新的便利途径。     

阳极氧化二氧化钛纳米管涂层地热水腐蚀和沉积特性

拟采用金属二次阳极氧化等表面工程技术抑制地热水的腐蚀和结垢现象。在纯钛和钛合金(Ti-6Al-4V)板基底上采用二次阳极氧化法制备了二氧化钛微纳米管阵列涂层,探讨了制备工艺参数对涂层结构的影响,并进一步采用浸渍法对涂层进行了超疏水化处理。通过场发射环境扫描电镜表征了涂层的微观结构形貌。应用视频光学接触角测量仪检测了涂层表面的静态接触角,估算了表面自由能。对涂层的粗糙度也进行了测量。采用静态浸渍法评估了涂层的防垢性能。采用电化学线性极化曲线法研究了涂层在地热水中的耐腐蚀效果。结果表明,在钛及钛合金基底上,采用二次阳极氧化和浸渍工艺,可以制得具有规整二氧化钛微纳米管阵列结构和较低表面能的功能涂层;该涂层与基底相比,在地热水中的耐腐蚀性能得以提高;在碳酸钙饱和溶液中的污垢沉积速率降低约15%。同时,涂层与基底有较好的结合性能,疏水涂层经历多次胶带剥离和砂纸磨损实验后,依然保持着较高的疏水性。     

Ni-P-PTFE复合镀层对颗粒污垢沉积特性影响研究

为探究Ni-P-PTFE复合镀层对颗粒污垢沉积特性的影响,利用化学镀工艺在碳钢表面制备Ni-P-PTFE复合镀层,以TiO₂纳米颗粒为研究对象,通过实验和理论分析的方式研究了不同表面能（PTFE浓度）下Ni-P-PTFE复合镀层在TiO₂悬浮液中的颗粒污垢沉积特性。结果表明：相比于碳钢试样,Ni-P-PTFE复合镀层对于TiO₂颗粒沉积具有较好的抑制效果。随着PTFE浓度的增加,复合镀层的表面能降低,污垢沉积量呈下降趋势,在表面能为26.8 mJ/m²（PTFE=12 ml/L）时,TiO₂颗粒污垢在Ni-P-PTFE复合镀层的沉积量最小。实验结果与应用扩展的DLVO理论计算出的最佳表面能结果相一致,也为针对不同类型颗粒在换热表面的沉积的抑垢提供了指导施镀的依据。     

Ni-P-PTFE复合镀层对颗粒污垢沉积特性影响研究

为探究Ni-P-PTFE复合镀层对颗粒污垢沉积特性的影响,利用化学镀工艺在碳钢表面制备Ni-P-PTFE复合镀层,以TiO₂纳米颗粒为研究对象,通过实验和理论分析的方式研究了不同表面能（PTFE浓度）下Ni-P-PTFE复合镀层在TiO₂悬浮液中的颗粒污垢沉积特性。结果表明：相比于碳钢试样,Ni-P-PTFE复合镀层对于TiO₂颗粒沉积具有较好的抑制效果。随着PTFE浓度的增加,复合镀层的表面能降低,污垢沉积量呈下降趋势,在表面能为26.8 mJ/m²（PTFE=12 ml/L）时,TiO₂颗粒污垢在Ni-P-PTFE复合镀层的沉积量最小。实验结果与应用扩展的DLVO理论计算出的最佳表面能结果相一致,也为针对不同类型颗粒在换热表面的沉积的抑垢提供了指导施镀的依据。     

TiCl4水解法水热制备Yb-P-TiO2纳米光催化剂及共掺杂的协同机制

利用水热技术以TiCl₄水解法制备介孔锐钛矿Yb-P-TiO₂纳米片.基于XRD、TEM、BET、XPS、FTIR、DRS和PL分析,探讨Yb和P共掺杂对TiO₂表面物理化学特性及光催化活性的影响机制.在模拟太阳光照射下,样品光催化降解4-氯酚活性顺序为:TiO₂ < Yb-TiO₂ < P25 < P-TiO₂ < Yb-P-TiO₂,表明Yb-P共掺杂对提高光催化活性产生协同作用.20 mg·L^-1的4-氯酚溶液在0.8 g·L^-1的Yb-P-TiO₂悬浮液中经模拟太阳光照射120 min后,TOC去除率达87.6%,表明4-氯酚能够被有效矿化.P掺杂对抑制TiO₂由锐钛矿向金红石相的转变和改善表面结构特性起决定性作用.Yb³⁺能俘获光生e^-生成Yb²⁺,Yb²⁺又易于将e^-转移给表面吸附O₂生成·O₂^-,有效抑制载流子复合.P 3p与O 2p轨道杂化能级与氧空位能级共同作用导致带隙窄化,改善光吸收性能.Yb-P共掺杂能进一步抑制光生e^-/h⁺复合,提高量子效率;进一步增加表面羟基,有利于俘获光生h⁺生成强氧化性羟基自由基.上述因素均有利于提高光催化活性.     

活性炭纤维负载Pr3+:Y2SiO5/TiO2复合材料的制备与性能

为了提高纳米TiO₂对太阳光的利用率和实现光催化剂的回收再利用,采用溶胶-凝胶法将上转换荧光材料与纳米TiO₂复合,通过负载于活性炭纤维（ACF）表面制备了Pr³⁺：Y₂SiO₅/TiO₂/ACF复合材料。运用XRD、FT-IR、SEM、FS、UV-vis DRS等对材料的结构及性能进行了综合表征,并以亚甲基蓝为模拟污染物评价复合材料的可见光催化活性,考察了材料制备过程中煅烧温度、负载次数等制备条件对复合材料可见光下催化性能的影响。结果表明,在浸渍2次、800℃煅烧的制备条件下,复合材料中TiO₂为锐钛矿相（占34.1%）与金红石相（占65.9%）的混合相,亚甲基蓝（15 mg·L^-1）12 h内去除率高达93.8%,反应符合拟一级动力学,反应速率常数为0.2471 h^-1,回收再生利用4次后去除率仍保持在75%以上。     

Removal of ammonium ions in wastewater by electrosorption with TiO2 modified graphene electrode

In this study, the TiO₂ modified graphene composite material (RGO/ TiO₂) was prepared by hydrothermal method, and its morphological structure and electrochemical properties were investigated. Then RGO/TiO₂ material was assembled into electrode, and NH₄⁺ ions electrosorption efficiencies of unmodified graphene (RGO) electrode and the RGO/TiO₂ electrode were compared. The effects of applied voltage, circulating velocity and initial concentration on NH₄⁺ ions electrosorption by RGO/TiO₂ electrode were investigated. The characteristics of NH₄⁺ ions electrosorption and the effect of advanced NH₄⁺ ions removal from simulated actual wastewater containing NH₄⁺ ions were also studied. The results showed that the RGO/TiO₂ composite material had a three-dimensional pore structure with specific surface area of 382.08 m²·g^-1 and specific capacitance of 325.80 F·g^-1 at a scan rate of 0.01 V·s^-1, which were better than those of the RGO material. The initial adsorption capacity of RGO/TiO₂ electrode was 28.3% higher than that of RGO electrode. After 10 cycles of regeneration adsorption, the adsorption capacity of NH₄⁺ ions of RGO/TiO₂ electrode only decreased 5.87%, and its cyclic regeneration adsorption property was better than that of RGO electrode. In addition, the applied voltage 2.0 V, circulating velocity 35 ml·min^-1 and initial concentration 1.0 mmol·L^-1 were the optimal NH₄⁺ ions electrosorption conditions for RGO/TiO₂ electrode. The electrosorption process of NH₄⁺ ions by RGO and RGO/TiO₂ electrodes was in accordance with the quasi-first-order kinetic model and the Freundlich isothermal adsorption model. The electrosorption of NH₄⁺ ions was a multi-layer adsorption behavior on heterogeneous surface and physical adsorption was the dominant. When the RGO/TiO₂ electrode was connected in 4-stage series, the removal efficiency of simulated actual NH₄⁺ refining purified water reached 86.84%.     

TiO2改性石墨烯电极电吸附去除污水中NH4+

通过水热法制备得到TiO₂改性石墨烯复合材料（RGO/TiO₂）,考察了其形貌结构和电化学性能。将其组装成电极,对比未改性石墨烯（RGO）电极和RGO/TiO₂电极的电吸附NH₄⁺性能。重点考察外加电压、循环流速、初始浓度等工艺参数对RGO/TiO₂电极电吸附NH₄⁺的影响,并对其电吸附NH₄⁺特性和对模拟实际含NH₄⁺废水深度脱NH₄⁺效果进行研究。结果表明：RGO/TiO₂复合材料具有三维孔洞结构,比表面积为382.08 m²·g^-1,比电容量在扫速为0.01 V·s^-1时达到325.80 F·g^-1,优于RGO材料。RGO/TiO₂电极的初次电吸附量较RGO电极提升了28.3%,循环再生吸附10次后,RGO/TiO₂电极的NH₄⁺吸附量仅降低了5.87%,循环再生吸附性能优于RGO电极。外加电压2.0 V、循环流速35 ml·min^-1和NH₄⁺初始浓度1.0 mmol·L^-1为RGO/TiO₂电极的最佳NH₄⁺电吸附条件。RGO和RGO/TiO₂电极电吸附NH₄⁺过程符合准一级动力学模型和Freundlich等温吸附模型,电吸附NH₄⁺为非均匀表面的多层吸附行为,以物理吸附为主。RGO/TiO₂电极4级串联时对模拟实际含NH₄⁺炼油净化水的去除率达到86.84%。     

硅藻土负载La~(3+)/TiO_2光催化剂的制备及其光催化性能

以钛酸四丁酯为前驱体,硅藻土为载体,采用溶胶-凝胶法制备TiO_2/硅藻土负载型光催化剂。以硝酸镧为镧源,采用等体积浸渍-焙烧法制备La~(3+)/TiO_2硅藻土光催化剂。通过XRD和SEM对制备的催化剂进行表征,以亚甲基蓝溶液模拟有机废水,考察n(Ti)∶n(Si)及La3+掺杂量对催化剂光催化性能的影响,结果表明,硅藻土可提高TiO_2分散性,降低TiO_2晶粒尺寸,并抑制其由锐钛矿相向金红石相的转变。在n(Ti)∶n(Si)=1∶1、焙烧温度550℃和La3+掺杂质量分数1%条件下,La~(3+)/TiO_2硅藻土光催化剂的光催化活性较好,紫外光连续照射180 min,亚甲基蓝降解率可达99.9%。