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1.
在Pd/TiO2上CO的光催化增强效应   总被引:4,自引:0,他引:4  
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.  相似文献   

2.
This paper reveals the fact that the O adatoms (O(ad)) adsorbed on the 5-fold Ti rows of rutile TiO(2)(110) react with CO to form CO(2) at room temperature and the oxidation reaction is pronouncedly enhanced by Au nano-clusters deposited on the above O-rich TiO(2)(110) surfaces. The optimum activity is obtained for 2D clusters with a lateral size of ~1.5 nm and two-atomic layer height corresponding to ~50 Au atoms∕cluster. This strong activity emerging is attributed to an electronic charge transfer from Au clusters to O-rich TiO(2)(110) supports observed clearly by work function measurement, which results in an interface dipole. The interface dipoles lower the potential barrier for dissociative O(2) adsorption on the surface and also enhance the reaction of CO with the O(ad) atoms to form CO(2) owing to the electric field of the interface dipoles, which generate an attractive force upon polar CO molecules and thus prolong the duration time on the Au nano-clusters. This electric field is screened by the valence electrons of Au clusters except near the perimeter interfaces, thereby the activity is diminished for three-dimensional clusters with a larger size.  相似文献   

3.
利用太阳能在温和条件下实现CO2还原反应,不仅可以缓解过度消耗化石能源造成的能源危机,还可以改善诸如温室效应和海洋酸化等环境问题.光热协同催化可以有效降低催化反应温度,具有较大的应用前景.本文利用Ru与暴露TiO2{001}晶面的TiO2载体产生的金属-载体相互作用,经过高温氢气煅烧后,获得具有丰富表面氧空位的Ru/TiO2催化剂.活性测试结果表明,具有丰富表面氧空位的Ru/TiO2表现出优异的CO2甲烷化活性,反应过程中甲烷的TOF值在300°C时可以达到22 h-1,但该催化剂却表现出较差的稳定性,在反应10小时后,甲烷的TOF值逐渐降低到19 h-1.将紫外光引入到Ru/TiO2热催化甲烷化体系中,甲烷的TOF值增加到30 h-1,且兼具高稳定性.热催化反应过程中逐渐消失的表面氧空位和部分氧化的Ru是活性降低的主要原因.在光热协同反应中,光生电子的产生稳定了Ru表面的电子密度,同时也再生了催化剂上表面氧空位,这有效地提高了反应的活性和稳定性.程序升温原位红外和X射线光电子能谱实验结果表明,当催化剂表面具有丰富的表面氧空位时,CO2可以有效地在Ru纳米粒子上解离成CO中间体,随后吸附在Ru上的CO中间体解离成表面碳物种,并加氢产生甲烷.在热催化反应过程中,Ru纳米粒子逐渐被氧化成Ru Ox物种,且表面氧空位被CO中间物种覆盖,降低了催化反应的稳定性.当紫外光引入到上述反应中,催化剂的表面氧空位可有效提高光生载流子的分离能力.TiO2载体产生的光电子转移至Ru表面,稳定了金属Ru纳米粒子的价态.另外,载体产生的光生空穴加速了H2质子化,提高了催化剂对氢气的活化迁移能力,促进了CO中间体的加氢甲烷化反应,进而再生表面氧空位.因此在紫外光照下,兼顾提高了热催化CO2甲烷化的活性和稳定性.值得注意的是,当Ru负载于暴露少量TiO2{001}晶面的TiO2载体上时,产生了强金属-载体相互作用并抑制了H2在催化剂上的吸附活化,不利于产生表面氧空位.因此暴露少量TiO2{001}晶面的Ru/TiO2催化剂也不利于光生载流的产生和分离,这导致热催化或光热协同催化反应活性较低.  相似文献   

4.
太阳能因其环保清洁和来源丰富的特性被认为是最理想的资源之一.而光催化水分解是将太阳能转化为化学能的众多转换技术中,使用最广泛的策略之一.但H2和O2的逆反应显著降低了光催化水分解的效率,并且在实际应用中需要高昂的气体分离成本.因此,找到一种既可实现光催化有效水分解,同时抑制逆反应的策略具有十分重要的意义.到目前为止,为了实现光生电荷的有效分离,构建一维(1D)异质纳米结构光催化剂,被认为是抑制逆反应最有效的策略之一.其中哑铃状纳米结构,如Au-SiO2,Au-Fe3O4,Cu1.94S-CuS,Au-PbS(PbSe),Cu-Ag,Ag-Fe3O4,在促进光生电荷有效分离方面具有很大优势.但关于上述哑铃状纳米结构材料合成条件相对复杂,生长机理尚不清楚.对此,我们通过一种简便的合成策略制备了Au纳米棒/TiO2纳米哑铃结构光催化剂(Au NRs/TiO2 NDs).TiO2纳米颗粒(NP)仅包裹在Au NRs的两端.由于其独特的结构,可以实现电子空穴的定向分离,并减少它们在光照射下的复合,从而显著地提高电荷分离效率.同时,形成了氧化和还原反应的空间分离区域,从而有效地抑制了逆反应.通过SEM,XRD,和UV-Vis研究了可控合成哑铃状结构形态的关键因素.发现反应温度和酸度对Au NRs末端TiO2的包裹量有显著影响.基于此,我们提出了Au NRs/TiO2 NDs结构光催化剂的合成机理.并且通过改变加入的NaHCO3含量精准调节TiO2在Au NRs两端的包覆量,从而逐步提高Au NRs/TiO2 NDs光催化剂的产氢活性.在不断优化条件下,H2产率可达60264μmol/g/h,大约是报道的Au/TiO2光催化剂6倍.而电化学测试结果显示,在UV光照射下,Au NRs末端TiO2的包裹量越大,光电流相应越大.进一步证明光生电子定向从TiO2注入到Au NRs中,发生还原反应,而空穴留在TiO2上,发生氧化反应,从而实现氧化还原反应的分区.  相似文献   

5.
Cu2+/TiO2对甲基橙的光催化降解机理   总被引:11,自引:1,他引:10  
以自制的掺铜离子的混晶型二氧化钛为光催化剂,考察了甲基橙光催化降解过程中pH值和光源的影响,提出了两种不同的光催化降解机理:在高压汞灯照射下,TiO2的价带电子被激发到导带,光生电子和空穴主要通过Cu2+ 的短路循环而复合,光催化剂的活性降低;在太阳光照射下,甲基橙发生自身光敏化氧化反应,受激电子从单线态或三线态的甲基橙分子跃迁到TiO2的导带,Cu2+起到电荷传递中继站的作用,加速了注入电子向H2O2的转移,从而促进了甲基橙的光催化降解。  相似文献   

6.
The physicochemical properties of the H(2)O molecules adsorbed on TiO(2) surfaces during UV light irradiation were fully investigated by near-infrared (NIR) absorption spectroscopy. It was found that the H(2)O molecules adsorbed on the TiO(2) surfaces desorb during UV light irradiation by the heating effect of the light source. Since the amount of the H(2)O adsorbed on the TiO(2) surfaces decreased, the distribution of the hydrogen bonds within the H(2)O molecules decreased, resulting in a decrease in the surface tension of the H(2)O clusters. The decrease in the surface tension of H(2)O under UV light irradiation was found to be one of the most important driving forces in which the H(2)O clusters on the TiO(2) surface spread out thermodynamically, forming H(2)O thin layers. The partial elimination of the hydrocarbons from the TiO(2) surface by the photocatalytic complete oxidation was seen to be the other important factor, providing free spaces on the surface where the H(2)O clusters could spill over and spread out to form the thin H(2)O layers. Moreover, the temperature changes of the TiO(2) powder samples during UV light irradiation were found to show a good correspondence with the changes in the contact angle of the H(2)O droplets on the TiO(2) thin film surfaces. Especially the time scale for the hydrophilic conversion on the TiO(2) surfaces under UV light irradiation was in good agreement with the decrease in the amount of H(2)O molecules adsorbed on the TiO(2) surfaces but not the amount of the hydrocarbons eliminated by the photocatalytic oxidation reactions, showing that the adsorption and desorption of H(2)O molecules are generally quite sensitive to the temperature changes of solid surfaces.  相似文献   

7.
最近在“氧化的”TiO2(即表面无氧空位和Ti3+)上进行的CO光催化氧化研究发现:室温下,以黑光灯(峰值λ=365nm)光照时,“氧化的”TiO2无CO催化氧化的活性,但以杀菌灯(峰值λ=253.7nm)光照时,则对CO产生显著的催化活性.参照CO在过渡金属表面的催化氧化机理,对本现象进行了解释:黑光灯照时,O2在TiO2表面只生成O2(a)-,而O2(a)-不能使CO氧化,只有以杀菌灯照时,TiO2表面产生O(a)-,CO氧化反应才能发生.  相似文献   

8.
Visible-light irradiation (λ > 450 nm) of gold nanoparticles loaded on a mixture of anatase/rutile TiO(2) particles (Degussa, P25) promotes efficient aerobic oxidation at room temperature. The photocatalytic activity critically depends on the catalyst architecture: Au particles with <5 nm diameter located at the interface of anatase/rutile TiO(2) particles behave as the active sites for reaction. This photocatalysis is promoted via plasmon activation of the Au particles by visible light followed by consecutive electron transfer in the Au/rutile/anatase contact site. The activated Au particles transfer their conduction electrons to rutile and then to adjacent anatase TiO(2). This catalyzes the oxidation of substrates by the positively charged Au particles along with reduction of O(2) by the conduction band electrons on the surface of anatase TiO(2). This plasmonic photocatalysis is successfully promoted by sunlight exposure and enables efficient and selective aerobic oxidation of alcohols at ambient temperature.  相似文献   

9.
在分子尺度上介绍了Au/TiO2(110)模型催化剂表面和单晶Au表面CO氧化反应机理和活性位、以及H2O的作用.在低温(<320 K), H2O起着促进CO氧化的作用, CO氧化的活性位位于金纳米颗粒与TiO2载体界面(Auδ+–Oδ––Ti)的周边. O2和H2O在金纳米颗粒与TiO2载体界面边缘处反应形成OOH,而形成的OOH使O–O键活化,随后OOH与CO反应生成CO2.300 K时CO2的形成速率受限于O2压力与该反应机理相印证.相反,在高温(>320 K)下,因暴露于CO中而导致催化剂表面重组,在表面形成低配位金原子.低配位的金原子吸附O2,随后O2解离,并在金属金表面氧化CO.  相似文献   

10.
采用溶胶-凝胶法制备了TiO2以及La2O3-TiO2载体, 再用沉积沉淀法制备Au/TiO2和Au/La2O3-TiO2催化剂, 并对催化剂的CO氧化反应活性进行测试. 结果表明, La2O3助剂可以显著提高催化剂催化氧化CO的活性. X射线衍射(XRD)、程序升温脱附(TPD)、N2吸附-脱附(BET)表征结果表明, La2O3助剂不仅提高了催化剂比表面积, 抑制了TiO2晶粒尺寸的长大, 并且增强了TiO2的晶格应变, 在O2气氛吸附过程中主要在TiO2表面形成O-物种. 原位傅立叶变换红外(FT-IR)结果进一步表明, La的掺杂不仅提高了吸附在Au活性位CO的氧化速率, 还使TiO2表面形成第二种活性位, 从而显著提高了催化活性.  相似文献   

11.
Gold-based catalysts have been of intense interests in recent years, being regarded as a new generation of catalysts due to their unusually high catalytic performance. For example, CO oxidation on Au/TiO(2) has been found to occur at a temperature as low as 200 K. Despite extensive studies in the field, the microscopic mechanism of CO oxidation on Au-based catalysts remains controversial. Aiming to provide insight into the catalytic roles of Au, we have performed extensive density functional theory calculations for the elementary steps in CO oxidation on Au surfaces. O atom adsorption, CO adsorption, O(2) dissociation, and CO oxidation on a series of Au surfaces, including flat surfaces, defects and small clusters, have been investigated in detail. Many transition states involved are located, and the lowest energy pathways are determined. We find the following: (i) the most stable site for O atom on Au is the bridge site of step edge, not a kink site; (ii) O(2) dissociation on Au (O(2)-->2O(ad)) is hindered by high barriers with the lowest barrier being 0.93 eV on a step edge; (iii) CO can react with atomic O with a substantially lower barrier, 0.25 eV, on Au steps where CO can adsorb; (iv) CO can react with molecular O(2) on Au steps with a low barrier of 0.46 eV, which features an unsymmetrical four-center intermediate state (O-O-CO); and (v) O(2) can adsorb on the interface of Au/TiO(2) with a reasonable chemisorption energy. On the basis of our calculations, we suggest that (i) O(2) dissociation on Au surfaces including particles cannot occur at low temperatures; (ii) CO oxidation on Au/inactive-materials occurs on Au steps via a two-step mechanism: CO+O(2)-->CO(2)+O, and CO+O-->CO(2); and (iii) CO oxidation on Au/active-materials also follows the two-step mechanism with reactions occurring at the interface.  相似文献   

12.
The surfaces of fumed silica materials were modified with a surface sol-gel process for catalysis applications. This surface-modification approach allows not only a monolayer growth of TiO(2) or Al(2)O(3) but also a stepwise double-layer growth of TiO(2)/TiO(2), Al(2)O(3)/Al(2)O(3), TiO(2)/Al(2)O(3), or Al(2)O(3)/TiO(2) on the surfaces of the silica materials with a monolayer precision. XRD analyses revealed that the coated monolayers and double layers of TiO(2) and Al(2)O(3) were amorphous. Gold nanoparticles were successfully deposited on the above six surface-modified silica materials via a deposition-precipitation method. The catalytic activities of these six gold catalysts for CO oxidation are highly dependent on the structures of their surface monolayers or double layers. The gold catalyst supported on the silica material functionalized with a TiO(2) monolayer (Au/TiO(2)) is the most active in both as-synthesized and oxidized forms, while the gold catalyst supported on the silica material functionalized with an Al(2)O(3)/TiO(2) double layer (Au/Al(2)O(3)/TiO(2)/SiO(2)) is the most active in the reduced form among the six catalysts. Surprisingly, the gold catalyst supported on the silica material functionalized with a TiO(2)/Al(2)O(3) double layer (Au/TiO(2)/Al(2)O(3)/SiO(2)) has much less activity than Au/Al(2)O(3)/TiO(2)/SiO(2) under all various treatments, underscoring the sensitivity of the catalytic activity to the structure of the supporting surfaces.  相似文献   

13.
Pd/MoO3-TiO2/SiO2光催化CO2与C2H6合成烃类氧化物的反应性能   总被引:2,自引:0,他引:2  
王希涛  钟顺和  肖秀芬 《催化学报》2005,26(10):900-904
 采用化学反应改性和等体积浸渍法制备了负载型Pd/MoO3-TiO2/SiO2催化剂,并用IR,FT-Raman,TPD-MS,UV-Vis DRS和活性评价等方法研究了催化剂的表面结构、光吸收性能、化学吸附性能及光催化CO2与C2H6合成烃类氧化物的反应性能. 结果表明,SiO2负载的MoO3和TiO2之间存在着强相互作用,并能部分形成Mo-O-Ti键联,使得两种氧化物微粒均匀分布于载体表面; 表面MoO3和TiO2的复合作用使TiO2/SiO2的吸光带边红移,扩展了其吸光域,Pd的引入明显提高了固体材料的可见光吸收率; CO2和C2H6能较好地吸附在催化剂表面,在紫外光的激发下,CO2吸附态能解离生成CO,而C2H6单位吸附态能部分转化为C和H同时吸附在两个晶格氧上的双位吸附态; 光促CO2和C2H6反应主要生成丙醛、乙醇和乙醛; 在合适的条件下,烃类氧化物的选择性可超过90%.  相似文献   

14.
The water-gas shift (WGS) reaction rate per total mole of Au under 7% CO, 8.5% CO(2), 22% H(2)O, and 37% H(2) at 1 atm for Au/Al(2)O(3) catalysts at 180 °C and Au/TiO(2) catalysts at 120 °C varies with the number average Au particle size (d) as d(-2.2±0.2) and d(-2.7±0.1), respectively. The use of nonporous and crystalline, model Al(2)O(3) and TiO(2) supports allowed the imaging of the active catalyst and enabled a precise determination of the Au particle size distribution and particle shape using transmission electron microscopy (TEM). Further, the apparent reaction orders and the stretching frequency of CO adsorbed on Au(0) (near 2100 cm(-1)) determined by diffuse reflectance infrared spectroscopy (DRIFTS) depend on d. Because of the changes in reaction rates, kinetics, and the CO stretching frequency with number average Au particle size, it is determined that the dominant active sites are the low coordinated corner Au sites, which are 3 and 7 times more active than the perimeter Au sites for Au/Al(2)O(3) and Au/TiO(2) catalysts, respectively, and 10 times more active for Au on TiO(2) versus Al(2)O(3). From operando Fourier transform infrared spectroscopy (FTIR) experiments, it is determined that the active Au sites are metallic in nature. In addition, Au/Al(2)O(3) catalysts have a higher apparent H(2)O order (0.63) and lower apparent activation energy (9 kJ mol(-1)) than Au/TiO(2) catalysts with apparent H(2)O order of -0.42 to -0.21 and activation energy of 45-60 kJ mol(-1) at near 120 °C. From these data, we conclude that the support directly participates by activating H(2)O molecules.  相似文献   

15.
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.  相似文献   

16.
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.  相似文献   

17.
The present study concerns an experimental microkinetic approach of the photocatalytic oxidation (PCO) of isopropyl alcohol (IPA) into acetone on a pure anatase TiO2 solid according to a procedure previously developed. Mainly, the kinetic parameters of each surface elementary step of a plausible kinetic model of PCO of IPA are experimentally determined: natures and amounts of the adsorbed species and rate constants (preexponential factor and activation energy). The kinetics parameters are obtained by using experiments in the transient regime with either a FTIR or a mass spectrometer as a detector. The deep oxidation (CO2 and H2O formation) of low concentrations of organic pollutants in air is one of the interests of the PCO. For IPA, literature data strongly suggest that acetone is the single route to CO2 and H2O and this explains that the present study is dedicated to the elementary steps involving gaseous and adsorbed C3H(x)O species. The microkinetic study shows that strongly adsorbed IPA species (two species denoted nd-IPA(sads) and d-IPA(sads) due to non- and dissociative chemisorption of IPA, respectively) are involved in the PCO of IPA. A strong competitive chemisorption between IPA(sads) and a strongly adsorbed acetone species controls the high selectivity in acetone of the PCO at a high coverage of the surface by IPA(sads). The kinetic parameters of the elementary steps determined in the present study are used in part 2 to provide a modeling of macroscopic kinetic data such as the turnover frequency (TOF in s(-1)) of the PCO using IPA/O2 gas mixtures.  相似文献   

18.
The one-electron redox processes of several compounds during polyoxometalate (POM)-mediated photocatalytic reactions of TiO(2) were investigated using the two-color two-laser flash-photolysis technique. The efficiency of the one-electron oxidation of aromatic sulfides by the trapped hole (h(tr) (+)) or the surface-bound OH radical (OH(s) (.)) is found to be significantly enhanced due to electron transfer from the conduction band (CB) of TiO(2) to the POM. The efficiency of the electron transfer from the CB of TiO(2) to the POM decreases in the order H(2)W(12)O(40) (6-) < SiW(12)O(40) (4-) < PW(12)O(40) (3-), that is, it depends on the reduction potential (E(red)) of the POMs. Electron injection from PW(12)O(40) (4-) in the excited state (PW(12)O(40) (4-*)) to the CB of TiO(2) was clearly observed using the two-color two-laser flash-photolysis technique. Storage of electrons in the TiO(2)/PW(12)O(40) (3-)/methyl viologen (MV(2+)) ternary system was also achieved upon two-color two-laser irradiation.  相似文献   

19.
Size-selected gold clusters, Au(n)(+) (n = 1, 3, 4), were deposited on an ordered Al(2)O(3) film grown on NiAl(110), and changes in morphology and electronic properties with deposition/annealing temperature and cluster size were investigated by X-ray photoelectron spectroscopy (XPS) and ion-scattering spectroscopy (ISS). Extensive agglomeration was observed by ISS for annealing temperatures above 300 K, accompanied by large shifts in the Au XPS binding energy. Agglomeration is more extensive in room-temperature deposition, compared to samples prepared by low-temperature deposition, then annealed to room temperature. Agglomeration is also observed to be dependent on deposited cluster size. CO adsorption was studied by ISS and temperature-programmed desorption, and we looked for CO oxidation under conditions where substantial activity is seen for Au(n)/TiO(2). No activity was observed for Au(n)/Al(2)O(3). The differences between the two systems are interpreted in terms of the nature of the metal-support interactions.  相似文献   

20.
路莹  陈硕  全燮  于洪涛 《催化学报》2011,(12):1838-1843
采用电沉积和旋转涂膜相结合的方法成功制备了高度有序的TiO2/Au纳米棒阵列催化剂.扫描电镜和透射电镜结果表明,TiO2薄膜均匀地包覆在Au纳米棒的表面,形成核壳型的一维阵列结构.X射线衍射分析表明所获得TiO2为(101)晶面优先生长的锐钛矿晶相.紫外-可见漫反射光谱显示,由于Au和TiO2间肖特基结的存在造成吸收红...  相似文献   

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