在Pd/TiO2上CO的光催化增强效应

在Pd(2％)/TiO2上CO催化氧化的研究中发现：室温下， 以黑光灯（λ=365 nm）照时， CO的氧化活性比暗态显著提高，产生了明显的光催化增强效应（两者速率常数比约为15）.但在TiO2上，无论暗态还是黑光灯（λ=365 nm）照，均无CO氧化反应发生.这可能是由于氧分子解离吸附时的键能减弱，使Pd表面氧原子（或O－）浓度增加和氧原子的溢流（oxygen spillover）两种效应结合产生的.     

Ag和Pd及其离子对TiO2光催化分解CH3CHO的影响

当用能量大于其禁带宽度的光照射通有氧气的TiO₂悬浮液时,在TiO₂微粒表面会产生反应活性很高的空穴和O₂^-、H₂O₂等多种活性氧.在上一篇文章中^[1]我们已报道了在通氧气和紫外光照的条件下,向TiO₂悬浮液中加入少量Ag⁺或Pd²⁺,将会大幅度提高体系中H₂O₂的生成量.另外,蔡汝雄等人也曾通过向TiO₂悬浮液中加入SOD的方法来提高其中H₂O₂的生成量^[2],而且证明了H₂O₂生成量的增多有助于杀死子宫癌细胞^[3].另一方面,利用TiO₂光催化来分解处理工业废水中的有机物已多见报道^[4～7].因此,为考察H₂O₂含量的增加是否有助于TiO₂催化分解有机物,我们以CH₃CHO为氧化对象,测定了经Ag和Pd表面修饰以及直接向悬浮体系添加Ag⁺或Pd²⁺离子前后,TiO₂光催化氧化分解CH₃CHO效率的变化,并对氮气和氧气气氛的实验结果进行了测定和比较.     

TiO2/UV/O2和TiO2/UV/N2体系降解水中对氯硝基苯

以商用TiO₂P25为催化剂,分别在TiO₂/UV/O₂和TiO₂/UV/N₂两种体系下进行降解对氯硝基苯(pCNB)试验.采用ESR对两种体系下光催化反应形成的·OH进行测定,利用LC-MS对两种体系下反应形成的中间产物进行了定性和定量分析,最后对pCNB降解过程中氯和硝基的存在形式进行了研究.结果表明:TiO₂/UV/O₂体系的催化降解效果要明显优于TiO₂/UV/N₂体系;两种反应体系都有·OH产生,并且TiO₂/UV/O₂体系产生的·OH的量多于TiO₂/UV/N₂体系产生的·OH的量;TiO₂/UV/O₂体系形成的中间产物的种类要多于TiO₂/UV/N₂体系形成的,苯环上的氢、氯、硝基均可被·OH取代形成对硝基酚(pNP)、5-氯-2-硝基酚(5-C-2-PN)等酚类物质;两种体系下均有Cl^-和NO₂^-存在,其中Cl^-生成势与pCNB的去除势一致,只有TiO₂/UV/O₂体系中存在NO₃^-.     

紫外光诱导氧合型肌红蛋白氧化反应及机理

肌红蛋白通常在无光条件下可进行输氧、储氧等重要功能,实验中我们发现紫外光照射可促进氧合肌红蛋白(MbO₂)的氧化反应,证实其在光照时部分生理功能会发生变化。紫外-可见(UV-Vis)吸收光谱数据显示,光照射时MbO₂的Soret带最大吸收波长蓝移、Q吸收带544和580 nm处还原峰强度下降,说明紫外光光照促进O₂解离, MbFe(Ⅱ)可被氧化至MbFe(Ⅲ)。四种波长光对光照氧化的影响程度为254 nm > 280 nm >430 nm > 409 nm;通入CO气体时氧合肌红蛋白较难发生光照氧化反应,即Fe的第六配位强度影响反应程度;溶液中的H⁺或OH^-对光照氧化反应有促进作用; 254、280 nm波长光照射时,苯丙氨酸(Phe)、酪氨酸(Tyr)、色氨酸(Trp)三种游离氨基酸均促进光照氧化反应的进行,而409、430 nm波长光照射时三种游离氨基酸对光照氧化反应的影响较小。以上数据表明体内光诱导MbO₂氧化反应过程中蛋白质内的Fe(Ⅱ)能否被光照激发形成未成对电子处于激发态是O₂离去和二价铁被氧化的关键。     

可漂浮CA/TiO2/RGO光催化剂的制备及其性能探究

首先利用氧化石墨烯(GO)改性TiO₂,然后以碳酸钙-碳酸钠为造孔剂，通过海藻酸钙(CA)固载TiO₂/GO制备CA/TiO₂/GO凝胶微球，最后该微球经抗坏血酸水浴还原GO,获得可漂浮CA/TiO₂/RGO微球作光催剂；并采用FT-IR、XRD、SEM、UV-Vis DRS以及TGA等测试手段对CA/TiO₂/RGO形貌及结构进行表征分析，初步探究CA/TiO₂/RGO对氨基黑10B降解性能和机理。结果表明：于30 mg/L氨基黑10B染料溶液中，投加CA/TiO₂/RGO光催剂浓度为1.84 g/L,220 min内CA/TiO₂/RGO对氨基黑10B的降解率可达80%,降解过程符合一级反应动力学模型，其光催化降解的主要活性物种是·O₂^-,而·OH和h⁺在本降解中起到作用相对较小。     

不同前驱物制备的MnOx/TiO2联合O3催化氧化NO性能

分别以乙酸锰（MnAc）、氯化锰（MnCl₂）和硝酸锰（Mn（NO₃）₂）为前驱物,采用浸渍法制备MnAc/TiO₂、MnCl/TiO₂和MnN/TiO₂三种催化剂,并采用氮吸附、SEM、H₂-TPR、O₂-TPD、XRD和XPS进行表征。在固定床反应器上研究了三种催化剂的联合臭氧催化氧化NO性能。结果表明,以乙酸锰为前驱物制备的MnAc/TiO₂催化剂联合臭氧催化氧化NO活性最高;MnAc/TiO₂催化剂颗粒分散性好,比表面积相对较大,催化剂表面Mn³⁺较多,因而具有较高的催化活性。     

C/Cr2O3/TiO2复合材料的制备及其光催化性能研究

本文以制革含铬革屑为原材料,基于矿物鞣剂复鞣的原理,将Ti(IV)均匀、稳定地负载到含铬革屑上,在氮气氛围下,经高温热解制备得到C/Cr₂O₃/TiO₂光催化剂,并研究了其对四环素(TC)的光催化降解效果及机理。结果表明,C/Cr₂O₃/TiO₂光催化剂具有明显的介孔结构,比表面积较大,为277.47 m²·g^-1,Cr₂O₃和TiO₂已实现复合并负载在生物炭(C)上。通过光催化降解发现,在模拟自然光照下,当催化剂用量为0.04 g,TC初始浓度为50 mg·L^-1,溶液pH为2时,TC的去除率可高达99.99%。结合自由基捕获实验发现,C/Cr₂O₃/TiO₂光催化剂对TC的降解作用主要依靠反应体系中产生的大量·O₂^-,·OH和h⁺。     

利用ESR技术研究α-蒎烯,β-蒎烯光敏氧化反应机理

本文主要利用电子顺磁共振(ESR)自旋捕获技术研究9,10 二氰基蒽(DCA)敏化α-蒎烯(αP),β-蒎烯(βP)光氧化反应.提供了在乙腈中α-蒎烯和β-蒎烯的光氧化反应过程中存在超氧负离子基(O₂^-)和单重态氧(¹O₂)的直接证据;在四氯化碳溶剂中只捕获到¹O₂;在正己烷中没有捕获到O₂^-或¹O₂.ESR实验结果进一步证明在乙腈中光敏氧化反应的¹O₂可能来自O₂^-和反应底物α、β-蒎烯正离子自由基之间的电荷复合(CR).     

采样极谱法测定SOD模型化合物催化超氧离子歧化反应速率常数

用采样极谱法研究了非质子溶剂中SOD模型化合物催化O₂^-的歧化反应,用简化的函数关系代替动力学微分方程的准确解.通过测定极限催化电流与极限扩散电流比随SOD模型化学物浓度及滴汞电极滴下时间的变化,确定催化O₂^-歧化反应速率常数K₁.     

低量La3+掺杂S-TiO2光催化剂的制备、表征及其光催化活性

采用溶胶-凝胶-浸渍法制备了La³⁺/S-TiO₂纳米光催化剂,通过XRD、BET、XPS、UV-Vis等手段进行了表征.以甲基橙溶液为光催化降解反应的模型化合物,考察了光催化剂的活性,探讨了低量La³⁺掺杂对TiO₂纳米粒子光催化活性的影响机制.实验结果表明:S改性TiO₂后明显提高了TiO₂纳米粒子的光催化活性,而La³⁺掺杂S-TiO₂后,进一步提高了TiO₂纳米粒子的光催化活性,La³⁺的最佳掺杂量(相对于TiO₂的质量分数)为0.369%;La³⁺/S-TiO₂(ω(La³⁺)=0.369%)为纳米光催化剂时,甲基橙的脱色率达到92.4%(光照120min);XRD和BET分析表明,低量La³⁺掺杂抑制了TiO₂由锐钛矿向金红石的转变,阻碍了TiO₂晶粒的生长,提高了TiO₂的比表面积;XPS分析表明,S、La³⁺掺杂可以导致粉体的表面羟基含量增加,掺杂S以S⁶⁺形式置换TiO₂晶格中的Ti⁴⁺;UV-Vis分析表明,光催化剂La³⁺/S-TiO₂比纯TiO₂具有较强的紫外光吸收性能.与纯TiO₂相比,La³⁺掺杂TiO₂纳米粒子光催化氧化活性的提高应归因于La³⁺掺杂增加了表面羟基含量,增大了比表面积,增强了样品表面的紫外光吸收能力.     

Mechanistic studies of the photocatalytic oxidation of trichloroethylene with visible-light-driven N-doped TiO2 photocatalysts

Visible-light-driven TiO2 photocatalysts doped with nitrogen have been prepared as powders and thin films in a cylindrical tubular furnace under a stream of ammonia gas. The photocatalysts thus obtained were found to have a band-gap energy of 2.95 eV. Electron spin resonance (ESR) under irradiation with visible light (lambda > or = 430 nm) afforded the increase in intensity in the visible-light region. The concentration of trapped holes was about fourfold higher than that of trapped electrons. Nitrogen-doped TiO2 has been used to investigate mechanistically the photocatalytic oxidation of trichloroethylene (TCE) under irradiation with visible light (lambda > or = 420 nm). Cl and O radicals, which contribute significantly to the generation of dichloroacetyl chloride (DCAC) in the photocatalytic oxidation of TCE under UV irradiation, were found to be deactivated under irradiation with visible light. As the main by-product, only phosgene was detected in the photocatalytic oxidation of TCE under irradiation with visible light. Thus, the reaction mechanism of TCE photooxidation under irradiation with visible light clearly differs markedly from that under UV irradiation. Based on the results of the present study, we propose a new reaction mechanism and adsorbed species for the photocatalytic oxidation of TCE under irradiation with visible light. The energy band for TiO2 by doping with nitrogen may involve an isolated band above the valence band.     

TiO2和ZnO表面CO光催化氧化活性研究

在TiO2和ZnO表面CO光催化氧化研究中发现,365 nm紫外光照下TiO2表面无活性,而ZnO表面却有明显的CO光催化氧化活性.研究表明,主要是由于紫外光照下,ZnO光分解而TiO2没有光分解,从而在表面产生不同吸附形态的氧所致.而且,ZnO表面CO光催化氧化反应活性可在27 h内保持稳定,暗示气相光催化反应中,ZnO不会因为光腐蚀而使其催化活性降低.     

水汽对TiO_2上CO光催化氧化反应的影响

在室温、杀菌灯照射下 ,对“氧化的”TiO2 催化剂上CO光催化氧化反应进行了研究 ,发现当原料气中加入分压为 3.36kPa水汽时 ,光催化氧化CO的活性明显降低 .这可能是由于杀菌灯照射下TiO2 表面生成的O-(a) 或O(a) 与H2 O反应生成·OH ,降低了表面的O-(a) 和O(a) 的浓度 ,而生成的·OH不能使CO氧化 ,从而降低了氧化CO的能力     

Kinetics of heterogeneous photocatalytic degradation of reactive dyes in an immobilized TiO2 photocatalytic reactor

The photocatalytic degradation of two reactive dyes has been investigated by UV/TiO2/H2O2 using an immobilized TiO2 photocatalytic reactor. Reactive Blue 8 (RB 8) and Reactive Blue 220 (RB 220) textile dyes were used as model compounds. Photocatalytic degradation processes were performed using a 5-L solution containing dyes. The initial concentrations of dyes were 50 mg/L. The radiation source was two 15 W UV-C lamps. A batch mode immersion photocatalytic reactor was utilized. UV-vis and ion chromatography (IC) analyses were employed to obtain the details of the photodegradation of the selected dyes. Colored synthetic waters were completely decolorized in relatively short time after UV irradiation in the presence of various concentrations of hydrogen peroxide. Formate, acetate, oxalate, and glyoxylate anions were detected as dominant aliphatic intermediates where they were further oxidized slowly to CO2. The UV/TiO2/H2O2 process was able to oxidize the dyes with partial mineralization of carbon, nitrogen, and sulfur heteroatoms into CO2, NO3-, and SO4(2-), respectively. Kinetics analysis indicates that the photocatalytic decolorization rates of the dye can be approximated by a pseudo-first-order model. The UV/TiO2/H2O2 process proved to be capable of decolorization and mineralization of the reactive dyes (RB 8 and RB 220).     

CO Preferential oxidation promoted by UV irradiation in the presence of H2 over Au/TiO2

The catalytic oxidation of CO was performed over Au/TiO(2) under UV irradiation in the presence of H(2) in different reaction systems. It was found that the introduction of H(2) enhanced the CO thermocatalytic oxidation in a CO pre-introduced system (CO/O(2)vs. CO/H(2)/O(2)), but suppressed that in an O(2) pre-introduced (O(2)/CO vs. O(2)/H(2)/CO) system. Although the CO oxidation in both CO/H(2)/O(2) and O(2)/H(2)/CO systems could be remarkably enhanced under UV irradiation, the oxidation of H(2) was suppressed under UV irradiation. It was proposed that the dissociative chemisorption H ([triple bond]Ti-H) at surface oxygen vacancy sites of TiO(2) could act as both the electron-acceptors for the photogeneration electrons and the electron-donors for the chemisorbed O(2) at TiO(2), and thus enhance the CO oxidation during the coinstantaneous process of thermocatalysis and photocatalysis. The suppression of H(2) thermocatalytic oxidation under UV irradiation might be ascribed to the electron transfer effect, i.e., the dissociative chemisorption H on Au (Au-H) could be desorbed at the H(2) molecule via accepting the photogenerated electrons from TiO(2).     

Size control synthesis of sulfur doped titanium dioxide （anatase） nanoparticles, its optical property and its photo catalytic reactivity for CO2 ＋ H2O conversion and phenol degradation

Sulfur doped anatase TiO2 nanoparticles (3 nm−12 nm) were synthesized by the reaction of titanium tetrachloride, water and sulfuric acid with addition of 3M NaOH at room temperature. The electro-optical and photocatalytic properties of the synthesized sulfur doped TiO2 nanoparticles were studied along with Degussa commercial TiO2 particles (24 nm). The results show that band gap of TiO2 particles decreases from 3.31 to 3.25 eV and for that of commercial TiO2 to 3.2 eV when the particle sizes increased from 3 nm to 12 nm with increase in sulfur doping. The results of the photocatalytic activity under UV and sun radiation show maximum phenol conversion at the particle size of 4 nm at 4.80% S-doping. Similar results are obtained using UV energy for both phenol conversion and conversion of CO2+H2O in which formation of methanol, ethanol and proponal is observed. Production of methanol is also achieved on samples with a particle size of 8 and 12 nm and sulfur doping of 4.80% and 5.26%. For TiO2 particle of 4 nm without S doping, the production of methanol, ethanol and proponal was lower as compared to the S-doped particles. This is attributed to the combined electronic effect and band gap change, S dopant, specific surface area and the light source used.     

甲醛光催化氧化的反应机理

采用程序升温脱附（TPD）, 电子自旋共振（ESR）及自旋捕获 电子自旋共振(ST ESR)等物理方法对甲醛光催化氧化过程中,反应物的吸附状态、自由基中间物种及反应机理 进行了研究.结果表明,在光催化氧化空气中微量甲醛的反应条件下,吸附在催化剂表面的空 气中的氧气被光生电子还原为•O－2,微量水被空穴氧化为•OH.二者为甲醛的深度氧化提供了高活性的氧化剂.甲醛是通过中间产物甲酸而氧化为终点 产物二氧化碳的.     

Localized Partial Oxidation of Acetic Acid at the Dual Perimeter Sites of the Au/TiO(2) Catalyst-Formation of Gold Ketenylidene

Chemisorbed acetate species derived from the adsorption of acetic acid have been oxidized on a nano-Au/TiO(2) (～3 nm diameter Au) catalyst at 400 K in the presence of O(2)(g). It was found that partial oxidation occurs to produce gold ketenylidene species, Au(2)═C═C═O. The reactive acetate intermediates are bound at the TiO(2) perimeter sites of the supported Au/TiO(2) catalyst. The ketenylidene species is identified by its measured characteristic stretching frequency ν(CO) = 2040 cm(-1) and by (13)C and (18)O isotopic substitution comparing to calculated frequencies found from density functional theory. The involvement of dual catalytic Ti(4+) and Au perimeter sites is postulated on the basis of the absence of reaction on a similar nano-Au/SiO(2) catalyst. This observation excludes low coordination number Au sites as being active alone in the reaction. Upon raising the temperature to 473 K, the production of CO(2) and H(2)O is observed as both acetate and ketenylidene species are further oxidized by O(2)(g). The results show that partial oxidation of adsorbed acetate to adsorbed ketenylidyne can be cleanly carried out over Au/TiO(2) catalysts by control of temperature.     

甲醇在纳米TiO2作用下进行光催化氧化反应的机理研究

以纳米TiO2为催化剂,以主波长为364 nm的汞灯为光源,用气相色谱法分别考察了0.1 mol/L的甲醇、甲醛和甲酸水溶液进行光催化氧化反应的动力学规律.Langmuir-Hinshelwood方程进行核算结果证明,该组反应均为零级反应.用TEM、 XRD、 SSA和XPS对催化剂进行表征.根据XPS的检测结果提出了甲醇光催化氧化的反应机理.TiO2光激发活化时间约为30～60 min,生成物及剩余反应物浓度随时间变化的曲线表明,该反应速率为HCH2OH相似文献