Synthesis of efficient N-containing TiO2 photocatalysts with high anatase thermal stability and the effects of the nitrogen residue on the photoinduced charge separation

Efficient N-containing TiO(2) nanoparticles with high anatase thermal stability were synthesized via a hexamethylenetetramine (HMT)-modified sol-hydrothermal process. The results showed that modification with proper amounts of HMT is effective in increasing the onset temperature of the phase transformation of TiO(2) from anatase to rutile. The enhancement of the anatase thermal stability of the modified TiO(2) was attributed to ammonia produced slowly by hydrolysis of the HMT molecules in the sol-hydrothermal process and, additionally, to the residual nitrogen species after the thermal treatment at high temperatures, as indicated by the XPS examination. Compared with the unmodified TiO(2), the modified TiO(2) obtained by a thermal treatment at high temperatures exhibited good photocatalytic performance under UV light and was found to even be superior to the commercially available P25-TiO(2). It was suggested that the residual N species (Ti-O-N), formed after the thermal treatment at high temperatures, along with the mixed phase composition, large surface area and the increase in the thermal stability, were responsible for the enhanced photocatalytic activity of modified TiO(2). It was demonstrated, by means of the surface photovoltage responses of the modified TiO(2) in different atmospheres along with the aid of an outer electric field, that the residual N species could effectively capture the photoinduced holes, which was favorable for the effective separation of the photoinduced charges. This work provides a feasible route to fabricate high-performance TiO(2)-based functional nanomaterials with high anatase thermal stability.     

Photoassisted NO reduction with NH3 over TiO2 photocatalyst

Photoassisted selective catalytic reduction of NO with ammonia (photo-SCR) at low temperature over irradiated TiO2 in a flow reactor was confirmed to proceed efficiently and the adsorbed ammonia reacted with NO under irradiation of TiO2.     

Highly selective ammonia synthesis from nitrate with photocatalytically generated hydrogen on CuPd/TiO2

Body-centered-cubic type CuPd nanoalloys were synthesized by a chemical reduction method. Photocatalytic hydrogen evolution and nitrate reduction were simultaneously examined over CuPd nanoalloys deposited on TiO(2) (CuPd/TiO(2)). The efficiency of hydrogen evolution over CuPd/TiO(2) was better than that over Pd/TiO(2). As for nitrate reduction, ammonia was selectively (78%) produced with hydrogen generated photocatalytically over CuPd/TiO(2). The continuous generation of nascent hydrogen atoms on the surface of the CuPd nanoalloy, where Cu and Pd are homogeneously mixed, led to the high selectivity for ammonia.     

A TiO2-nanotube-array-based photocatalytic fuel cell using refractory organic compounds as substrates for electricity generation

A TiO(2)-nanotube-array-based photocatalytic fuel cell system was established for generation of electricity from various refractory organic compounds and simultaneous wastewater treatment. The present system can respond to visible light and produce obviously enhanced cell performance when a narrow band-gap semiconductor (i.e. Cu(2)O and CdS) was combined with TiO(2) nanotubes.     

顶空气相色谱法快速测定污水中氨氮含量

研究了一种基于化学反应型顶空气相色谱的快速检测污水氨氮含量新方法。首先在顶空瓶中用过量的甲醛与NH₄⁺反应产生等物质的量的强酸，再用NaHCO₃与新生成的酸反应产生CO₂，最后经过气相色谱定量CO₂，间接得出样品中氨氮的含量。结果表明，氨氮含量与气相色谱信号值之间存在良好的线性相关性，相关系数为0.999，定量限为0.786 mg/L（以N的质量浓度计），相对标准偏差小于2%，加标回收率在95%~105%之间。与国标纳氏试剂法相比，该方法测定结果的相对偏差在±5%以内。该方法检测效率高，适用于快速批量检测污水中氨氮的含量。     

二氧化钛载Ir催化剂对氨氧化的电催化性能

用同一方法制备了Ir含量相同而载体TiO2-晶体结构不同的TiO2-载Ir（Ir/TiO2）催化剂,研究了TiO2-晶体结构对Ir/TiO2催化剂对氨氧化的电催化性能的影响,发现具有金红石结构的TiO2-载Ir（Ir/TiO2-R）催化剂对氨氧化的电催化性能远好于具有锐钛矿型结构的TiO2-载Ir（Ir/TiO2-A）催化剂。 物理化学和电化学的表征揭示了Ir/TiO2-R催化剂对氨氧化的电催化性能好的可能原因归结于Ir纳米粒子在TiO2-R上的均匀分布。     

氮-硫共掺杂二氧化钛光催化剂的制备及其可见光催化活性

采用研磨煅烧法,以硫脲(TU)作为氮源和硫源,H2TiO3(HT)为TiO2的前驱体,制备了不同TU/HT比例的N,S共掺杂TiO2光催化剂(NS/TiO2);利用X射线衍射仪、透射电镜、X射线光电子能谱仪、拉曼光谱仪、紫外-可见吸收光谱仪等分析了NS/TiO2的晶体结构、显微形貌、典型元素的化学状态以及光谱性质;利用BET法测定了NS/TiO2的比表面积,同时测定了其在可见光照下催化降解罗丹明B的活性.结果表明,当TU/HT质量比为0.5时,NS/TiO2的光催化活性最佳,光照70min时的罗丹明B降解率为44.4%.氮元素以NH3形式吸附在TiO2表面,硫元素以S6+形式存在,部分S6+取代Ti 4+的位置.与此同时N,S共掺杂使得TiO2的禁带宽度减小,可见光催化活性提高.     

Flow-injection determination of inorganic forms of nitrogen by gas diffusion and conductimetry

A flow-injection—conductimetric method was applied to the determination of ammonia, nitrate and nitrite at concentrations down to 5, 20 and 20 ng ml^?1, respectively. Ammonia was determined by merging the injected sample with an alkaline solution (NaOHEDTA) and passing the mixture through a diffusion cell. The ammonia released was collected by a flowing stream of deionized water that passed through a conductance flow cell. Nitrate and nitrite concentrations were determined after reduction to ammonia in alkaline medium using a column filled with metallic zinc. The ammonia produced was then measured as described above. About 60 samples per hour can be processed with a relative standard deviation of about 1%. Satisfactory agreement was observed between results for ammonia in samples of natural water and nitrate in tap and mineral water determined by the proposed method and by standard spectrophotometric procedures. Speciation can be achieved by adding sulphanilic acid to remove nitrite from the sample and determining the ammonia without the use of the column.     

微乳法合成纳米SiO2/TiO2及其光催化性能

采用聚乙二醇辛基苯基醚(Triton X-100)/正己醇/环己烷/氨水微乳体系合成了纳米TiO2和SiO2/TiO2复合物,用X射线衍射、红外光谱和透射电镜对其结构进行了表征,并以甲基橙降解评价了其光催化性能,讨论了SiO2/TiO2摩尔比、晶相组成及粒径与光催化活性的关系.结果表明,SiO2/TiO2催化剂中形成了新的Ti-O-Si键和无定形SiO2;在纳米TiO2中复合SiO2能有效抑制锐钛矿向金红石的转变,增加锐钛矿的稳定性,并阻止TiO2晶粒的聚集生长.催化剂的光催化活性随金红石含量的增加而降低,加入适量SiO2能明显提高TiO2的光催化活性,其中摩尔比为1/7的SiO2/TiO2光催化活性最高.     

WO3对MnOx/TiO2低温脱硝SCR催化剂的改性研究

以醋酸锰为前驱物通过浸渍法制备了MnO_x/TiO₂催化剂,用WO₃对载体进行改性制得一系列MnO_x-WO₃/ TiO₂催化剂,采用X射线衍射（XRD）、比表面积测定(BET)、拉曼光谱(LRS)、原位红外(FT-IR)光谱等表征技术进行相关的微观表征分析,同时在模拟氨气选择性催化还原NO_x（NH₃-SCR）的反应条件下对催化剂的脱硝反应活性进行了考察。研究表明,添加5%的WO₃拓展了载体的比表面积,提高了催化剂的抗热性,增加了催化剂表面的Brnsted酸位,拓宽其选择性催化还原脱硝活性温度窗口,对MnO_x/TiO₂催化剂有很好的改性作用;先钨后锰的负载顺序优于先锰后钨;随着温度的升高,化学催化反应速率提高,催化剂表面NH₃吸附峰呈减弱或消失趋势,故催化剂脱硝活性温度曲线呈中间高、两头低。     

氨法选择性还原氮氧化物 V2O5/TiO2-PILC催化剂的抗硫性能

选择性催化还原(SCR)是目前去除氮氧化物最有效的方法之一. V2O5/TiO2催化剂被广泛应用于氨法选择性还原氮氧化物(NH3-SCR)反应,但该催化剂存在工作温度高(300–400oC)及 SO2氧化率高引起设备腐蚀和管路堵塞等问题,开发低温 SCR催化剂具有重要意义.过渡金属氧化物(如 Fe2O3, MnOx和 CuO等)催化剂用于低温SCR先后见诸文献报道,但这些催化剂在 SO2和 H2O存在下易失活.近年来柱撑黏土(PILC)引起科学家广泛关注, Yang等首次将 V2O5/TiO2-PILC催化剂应用于 NH3-SCR反应,发现其催化活性高于传统 V2O5/TiO2催化剂.柱撑黏土基催化剂在 NH3-SCR反应中也显示出良好抗硫性能,但 V2O5/TiO2-PILC催化剂的抗硫机理至今尚未见深入研究.因此我们制备了一系列 V2O5/TiO2-PILC催化剂,采用原位漫反射红外等方法详细研究了其抗硫性能较好的原因.
　　首先采用离子交换法制备出 TiO2-PILC载体,之后采用浸渍法制备了不同钒含量(质量分数x/%=0,3,4,5)的xV2O5/TiO2-PILC催化剂.同时,制备了传统 V2O5/TiO2和 V2O5-MoO3/TiO2催化剂作为对比.活性评价结果显示,4V/TiO2-PILC催化剂具有最高的催化活性,其催化性能与传统钒钛催化剂相当.在160oC时, NO转化率可达80%以上.同时,4V/TiO2-PILC催化剂还具有较宽的反应温度窗口,在260–500oC范围内, NO转化率保持在90%以上.向反应体系中加入0.05% SO2和10% H2O后,在低温(160oC以下)时所有催化剂的反应活性都有一定提高,可能是由于 SO2的加入提高了催化剂的表面酸性.继续升高温度,4V/TiO2和4V6Mo/TiO2催化剂活性均明显下降,而4V/TiO2-PILC催化剂的活性则未出现明显下降.原位漫反射红外光谱结果显示, SO2在三种催化剂表面的吸附以表面硫酸盐或亚硫酸盐物种以及离子态 SO42–物种形式存在,而在4V/TiO2-PILC催化剂表面离子态 SO42–物种的量最少. X射线光电子能谱及 O2程序升温脱附结果显示,在4V/TiO2-PILC催化剂上,表面吸附氧(Oads)的量最少.综合上述分析可以得出,在 SO2气氛下,离子态 SO42–物种在 SCR催化剂表面的累积可能是导致其失活的主要原因,而离子态 SO42–物种的形成可能与催化剂表面吸附氧的量有关.     

Photocatalytic degradation of high ammonia concentration water solutions by TiO2

Recent studies reported the use of suspended TiO2 powder as photo catalyst in the degradation process of several organic and inorganic substances in water, like chlorinated hydrocarbons, alkyl- and alkanoloammines and ammonia. In order to evaluate the possibility of using this method for a further removal of ammonia from wastewater after a biological nitrification/denitrification treatment, a kinetic study of photo oxidation over TiO2 of NH3/NH4 in the high concentration range of 26 - 214 mg/I, has been carried out. Effects of pH, TiO2, ammonium and dissolved O2 concentration on the degradation efficiency and reaction products distribution (NO2-, NO3- e N2) were studied. The results have shown that, at a catalyst concentration of 0.012% (p/v), the photo catalytic oxidation of ammonia can be described with the Langumuir- Hinshelwood kinetic model, as reported by several authors.     

P3HT/CdS/TiO2/ZnO一维有序核壳式纳米棒阵列的构制及其在杂化太阳电池中的应用研究

采用恒电位法在铟锡氧化物导电玻璃(ITO)上制备了高度有序一维ZnO纳米棒阵列,将ZnO纳米棒阵列在TiO2溶胶中采用提拉法制备出了一维TiO2/ZnO核壳式纳米棒阵列.在一维TiO2/ZnO核壳式纳米棒阵列上电沉积CdS纳米晶得到一维CdS/TiO2/ZnO核壳式纳米棒阵列,然后在一维CdS/TiO2/ZnO核壳式纳米棒阵列上电沉积聚3-己基噻吩(P3HT)薄膜得到P3HT/CdS/TiO2/ZnO核壳式纳米结构薄膜.以该纳米结构薄膜电极为光阳极制备出新型纳米结构杂化太阳电池,研究了该类电池的光电转换性能,初步探讨了该类电池的工作机理.     

MoO3、NiO、ZnO在小表面金红石上的分散行为

Dispersion of MoO3, NiO, ZnO on rutile TiO2 with low specific surface area was studied with Mercury Porosimeter, SEM, XPS and Ammonia Extraction method. The dispersion thresholds of MoO3, NiO, ZnO on three rutile TiO2 carriers were obtained with XPS, and com-pared with those on anatase TiO2 with high specific surf are area. Ammonia Extraction method was used to identify the surface oxide species interarting with support surface in different strength and it was found that the proportions of oxides that can not be extracted by ammonia extraction are different for MoO3, NiO and ZnO which are supported on rutile TiO2.     

N掺杂TiO_2光催化剂的微结构与吸光特性研究

以紫外可见漫反射光谱(UV-VIS-DRS)和X射线光电子能谱(XPS)分析和研究了四种方法制备的N掺杂TiO2光催化剂的结构,即水解法(N/TiO2-H)、氨热还原法(N/TiO2-A)、机械化学法(N/TiO2-M)和尿素热处理法(N/TiO2-T)等.结果表明,N/TiO2-H和N/TiO2-T两种催化剂在490 nm处有吸收带边,可见光激发途径是掺杂的N以填隙方式形成的杂质能级吸收电子发生的跃迁引起的;而N/TiO2-A和N/TiO2-M两种催化剂在整个可见光区域内具有可见光吸收,其对可见光的激发途径是掺杂N和氧空缺共同作用的结果.理论计算的N杂质能级位于价带上0.75 eV,与实验观察到的吸收带边结果十分吻合.XPS结果表明,几种催化剂的N1 s结合能位置都在399 eV附近,显示为填隙掺杂的N原子.填隙掺杂的N/TiO2,其Ti原子的2p结合能与未掺杂的TiO2相比增加了+0.3-+0.6 eV,而O1s电子的结合能增加了+0.2-+0.5eV,这是因为填隙的N原子夺取Ti和O的电子,Ti和O原子周围的电子密度降低了.电子能谱和吸光特性的研究都表明,掺杂的机理是在TiO2晶格内形成N原子的填隙.     

MoO_3、NiO、ZnO在小表面金红石上的分散行为

氧化物、盐类在氧化物载体表面的自发分散是一种广泛存在的现象，文献中已报导过大量氧化物和盐类在高比表面载体上分散的研究结果［'－3］TIO。作为一种较新型的载体，与Y－AI。O。、硅胶等传统载体相比，有许多不同特性．活性组分在TIO。表面的分散状态及所得催化剂的性能已有不少报导［'－'］，但所用的TIOZ主要是较高比表面的锐钛矿型TIOZ（刘金红石型TIO。（r）和锐钛矿型TIOZ（a）的结构不同，它是高温生成相，比表面较小［'］．氧化物在金红石上的分散行为仍未见报导．我们制备了三种具有不同比表面的TIO水），系统地研…     

Preparation of nanoporous MgO-coated TiO2 nanoparticles and their application to the electrode of dye-sensitized solar cells

Sol-gel-derived Mg(OH)(2) gel was coated onto TiO(2) nanoparticles, and the subsequent thermal topotactic decomposition of the gel formed a highly nanoporous MgO crystalline coating. The specific surface area of the electrode that was prepared from the core-shell-structured TiO(2) nanoparticles significantly increased compared with that of the uncoated TiO(2) electrode. The increase in the specific surface area of the MgO-coated TiO(2) electrode was attributed to the highly nanoporous MgO coating layer that resulted from the topotactic reaction. Dye adsorption behavior and solar cell performance were significantly enhanced by employing the MgO-coated TiO(2) electrode. Optimized coating of a MgO layer on TiO(2) nanoparticles enhanced the energy conversion efficiency as much as 45% compared to that of the uncoated TiO(2) electrode. This indicates that controlling the extrinsic parameters such as the specific surface area is very important to improve the energy conversion efficiency of TiO(2)-based solar cells.     

负载金的掺氮二氧化钛的制备及其可见光催化性能

以纳米管钛酸为前驱体,采用水热法先制备得到新型N掺杂二氧化钛,然后用沉积沉淀法在N掺杂二氧化钛表面负载微量贵金属Au,制备得到负载Au的掺N二氧化钛.利用TEM、XRD、XPS、ESR和DRS等手段研究了样品的形貌、晶体结构、元素化学态和光谱吸收性质.样品光催化活性通过可见光催化降解丙烯进行评价,结果表明,样品N-TiO₂和Au/N-TiO₂具有明显的可见光(λ≥420 nm)催化活性.ESR结果表明,掺氮过程中生成的束缚单电子的氧空位是样品具有可见光响应的原因.     

中空TiO_2微球的制备及对聚丙烯酸酯薄膜性能的影响

采用阳离子聚苯乙烯微球作为模板,钛酸四丁酯为钛源,氨水为催化剂,制备了中空TiO_2微球.采用X射线衍射、扫描电镜及比表面测定仪对其形貌和结构进行了表征,并考察了模板粒径、钛源用量以及催化剂用量对中空TiO_2微球形貌的影响.通过物理共混法将其引入至聚丙烯酸酯乳液中并成膜,研究了复合薄膜的保温性能、抗紫外性能及力学性能.结果表明,锐钛矿相中空TiO_2微球模板粒径、钛源用量以及催化剂用量影响中空TiO_2微球的空心尺寸、壁厚及壳层致密性.中空TiO_2微球可显著提升聚丙烯酸酯薄膜的保温性能、抗紫外性能和力学性能.采用不同粒径的模板制备的中空TiO_2微球对复合薄膜的各项性能均有影响,其中模板粒径为140 nm时复合薄膜性能最优,光反射率提升63%,导热系数降低27%,且在波长小于360 nm范围内,紫外透过率几乎为0,抗张强度增加100%,断裂伸长率提升62%.     

Ce及N共掺杂改性TiO_2光催化性能及Ce组分的作用

以钛酸正丁酯、硝酸亚铈及氨水为前驱体运用溶胶-凝胶法对TiO2进行Ce及N单一和共掺杂改性,以甲基橙光催化降解为探针考察掺杂组分对催化剂的紫外、可见光活性影响,观察到了Ce及N的单一掺杂及共掺杂催化剂紫外、可见光活性的明显提升。运用X射线衍射(XRD)、低温氮气吸附(BET)、紫外-可见漫反射吸收光谱(DRS)、程序升温氧脱附(TPD)和程序升温氧化(TPO)等表征手段从催化剂的晶体结构及形貌、比表面积、紫外及可见光响应特性、表面吸附氧量及吸附氧循环性能等方面尝试理解掺杂组分的光活性影响机制。实验结果表明掺杂改性催化剂中适量Ce组分的作用在于通过抑制催化剂的晶粒长大、团聚和锐钛结构向金红石结构的相转变,提高催化剂的光相应强度和拓展光响应范围,增加催化剂表面吸附氧容量和促进催化剂的表面氧循环,有效捕获光生载流子,衍生各类高活性自由基物种和增大催化剂比表面积等方面增进催化剂的光催化性能。