Pt／TiO2膜光催化氧化降解高聚物的研究

以250W高压泵灯为光源,通过光化学沉积法在TiO2表面上担载1％Pt制备的催化剂对难降解高聚物PVA具有很好的光催化活性,固定相活性提高后的该类催化剂在用量为30g/m∧2时,光照60min,PVA的光解率可达78．3％。研究发现,PVA的光催化氧化可分为两个阶段,前一阶段PVA主要生成中间产物,后一阶段,PVA被彻底氧化分解,1％Pt/TiO可以明显地缩短前阶段反应时间,增强后阶段PVA的矿化作用,增加矿化阶段反应级数与反应速度常数。     

Pt/TiO_2膜光催化氧化降解高聚物的研究

以 2 5 0W高压汞灯为光源 ,通过光化学沉积法在TiO2 表面上担载 1%Pt制备的催化剂对难降解高聚物PVA具有很好的光催化活性 ,固定相活性提高后的该类催化剂在用量为 30g/m2 时 ,光照 6 0min ,PVA的光解率可达78 3%。研究发现 ,PVA的光催化氧化可分为两个阶段 ,前一阶段PVA主要生成中间产物 ,后一阶段 ,PVA被彻底氧化分解 ,1%Pt/TiO2 可以明显地缩短前阶段反应时间 ,增强后阶段PVA的矿化作用 ,增加矿化阶段反应级数与反应速度常数。     

微波强化光催化处理罗丹明B染料废水

采用微波无极灯强化光催化(MWL/TiO_2)对罗丹明B模拟废水进行处理。初步研究催化剂TiO_2的用量、罗丹明B初始浓度、微波功率、溶解氧、pH、反应温度、外加氧化剂H_2O_2量等因素对罗丹明B降解效果的影响。实验结果表明:最佳催化剂TiO_2的投加量为4g/L;较低pH、高溶解氧浓度、高微波功率、外加氧化剂H_2O_2有利于罗丹明B的降解。与常规光催化相比,微波减弱pH、染料初始浓度对降解效率的影响,同时增强温度对降解效率的影响。     

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。     

Ag/TiO2光催化膜降解高浓度对氯苯酚溶液的研究

依据光催化还原原理 ,在活性碳负载的TiO2 纳米粒子膜表面上制备出载银光催化剂 ,采用该催化剂对初始COD≥ 6 0 0mg·L-1的高浓度 4 氯苯酚水溶液进行降解研究 ,分别考察了光催化剂的用量、反应液初始浓度和初始 pH值等对降解性能的影响 ,并与DegussaP2 5微粉光催化剂等进行比较 ,得出负载型Ag/TiO2 光催化膜具有光催化活性高、固液易分离的特点。     

太阳光TiO2薄层光催化降解有机磷农药的研究

研究了在太阳光的照射下，ＴｉＯ２薄层光催化降解有机磷农药的可行性。结果表明，０．６５×１０－４ｍｏｌ·Ｌ－１的久效磷、甲拌磷农药光照他可完全降解至ＰＯ４３－；加入微量的Ｈ２Ｏ２或通入空气可大大提高光解率；有机磷农药初始浓度增加，其光解率下降；光照１２０ｈ后ＴｉＯ２薄层的光催化活性没有减弱，可以连续使用。初步探讨了有机磷农药光催化降解的机理，认为·ＯＨ和Ｏ２２－是最主要的氧化剂。     

纳米Fe2O3/Fe3O4光催化法处理造纸废水的研究

以纳米Fe_2O_3/Fe_3O_4为催化剂,用光催化氧化法处理造纸废水。研究结果表明:该催化剂能有效、快速地降低废水中的COD_(Cr),催化剂用量、H_2O_2用量、pH值、反应时间等各因素对处理效果的影响大小依次为:光照时间>H_2O_2用量>催化剂用量>溶液pH值;室温下最佳反应条件为:催化剂用量0.5g·L~(-1)、30%的H_2O_2用量为5‰(V/V)、pH=3.0,300W高压汞灯光照4h,废水的COD_(Cr)值从800 mg·L~(-1)降到48mg·L~(-1),去除率达到94%。实验进一步考察了太阳光照射下催化剂对废水的降解效果,表明太阳光光照下催化剂对废水也有较好的处理效果。Fe_3O_4的存在使催化剂具有一定磁性,可利用磁分离法将催化剂从体系中分离。     

掺铋纳米TiO_2制备及可见光催化降解有机污染物

采用在酸性条件下超声沉淀的方法低温制备了Bi掺杂TiO_2纳米粉体,采用X射线光电子能谱(XPS)、X射线衍射(XRD)和透射电镜(TEM)对催化剂进行了初步表征,发现其禁带宽度变窄,主要为锐钛矿(82.7%)和金红石(17.3%)混晶,纳米尺寸为25.8nm。以酸性桃红(SRB)和无色小分子2,4-二氯苯酚(2,4-dichlorophenol,2,4-DCP)作为探针反应,在可见光照射下(λ420nm)测定了SRB降解过程中总有机碳(1OC)的变化,发现SRB的TOC去除率为61.6%。跟踪测定光催化反应体系中氧化物种,表明光催化涉及羟基自由基(·OH)过程,所制备的催化剂在可见光下具有较高的催化氧化活性。     

WO_3/TiO_2薄膜在光催化降解溴酚蓝方面的应用

采用溶胶-凝胶法,在玻璃珠表面涂覆均匀透明的WO3/TiO2薄膜并制成光催化反应器,对水溶液中溴酚蓝(BPB)的光催化降解进行了研究.采用XRD对催化剂进行了表征,讨论了催化剂的组成、煅烧温度、溴酚蓝的起始浓度、pH值、光照时间等因素对光催化反应活性的影响.实验结果表明:当ω(WO3)=3%,煅烧温度为500℃,[BPB]=20 mg/L,pH=8.1,光照时间为10h,溴酚蓝的脱色率可达95.1%.     

有机污染物的半导体光催化降解研究进展

以半导体催化剂TiO2为例，讨论了光催化降解有机污染物的机理，介绍了其晶型、粒径大小和制备方法等对催化活性的影响。同时讨论了光强、污染物溶液的pH值、温度、O2，O3及H2O2等因素对反应速度的影响。总结了半导体光催化降解在消除重要的水污染物(有色燃料、氯代物和芳香类化合物、农药、表面活性剂)方面的应用。     

Photocatalytic H2 production over RuO2@ZnS and RuO2@CuS nanostructures

Photocatalytic hydrogen production is a promising approach of sustainable economy, because a use of sunlight and water to produce a fuel will solve a problem of fossil fuels depletion. Metal sulfides are well known photocatalysts in water splitting process, but in absence of sacrificial electron donor they undergo a photocorrosion. In this paper we studied a possible strategy to protect the sulfide photocatalysts and to improve its photostability by a deposition of small amount of ruthenium oxide at surface of sulfides. Nanocrystalline zinc sulfide and copper sulfide were prepared in a hydrothermal way and have been functionalized by RuO₂. As prepared photocatalysts showed good activity towards hydrogen formation. Modification of sulfides with ruthenium oxide had a few positive effects: it expanded a light absorption range by photocatalysts, enhanced the photocatalytic activity towards H₂ formation, improved a photostability in comparison with neat ZnS and CuS as well as protected from the electronic and structural changes within semiconductors due to irradiation.     

Evaluation of in-situ formed La2O3–TiO2–La2O2CO3 nanocomposite photocatalyst for H2 production

The photocatalytic evolution of H₂ over La₂O₃ decorated TiO₂ catalyst was examined under solar light. It was observed that during the course of the reaction, the transformation of La₂O₃/TiO₂ into La₂O₃–TiO₂–La₂O₂CO₃ occurred and these species effectively suppressed electron-hole pair recombination by forming electron trapping centres on the surface, resulting in an increased visible light absorption and improved H₂ yield. The 2 wt%La₂O₃/TiO₂ nanocomposite demonstrated better H₂ yield (～8.76 mmol (g_cat)^?1) than the bare TiO₂ (～1.1 mmol (g_cat)^?1). The catalyst was stable even after several consecutive recycles with no substantial loss of hydrogen production rate. The H₂ rates were correlated with the physicochemical characteristics of the catalysts examined by BET–SA, H₂-TPR, XRD, UV-DRS, Raman spectroscopy, FTIR, HRTEM, EPR and PL spectroscopy.     

Numerical study of the O2/CO2, O2/CO2/N2, and O2/N2-syngas MILD combustion: Effects of oxidant temperature,O2 mole fraction,and fuel blends

Moderate or Intense Low-oxygen Dilution (MILD) combustion of a syngas fuel under air-fuel, oxygen-enhanced, and oxy-fuel condition are numerically studied with using counterflow diffusion flame. Fuel composition, temperature of oxidant (T_ox), and oxygen mole fraction (X_O2) are selected as the main parameters. Fake species (FCO₂) with the same CO₂ physical properties is used for separation the physical and chemical effects of replacing CO₂ with N₂. According to the results, under the high preheating temperatures, the chemical effect of changing the oxidant composition from N₂ to CO₂ is the main reason of the changes in flame structure, ignition delay time (IDT) and heat release rate (HRR) while physical differences play a more prominent role in the low preheating temperature MILD combustion. In all X_O2, the physical and chemical effects of replacing CO₂ with N₂ have almost the same role on the maximum flame temperature. The results of IDT expressed that chemical discrepancies of CO₂ and N₂ play a key role on IDT enhancement by increasing CO₂ in the oxidant composition. The sensitivity analysis of CH₂O for variations of T_ox and X_O2 shows that reactions R54, R56, R58, and R101 are the main responsible of lower HRR and higher IDT by moving from air-syngas to oxy-fuel MILD combustion.     

保护气氛烧结炉

介绍了HIC封装管壳中玻璃绝缘子网带烧结炉的特殊机械结构、氮氢保护气氛系统和电气保护措施。确立了网带炉低速爬行力学模型及炉内合理的气氛流向。     

New gas chromatographic packing ZIF-67@NH2–SiO2 for separation of hydrogen isotope H2/D2

ZIF-67@NH₂–SiO₂ composites were prepared by loading the metal-organic frameworks ZIF-67 on amino modified SiO₂ gel particles (NH₂–SiO₂, 80–100 mesh) through layer-by-layer self-assembly method. Systematic investigation on the effects of ZIF-67 loading amounts on NH₂–SiO₂ packed stainless steel chromatographic column (specification 1.0 m×2.0 mm I.D.), the flow rate of He as carrier gas and the injection amount of mixed gas (H₂/D₂) on the hydrogen isotope H₂/D₂ separation performance at liquid nitrogen temperature, unraveled the optimal conditions for H₂/D₂ isotope separation. The results showed that the optimal stationary phase materials under the optimized conditions can effectively separate H₂ and D₂ with separation resolution R = 1.52 and the separation time t = 10.15 min. The superior performance of the ZIF-67 is tentatively thought to be due to kinetic quantum sieving (pore size 3.3 Å) effect and chemical affinity sieving effect of Co ion in ZIF-67.     

Photocatalytic reduction of CO2 using TiO2 powders in supercritical fluid CO2

The photocatalytic reduction of CO₂ was investigated using TiO₂ powders in supercritical fluid CO₂. These were irradiated in a stainless steel vessel at 9.0 MPa and 35°C. After reducing the CO₂ pressure to the ordinary state, pure water was added to the vessel while avoiding air contamination. No gaseous reduction products were observed. Formic acid was obtained only in aqueous solution. The optimal irradiation time for the production of formic acid was 5 h. Addition of acidic solutions rather than pure water was preferable for formic acid formation. Formic acid seems to be produced through the protonation of reaction intermediates on TiO₂ powders in solutions. The CO₂-reduction system described here may be of practical value for efficient CO₂-conversion and fixation, storage of solar energy, and production of raw materials for the photochemical industry.     

Photocatalytic reduction of CO2 with H2O on CuO/TiO2 catalysts

Carbon dioxide was photocatalytically reduced to produce methanol and ethanol in the presence of CuO-loaded titania powders suspended in water containing Na₂SO₃ as the hole scavenger. The photocatalysts were synthesized by an impregnation method using P25 (Degussa) as support. At the optimum amount of copper oxide loading (3 wt%), the methanol and ethanol yields were 12.5 and 27.1 μmol/g-catal., respectively, following 6 h of UV illumination. The redistribution of photogenerated charge carriers in CuO/TiO₂ facilitates electron trapping and prohibits the recombination of electrons and holes, which significantly increases photoefficiency. The addition of Na₂SO₃ promotes the formation of ethanol.     

Effects of CO2 addition on flame structure in counterflow diffusion flame of H2/CO2/N2 fuel

Numerical analysis on flame structure in a counterflow diffusion flame has been conducted for understanding the effects of CO₂ addition to fuel, systematically varying initial concentration of CO₂ and axial velocity gradient. The effects of CO₂ addition to fuel side in a counterflow diffusion flame are globally divided into two categories: diluent effects due to the relative reduction in the concentrations of the reactive species, and direct chemical effects caused by the breakdown of CO₂ through the reactions of third‐body collision and thermal dissociation. The deflection of CO₂ mole fraction profile with mixture fraction clarifies that the converted CO quantity from CO₂ is not negligible at low axial velocity gradients. It is also known that the addition of CO₂ does not alter the basic skeleton of the H₂–O₂ reaction mechanism, but contributes to the formation and destruction of hydrocarbon products such as HCO. At high axial velocity gradients the CO converted reaction is suppressed and then CO₂ plays the role of a diluent at these conditions. Copyright © 2001 John Wiley & Sons, Ltd.