Pd/TiO2/C复合催化剂的制备及其在碱性溶液中对乙醇氧化的电催化性能

钛酸四丁酯前驱体水热合成制备纳米TiO₂颗粒,在TiO₂和Vulcan XC-72活性炭复合载体上液相还原负载Pd纳米颗粒,制得Pd/TiO₂/C复合催化剂. 通过透射电镜（TEM）和X射线衍射（XRD）测试表明其具有面心立方结构,Pd金属粒子（粒径约3 ~ 4 nm）均匀分散在锐钛矿型的纳米TiO₂和活性炭的复合载体上. 循环伏安和计时电流曲线测试表明,与相同Pd载量的Pd/C相比,20% Pd载量的Pd/TiO₂/C颗粒在常温常压下对乙醇的电催化氧化有很高活性和稳定性. 这主要归功于纳米TiO₂改变了Pd表面的电子特性,且增大了其比表面积.     

锐钛矿型TiO2担载的Pd催化剂用于乙炔选择加氢的催化性能及其表征

Anatase TiO₂ nanospindles containing 89% exposed {101} facets (TiO₂-101) and nanosheets with 77% exposed {001} facets (TiO₂-001) were hydrothermally synthesized and used as supports for Pd catalysts. The effects of the TiO₂ materials on the catalytic performance of Pd/TiO₂-101 and Pd/TiO₂-001 catalysts were investigated in the selective hydrogenation of acetylene to polymer-grade ethylene. The Pd/TiO₂-101 catalyst exhibited enhanced performance in terms of acetylene conversion and ethylene yield. To understand these effects, the catalysts were characterized by H₂ temperature-programmed desorption (H₂-TPD), H₂ temperatureprogrammed reduction (H₂-TPR), transmission electron microscopy (TEM), pulse CO chemisorption, X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA). The TEM and CO chemisorption results confirmed that Pd nanoparticles (NPs) on the TiO₂-101 support had a smaller average particle size (1.53 nm) and a higher dispersion (15.95%) than those on the TiO₂-001 support (average particle size of 4.36 nm and dispersion of 9.06%). The smaller particle size and higher dispersion of Pd on the Pd/TiO₂-101 catalyst provided more reaction active sites, which contributed to the improved catalytic activity of this supported catalyst.     

LaCoO_3-TiO_2纳米管阵列的构筑及可见光光催化性能

TiO_2纳米管阵列具有较高的光催化活性,但可见光吸收弱,限制了其太阳能利用和环境应用。窄带隙的钙钛矿(ABO3)型氧化物能够吸收大范围波段的可见光,且稳定性高,但光催化活性低。本文首先采用溶胶-凝胶法合成了LaCoO_3纳米颗粒,然后利用电泳沉积技术将LaCoO_3纳米颗粒修饰于TiO_2纳米管阵列表面,构筑了LaCoO_3-TiO_2纳米管阵列。扫描电子显微镜(SEM)、透射电子显微镜(SEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)的表征结果显示溶胶-凝胶法合成的纳米颗粒为LaCoO_3,其尺寸均匀,结晶度高,平均粒径约为100nm。LaCoO_3纳米颗粒与TiO_2纳米管阵列之间的结合力好。紫外可见吸收光谱(DRS)显示,随着电泳沉积时间的延长,LaCoO_3-TiO_2纳米管阵列的吸收带边逐渐红移700nm。可见光下光催化降解甲基橙(MO)的结果表明,电泳沉积15 min制得的LaCoO_3-TiO_2纳米管阵列对MO的光催化效率最高,其降解速率是相同条件下TiO_2纳米管阵列的4倍。光致发光光谱和电化学阻抗谱证实LaCoO_3纳米颗粒的负载有效地促进了光生电荷的分离和传输,可见光光催化活性明显增强。     

氮铋共掺杂TiO2的合成及其可见光催化性能研究

以纳米管钛酸为钛的前驱体,Bi(NO₃)₃·5H₂O为N源和Bi源,采用水热法制备了N、Bi共掺杂的TiO₂;并以甲基橙为目标降解物考察了所制备样品的可见光催化性能(λ≥420 nm).利用XRD、XPS、UV-Vis DRS、TEM等技术对不同条件下制备的产物进行了表征.结果表明,所得样品主要为锐钛矿型,粒径20 nm左右,掺杂的Bi主要以Bi₂O₃和BiONO₃两种形式存在.N元素除了以NO₃^-的形式存在于BiONO₃中,还有少量N以间隙氮掺杂于TiO₂中形成Ti-O-N键.N、Bi共掺杂的TiO₂在可见光下表现出了优越的光催化性能,其中水热温度为130 ℃,Bi/Ti摩尔比为1%时,催化活性最高.催化活性的提高源于N和Bi的掺杂增加了样品对可见光的利用效率,降低了光生电子空穴的复合速率.     

Pd/γ-Al2O3-TiO2催化剂上乙醇乙醛的催化氧化性能研究

采用混胶法和机械混合等方法制备了Pd质量分数为1%的Pd/γ-Al₂O₃-TiO₂催化剂,并对其催化活性、影响条件进行了考察。结果说明,由混胶法制备的Pd/γ-Al₂O₃-TiO₂催化剂对乙醇和乙醛的完全氧化表现出优异的催化性能,其活性明显高于单一载体催化剂Pd/TiO₂和Pd/Al₂O₃,150℃时乙醇和乙醛的转化率分别达到98.9%和98.5%。在较宽温度范围内和高空速条件下表现出良好的稳定性。同时运用XRD、TEM和FT-IR等技术对催化剂进行了表征。结果表明,在Pd/γ-Al₂O₃-TiO₂催化剂中Al₂O₃与TiO₂之间存在着较强的相互作用,使γ-Al₂O₃-TiO₂的比表面积和孔容积均调变到一个适中的数值,同时在催化剂表面Al₂O₃参与形成了有利于其催化活性的表面结构。     

Pd增强缺陷态TiO2纳米管阵列的光催化产氢性能

通过光还原沉积法, 利用氧空位诱导作用, 在Ni掺杂的缺陷态TiO₂纳米管阵列(TNT-Ni)上得到金属 Pd含量不同的Pd-TNT-Ni催化剂. 采用场发射扫描电子显微镜(SEM)、 X射线光电子能谱(XPS)、 紫外-可见 漫反射(UV-Vis DRS)、 表面光电压(SPV)、 光致发光光谱(PL)和电化学测试等表征手段, 探究了Pd与Ni掺杂的缺陷态TiO₂纳米管阵列之间的强相互作用对其光吸收特性和载流子分离及传输效率的影响, 阐明了强相互 作用对材料光催化活性的调控机理, 提出了Pd增强Pd-TNT-Ni光催化性能的作用机理. 结果表明, 通过光还 原法制备的Pd纳米颗粒尺寸为10~20 nm的Pd₁₂₀-TNT-Ni样品的光响应值为4.22 mA/cm², 是未负载Pd样品光 响应值(1.14 mA/cm²)的3.7倍, 其具有最佳的平均产氢速率(5.16 mmol·g^?1·h^?1), 是TNT样品平均产氢速率 (0.45 mmol·g^?1·h^?1)的12倍, 表明Pd与缺陷态TiO₂纳米管阵列之间的强相互作用驱动了载流子的分离及传输, 且Pd作为电子捕获势阱及反应活性位点, 显著提高了材料的光催化性能.     

Photocatalytic reaction of neat alcohols by metal-loaded titanium(IV) oxide particles

The photocatalytic reaction (excitation wavelength, greater than 300 nm) of neat alcohols (ethanol or 2-propanol) by metal-loaded titanium(IV) oxide (TiO₂) was conducted under argon at room temperature. The dehydrogenation products hydrogen (H₂) and acetaldehyde (or acetone in the case of 2-propanol) were found in the absence of additives. The corresponding acetals, ethers, and alkanes were obtained by the addition of concentrated hydrochloric acid (HCl). The measurement of the product yields during the post-irradiation dark reaction in the presence of photocatalyst (TiO₂) loaded with platinum(IV) oxide (PtO₂) revealed that the production of ether and ethane and the regeneration of ethanol proceed by the hydrogenation of acetal over loaded metal, presumably via a hemiacetal intermediate. X-ray diffraction (XRD) analyses showed that the loaded PtO₂ is reduced to platinum metal during the course of the photocatalytic reaction. For the production of ether from HCl-acidified ethanol, Pd-loaded catalysts, especially prepared by precipitation—reduction, exhibit the highest activity of several metal-loaded TiO₂ catalysts. From XRD and X-ray photoelectron spectroscopy studies of Pd-loaded TiO₂ particles, it was shown that the smaller the size of the Pd particles, the higher the selectivity for ether production from the acidified ethanol suspension. The application of this photocatalytic O-alkylation to the synthesis of cyclic ethers was demonstrated.     

Characterization and photocatalytic properties of silver and silver chloride doped TiO2 hollow nanoparticles

Using polystyrene（PSt） particles as template,PSt/TiO₂ composite particles with AgCl incorporation were prepared through hydrolysis of tetrabutyl titanate in the presence of AgNO₃ and NaCl.AgCl doped TiO₂ hollow particles were successfully prepared with the PSt/TiO₂ composite microspheres pretreated at 180℃followed by calcination.The morphology of PSt/TiO₂ particles and the crystal structures of the AgCl doped TiO₂ hollow particles were characterized.The photocatalytic activity of the doped TiO₂ hollow particles in degradation of Rhodamine B was tested under UV and visible lights and compared to that with Ag doped TiO₂ particles.The results showed that TiO₂ hollow particles,either doped with Ag or AgCl,demonstrated higher photocatalytic activity than the pure TiO₂ particles.This enhancement in photocatalytic activity was more significant with AgCl doped TiO₂ than that with Ag doped,and more distinct when the degradation was done under visible light than that under LTV light.     

The nature of the surface site for isocyanate produced in the reaction of ammonia and carbon monoxide over supported catalysts

The reaction of CO and NH₃ was performed over M/X (M=Rh, Ru, Pd; X=Al₂O₃, SiO₂, TiO₂) films. Infrared spectroscopy was used to monitor the formation of surface intermediates. Isocyanate (NCO) was detected for all of the metals when the support was Al₂O₃ or SiO₂, but not for TiO₂. The NCO resided on the Al₂O₃ support for all M/Al₂O₃ catalysts, but on the metal when the support was SiO₂. It was concluded that the formation and location of the NCO was dependent upon the extent of NH₄⁺ formation on the various supports.     

Scanning tunneling microscopy studies of metal clusters supported on TiO2 (110): Morphology and electronic structure

A brief review of our laboratory's recent scanning tunneling microscopy (STM) studies on nanoclusters supported on TiO₂(110) is presented. Particular emphasis is placed on the system Au/TiO₂(110). The nucleation and growth of the clusters, which were vapor-deposited on TiO₂(110) under ultra high vacuum (UHV) conditions, were investigated using STM. It was found that Au, Pd, and Ag clusters all grow in a three-dimensional (3D) (Volmer-Weber) fashion on TiO₂(110), but that at low coverages, quasi-two dimensional (quasi-2D) Au and Pd clusters were observed. These quasi-2D clusters are characterized by heights of 1–2 atomic layers. Annealing studies show that Au and Pd clusters form large microcrystals with well-defined hexagonal shapes. Al clusters, which have a strong interaction with the substrate, are oxidized upon deposition, “wetting” the surface and forming small clusters. In addition to the topographic studies, the local electronic properties of these clusters have been studied using scanning tunneling spectroscopy (STS) to measure the cluster band gaps. The electronic structure was found to be cluster size-dependent, as seen by the appearance of a band gap as the cluster size decreased. More specifically, the onset of cluster metallic properties correlates with the transition from quasi-2D to 3D cluster growth.     

微波辅助溶剂热合成In-Si共改性TiO_2的增强光催化性能

利用微波辅助溶剂热法合成了In-Si共改性的TiO2光催化剂.粉末X射线衍射(XRD)、激光拉曼(Raman)光谱、N2吸脱附(BET)、X射线光电子能谱(XPS)、光致发光(PL)光谱和紫外-可见漫反射光谱(UV-Vis DRS)等实验表明,尽管掺杂和改性后TiO2结晶度略有降低,但不影响光催化剂锐钛相的形成.Si掺杂入TiO2晶格使颗粒变小,比表面积变大.In不能进入TiO2晶格,在TiO2表面形成了In2O3.罗丹明B(RhB)降解实验显示,In-Si共改性TiO2表现出很高的紫外和可见光催化活性,Si:In:Ti的摩尔比为0.03:0.02:1的样品(IST-2)光催化活性最高,紫外光下3 min即可将RhB降解完全,可见光下120 min RhB降解率为97%,这是由材料的高表面积,In2O3-TiO2复合半导体之间高效电荷转移及染料敏化等共同作用所致.对于苯酚,光催化降解则相对缓慢,700 min内尚不能降解完全.     

The photocatalytic activity of TiO2 foam and surface modified binary oxide titania nanoparticles

Surface modified titania dioxide composite nanoparticles prepared by hydrogen reduction reaction and a mesoporous TiO₂ foam made from a surface modifier and a long chain organic surfactant were characterized by diffractive, spectroscopic and microscopic techniques and studied for their catalytic activity towards the decomposition of an industrial water pollutant, methyl orange. The surface deposition of ruthenium and silicon particles improved the photocatalytic activity of the composite particles resulting in a faster decomposition of the methyl orange compared to commercial TiO₂ alone. Modification of TiO₂ with RuO₂ only offered a marginal benefit over TiO₂ while the incorporation of RuO₂ and SiO₂ into TiO₂ resulted in a marked increase in the rate constant and catalytic activity. These results are consistent with the enhanced surface properties of the composite materials resulting from the modification of TiO₂ with RuO₂ and SiO_2. This surface enhancement effects appear synergetic to the charge separation process and hence the photocatalytic results are explained on the basis of a mechanism involving efficient charge transfer across the interfaces of the composites involving photogenerated electron–hole pairs. Results obtained in this study show that the percentage degradation after 1 h of illumination was 47.15% for TiO₂ foam, 75.5 and 106.4%, respectively, for TiO₂/RuO₂ (SiO₂ 5%, w/w) and TiO₂/RuO₂(SiO₂ 10%, w/w) and 34.15% for commercial TiO₂.     

一维TiO2锐钛矿/金红石异相结的制备及光催化降解甲醛性能

TiO₂异相结主要通过高温方法制备,所制备材料的形貌和组成较难控制,尤其是在较低温度下一步制备一维TiO₂异相结仍具有一定的挑战性。采用简单、方便的一步水热法,在较低温度下(180℃)制备了一维纳米TiO₂异相结材料。X射线衍射(XRD)和高分辨透射电镜(HRTEM)分析表明,制备的材料以一维金红石相TiO₂纳米棒(长度：(400±50) nm,直径：(60±5) nm)为基本结构,粒径分布均匀的锐钛矿相TiO₂纳米粒子(直径：(9.5±0.5) nm)高密度、单分散地负载在纳米棒上。通过控制水热反应时间成功调控了异相结中锐钛矿相TiO₂的含量(20%～50%),进而实现了其光催化降解HCHO性能的调控。实验结果表明,当锐钛矿相TiO₂的含量为33%时(TiO₂-24,水热时间24 h制备的样品),异相结光催化剂表现出最佳的HCHO降解性能：在低光强LED灯(波长为365 nm,光强为12.26 mW·cm     

Catalytic Performance of MnO_x-WO_3/TiO_2 Catalyst for Selective Catalytic Reduction of NO_x with NH_3 and Its Tolerance Towards SO_2

The performance of Mn-W/TiO₂ for selective catalytic reduction(SCR) of NO_x with NH₃ and its resistance to different concentrations of SO₂ at various temperatures were investigated. The results show that WO₃ increased the active sites and enhanced the strength of acid, so it was an effective promoter of MnO_x/TiO₂. The NO_x conversion on Mn-W/TiO₂ ranges from 80.3% to 99.6% between 100 °C to 350 °C at GHSV=18900 h^–1, while N₂ product selectivity changes from 100% to 98.7%. In the presence of 0.01% SO₂ and 6% H₂O, NO_x conversion maintained 98.5% at 120 °C. The influence of more than 0.01% SO₂ on the activity of MnO_x-WO₃/TiO₂ will disappear if the temperature rises above 250 °C. By means of heating and sweeping with He, the activity of the catalysts can be recovered. At 300 °C, NO_x conversion yielded 99% with 0.07% SO₂ and reached the level of commercial V-W/TiO₂ catalysts. The Mn-W/TiO₂ catalyst showed excellent performance for SCR of NO_x with NH₃ in a wider range of temperature with strong tolerance to SO₂.     

TiO_2载体掺杂对Mn-Ce/TiO_2催化剂低温脱硝性能影响研究

以TiO_2、TiO_2-Al_2O_3及TiO_2-SiO_2为载体,选取Mn为活性组分,Ce为活性助剂,采用分布共混法制备低温SCR催化剂,分析了TiO_2载体掺杂Al_2O_3、SiO_2改性后对Mn-Ce/TiO_2催化剂低温脱硝活性的影响,运用BET、SEM、XRD、H2-TPR以及NH_3-TPD等测试手段对催化剂进行了表征。结果表明,TiO_2载体经掺杂改性后,Mn-Ce/TiO_2催化剂的比表面积、孔结构参数以及表面孔结构形貌均得到改善和提高;Mn-Ce/TiO_2-Al_2O_3和Mn-Ce/TiO_2-SiO_2催化剂中TiO_2的结晶度均有不同程度降低;经TiO_2载体掺杂改性后的催化剂表面低温还原峰面积及催化剂表面酸性位种类及酸性大小显著改善,这都有助于提高催化剂的脱硝活性。通过对TiO_2载体掺杂SiO_2和Al_2O_3改性后,催化剂的脱硝活性明显提高,反应温度在80-140℃时,催化剂SCR脱硝活性的顺序是:Mn-Ce/TiO_2-SiO_2M n-Ce/TiO_2-Al_2O_3M n-Ce/TiO_2。     

脉冲沉积制备Cu_2O/TiO_2纳米管异质结的可见光光催化性能

在用阳极氧化法制备有序排列TiO2纳米管阵列薄膜的基础上,引入脉冲沉积工艺,成功实现了均匀、弥散分布的Cu2O纳米颗粒修饰改性TiO2纳米管阵列,形成Cu2O/TiO2纳米管异质结复合材料.利用场发射扫描电镜(FESEM)、场发射透射电镜(FETEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)和紫外-可见漫反射光谱(UV-Vis DRS)对样品进行表征,重点研究了Cu2O/TiO2纳米管异质结的光电化学特性和对甲基橙(MO)的可见光催化降解性能.结果表明,Cu2O纳米颗粒均匀附着在TiO2纳米管阵列的管口和中部位置,所制备的Cu2O/TiO2纳米管异质结具有高效的可见光光催化性能;在浓度为0.01 mol?L-1的CuSO4溶液中制得的Cu2O/TiO2纳米管异质结表现出最好的电化学特性和光催化性能;另外,对Cu2O纳米颗粒影响光催化活性的机理进行了讨论.     

Sn4+掺杂对TiO2纳米颗粒膜光催化降解苯酚活性的影响

金属离子掺杂能改善TiO2纳米微粒光催化活性,在光降解大气和水污染物的研究中,已引起人们的重视[1,2].实验证明,掺杂物的浓度、掺杂离子的分布、掺杂能级与TiO2能带匹配程度、掺杂离子d电子的组态、电荷的转移和复合等因素对催化剂的光催化活性有直接影响[3].Kamat等[4]曾利用TiO2颗粒与SnO2颗粒混合制膜,使光催化剂活性得到提高.但Sn4+掺杂TiO2用于光催化剂尚少见报道.本文采用等离子体化学气相沉积法(PECVD)[5]制备了Sn4+离子掺杂的TiO2纳米颗粒膜催化剂(TiO2-Sn),考察了其对苯酚的光催化降解活性,讨论了Sn4+离子的掺杂方式及光催化活性提高的机理.     

Synthesis and study of Bi2Ti2O7/TiO2 composites as efficient visible-light-active photocatalysts in the reduction of aqueous Cr(VI)

In this work, Bi_2Ti_2O_7/TiO_2 composites were synthesized and studied as potential visible-light-activated photocatalysts in the reduction of aqueous Cr(VI). Bi_2Ti_2O_7/TiO_2 composites with tunable compositions were synthesized via a solvothermal-calcination two-step method, simply by changing the molar ratios of Bi(NO_3)_3·5H_2O to tetrabutyl titanate in the reactants. The compositions, structures and optical properties of the as-synthesized Bi_2Ti_2O_7/TiO_2 composites were characterized by X-ray diffraction, field emission scanning electron microscopy and UV–vis diffuse reflectance spectra. The photocatalytic activity of the as-synthesized Bi_2Ti_2O_7/TiO_2 composites was tested in the reduction of aqueous Cr(VI)under visible-light(λ420 nm) irradiation, and compared with that of TiO_2 nanoparticles. It was observed that the as-synthesized Bi_2Ti_2O_7/TiO_2 composites exhibited much higher photocatalytic activity than TiO_2 nanoparticles, and the most efficient composite(300 mg) can achieve the complete reduction of Cr(VI) in 300 mL of 50 mg/L K_2Cr_2O_7 aqueous solution under visible-light(λ420 nm)irradiation in 90 min.     

碳包覆Pd/TiO2光催化产氢协同胺类选择性氧化合成亚胺(英文)

负载型金属纳米催化剂由于其优异的光催化性能,被广泛应用于光催化产氢协同胺类氧化偶联合成高附加值亚胺体系。但在反应过程中,金属表面对H原子和亚胺表现出较强的吸附能力,导致了亚胺易于发生自氢化反应而生成仲胺,显著降低了亚胺的选择性。在本文中,我们证实了在Pd/Ti O₂表面构建超薄碳层(Pd/Ti O₂@C)是一种解决上述问题的有效策略。在Pd/Ti O₂表面构筑的超薄碳层可以有效调控H原子和亚胺在其表面的吸附行为,避免了光催化氧化偶联过程中亚胺的自氢化。因此,Pd/Ti O₂@C光催化剂在光催化产氢协同胺类选择性氧化合成亚胺体系中展现出优异的亚胺选择性。本研究提供了一种便捷有效的策略推动负载型金属纳米催化剂在光催化产氢协同合成高附加值产物体系中的应用。