偏压控制Cu2O和Cu在TiO2表面的生长及其光电化学性质

基于TiO2/Ti电极在含Cu2+溶液中的循环伏安图,调节电沉积的沉积电压,我们在TiO2平整表面制备出Cu2O和/或Cu颗粒.通过扫描电镜(SEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)表征,发现Cu2O和Cu有不同的生长机制:Cu2O颗粒在TiO2表面分散结晶,而Cu颗粒是在已生长的颗粒上成核,从而形成堆积颗粒结构.这是由于在Cu2O/TiO2界面和Cu/TiO2界面形成不同的能带结构,使得电子的转移方式不同.与纯TiO2光阳极比较,可以观察到Cu2O/TiO2和Cu/TiO2异质结构的光电流均有显著增强.特别地,存在一个电压区间使得Cu2O和Cu同时生长在TiO2表面,此时对应的光电流比较稳定并且能达到最大.紫外-可见(UV-Vis)漫反射光谱、电化学阻抗谱(EIS)和光电流-电压特性曲线均显示,Cu2O和Cu明显有助于光的可见光吸收,同时Cu/TiO2在光电转换过程中显示更宽波段的可见光利用率.此外,开路电压的增加、有效的电荷分离和电极/电解质界面上载流子的快速迁移也增强了材料的光电化学性质.     

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.     

不同晶相TiO2负载Cu2O催化甲醛乙炔化反应

分别以金红石相和锐钛矿相TiO₂为载体, 采用液相还原-沉积法制备了Cu₂O/TiO₂催化剂. 采用氮气物理吸附-脱附(N₂-physisorption)实验、 氢气程序升温还原(H₂-TPR)、 X射线衍射(XRD)、 X射线光电子能谱(XPS)、 CO红外光谱(CO-IR)及高分辨透射电子显微镜(HRTEM)等技术, 研究了不同晶相TiO₂载体对Cu₂O/TiO₂结构及其催化甲醛乙炔化反应性能的影响. 结果表明, 以金红石相TiO₂为载体的催化剂炔化活性明显高于以锐钛矿相TiO₂为载体的催化剂, 原因在于金红石相TiO₂主要暴露(110)晶面, 其与铜物种的配位环境及较高的空位密度形成了更多的Cu—O—Ti结构物种, 表现为Cu₂O与TiO₂之间强的相互作用. 这导致Cu₂O高效转变为乙炔亚铜活性物种, 并保持了较高的分散度与稳定性, 抑制了过度还原物种金属Cu的生成, 进而使催化剂表现出较高的催化性能.     

Template Synthesis and Characterization of Cu2O/TiO2 Coaxial Nanocable for Photocatalysis

Coaxial nanocable consisted of p-type Cu₂O nanowires and n-type TiO₂ nanotubes arrays was prepared in the porous anodic aluminum oxide(AAO) template via the sol-gel method and subsequent electrodeposition method. X-ray diffraction analysis identified an anatase structure of the TiO₂ nanotubes and cubic structure of the Cu₂O nanowires. The obtained samples were also characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM) and energy dispersive X-ray spectroscopy(EDS). The diffrence of open circuit potential of the coaxial nanocable electrode was larger than that of the TiO₂ nanotubes electrode under ultraviolet illumination, which means doping with Cu₂O could improve the photovoltage effectively. Meanwhile, nanocable arrays exhibited a high activity for photodegrading Rhodamine B under Xe lamp irradiation and the photocatalysis degradation efficiency was up to 98.69% after degradation for 7 h. The enhanced photocatalytic activity could be attributed to the high migration efficiency of photoinduced electrons, which may suppress the charge recombination effectively.     

放射性碘分子在Cu2O表面的吸附:第一性原理密度泛函研究

采用第一性原理密度泛函计算方法和周期性平板模型系统研究了放射性碘分子在Cu₂O三个低指数表面的吸附行为。通过计算若干平衡吸附构型的结构参数和吸附能评估了不同特征吸附位的作用。构型优化计算表明所选晶面存在适度的结构弛豫。计算结果表明,与Cu₂O（110）表面相比,Cu₂O（100）和（111）晶面表现出更高的碘分子吸附反应活性。其中,表面氧原子位（O_S）和配位未饱和铜原子位（Cu_CUS）分别为Cu₂O（100）和（111）晶面的能量最优吸附位点。此外,针对几种典型吸附结构计算分析了其电子结构信息,以进一步阐明吸附体系之间的相互作用机理。     

N_2O在钾改性Cu-Co尖晶石型复合氧化物上的催化分解(英文)

制备了几个不同组成的Cu-Co尖晶石型复合氧化物,用于N2O分解反应,在活性较高的Cu0.8Co0.2Co2O4表面浸渍碱金属盐溶液,制备改性催化剂,考察了碱金属助剂类型、钾前驱物和钾负载量等对改性催化剂活性的影响。用BET、XRD、SEM、XPS等方法表征了催化剂结构。结果表明,几种碱金属碳酸盐改性Cu0.8Co0.2Co2O4的催化活性发生了显著变化,其中,K改性催化剂的活性有明显提高,而Cs的表面改性反而降低了催化剂活性;钾前驱物对K/Cu-Co的催化活性也有较大影响,其中,加入碳酸钾明显提高了催化剂的活性,而加入硝酸钾和醋酸钾反而降低了催化剂活性;有氧无水、有氧有水气氛中,400!C下N2O在碳酸钾改性催化剂0.05K/Cu0.8Co0.2Co2O4上的转化率分别达到了100%和87.6%;该催化剂在400!C下的恒温反应活性和稳定性均高于未改性催化剂。     

改性活性炭纤维可见光催化联合脱硫脱硝的研究

利用水合肼还原法制备的TiO₂/Cu₂O复合光催化剂对活性炭纤维(ACF)进行改性,利用SEM、XPS、BET以及XRD对其进行表征,研究改性后ACF的性质及其脱硫脱硝效果。研究表明,TiO₂/Cu₂O同时改性后的ACF表面孔径减小,但表面石墨碳和羰基(C=O)官能团增加,增强了ACF对NO和SO₂的吸附能力,从而提高了脱硫脱硝的效率,该催化剂在40℃、可见光的催化下脱硫效率达90%,脱硝效率达60%。     

金纳米颗粒在不同包裹介质中的超快等离子体动力学

Herein, we prepared four samples, namely gold/poly(sodium-p-styrenesulfonate) (Au/PSS), gold/silicon dioxide (Au/SiO₂), gold/titanium dioxide (Au/TiO₂), and gold/cuprous oxide (Au/Cu₂O) core/shell nanocomposites, to investigate how the surrounding medium affects the ultrafast plasmon dynamics of Au nanoparticles (NPs). We recorded femtosecond transient absorption spectra of Au NPs in Au/PSS, Au/SiO₂, Au/TiO₂, and Au/Cu₂O core/shell nanocomposites at various time delays. We found that the spectral features in the femtosecond transient absorption spectra of Au NPs in Au/TiO₂ and Au/Cu₂O core/shell nanocomposites were dramatically different from those of Au NPs in Au/PSS and Au/SiO₂ core/shell nanocomposites. A comprehensive analysis of the ultrafast plasmon dynamics of Au NPs in the core/shell nanocomposites revealed that following excitation of the resonance plasmon band of Au NPs, the exited electrons could be efficiently transferred into the conduction bands of TiO₂ and Cu₂O in Au/TiO₂ and Au/Cu₂O core/shell nanocomposites.     

基于氨基化煤基碳点的复合光催化剂的制备及对CO2还原的催化性能

采用过氧化氢氧化法剥离出煤炭结构中的晶体碳[煤基碳点(CDs)], 并通过亚硫酰氯氯化及乙二胺钝化等步骤对其进行氨基化修饰, 制得N, S共掺杂的氨基化煤基碳点(NH₂-CDs), 再利用其表面的氨基和含氧基等官能团的配位及分散作用, 将由氯化铜原位还原得到的氧化亚铜(Cu₂O)纳米粒子包覆于其中, 制备了复合催化剂Cu₂O/NH₂-CDs, 表征了其结构和形貌, 并考察了其可见光催化还原CO₂/H₂O的性能. 结果发现, NH₂-CDs的存在使复合催化剂不仅具备了较强的CO₂吸附性能, 而且还具有了高效的电子-空穴对分离和电子转移能力, 从而表现出优异的光催化还原CO₂制备HCOOH的性能. 反应6 h时, 产物HCOOH的量为2582.4 μmol/g cat, 约为同条件下纯Cu₂O作为光催化剂时产物HCOOH产率的7.3倍.     

1-辛基-3-甲基咪唑功能化石墨片负载氧化亚铜催化二氧化碳电还原制乙烯

电催化还原二氧化碳制备乙烯是备受关注的热点问题,高效催化剂的制备是决定乙烯产率的关键因素。本文在1-辛基-3-甲基咪唑氯的水溶液(OmimCl : H₂O = 1 : 5,体积比)中通过电剥离石墨棒制备了1-辛基-3-甲基咪唑功能化石墨片(ILGS),在水溶液中负载氧化亚铜后得到氧化亚铜/1-辛基-3-甲基咪唑功能化石墨片复合材料(Cu₂O/ILGS),通过透射电镜、X射线光电子能谱、拉曼光谱和X射线衍射对其组成和结构进行了系统研究,发现ILGS由多层石墨烯组成,表面富含缺陷。这些缺陷被1-辛基-3-甲基咪唑通过共价键修饰,形成类似鸟巢状的微结构,平均直径5 nm的Cu₂O纳米颗粒在石墨片表面均匀分散。在0.1 mol∙L⁻¹碳酸氢钾水溶液中,研究了Cu₂O/ILGS在不同电压下催化CO₂电还原的性能。结果表明,Cu₂O是主要活性中心并在CO₂还原过程中被逐渐还原成铜,导致产物的法拉第效率随着反应时间而变,在−1.3 V (vs RHE)电压下,乙烯的法拉第效率最高达到14.8%,其性能归因于Cu₂O/ILGS复合材料中的鸟巢状微结构对Cu₂O纳米颗粒的稳定作用。     

γ-Al2O3对SCR脱硝催化剂V2O5-WO3/TiO2的改性研究

采用溶胶凝胶法制备了不同γ-Al₂O₃含量的钛铝复合载体,以此为载体采用浸渍法负载V₂O₅和WO₃制备了一系列催化剂。采用X射线衍射(XRD)、比表面积测定(BET)、程序升温还原(H₂-TPR)、高分辨率透射电子显微镜(HRTEM)等表征技术对催化剂表面形态进行分析,同时在模拟氨气选择性催化还原NO(NH₃-SCR)的反应条件下,对催化剂的脱硝反应活性和SO₂抗中毒进行考察。结果发现,TiO₂和γ-Al₂O₃之间的协同作用使得V₂O₅-WO₃/TiO₂-γ-Al₂O₃催化剂的脱硝效率及活性窗口明显优于单一载体制备的催化剂,表现出了良好的热稳定性和抗SO₂毒化能力,特别是V₂O₅-WO₃/TiO₂-15% γ-Al₂O₃在310~460 ℃,NO的转化率均在80%以上,反应窗口最宽。各种表征结果表明,TiO₂-γ-Al₂O₃复合载体中γ-Al₂O₃高度分散在TiO₂上,复合载体具有较大的比表面积,同时具有较强的还原能力。     

ZrO2修饰Cu催化剂还原以及反应过程中表面组成的变化

通过热分解法制备Cu模型催化剂,然后经浸渍制备ZrO₂/Cu催化剂,采用SEM、XPS考察了催化剂表面形态和组成,并采用in-situ Raman考察了催化剂在还原和吸附CO和水的过程中随时间的变化。结果表明,还原前Cu催化剂表面主要存在CuO物种,而在ZrO₂/Cu表面,除了CuO物种,还存在着大量的表面羟基物种。ZrO₂/Cu相对Cu更加容易还原为Cu⁰,同时,ZrO₂在催化剂表面聚集形成絮状态,而Cu催化剂还原后主要形成Cu₂O物种。Cu催化剂表面吸附CO后,除了形成Cu-CO外,Cu₂O物种均会迅速消失形成CO₂。Cu催化剂对水的作用比较弱,但是ZrO₂/Cu催化剂和水作用较强,并且通过Cu-OH中间物形成Cu₂O物种。     

TiO2负载Cu-Mn复合氧化物催化燃烧正己醛

通过调控Cu负载量及Cu/Mn原子比,探究其对TiO₂负载Cu-Mn复合氧化物(Cu_xMn_y/TiO₂)催化材料中活性组分间相互作用的影响,结果表明,铜负载量为15% (w,质量分数)和Cu/Mn原子比为1 : 1时有利于类铜锰尖晶石相Cu_1.5Mn_1.5O₄的形成,随着Cu负载量的增加促使氧物种从晶格氧向表面吸附氧转移。复合催化材料中铜负载量的变化及Cu/Mn原子比对活性组分和催化活性间的相互作用影响显著。结果发现Cu₁₅Mn₁₅/TiO₂在225 ℃时使正己醛转化率达到90% (T₉₀),材料良好的性能归因于其具有较高的Cu²⁺与O_ads含量,并可与Mn²⁺实现双还原氧化过程。结果表明,Cu₁₅Mn₁₅/TiO₂复合材料中的类铜锰尖晶石活性组分可完成redox循环,以保持催化材料较高的稳定性。     

Pt/H-TiO2催化剂制备及其甲醇电催化氧化性能

以四氯化钛为前驱体,采用水热法合成二氧化钛纳米棒（TiO₂,白色）,在纯H₂气氛,将其550 ^oC热处理2 h,即得有氧缺陷和Ti³⁺填隙原子的二氧化钛纳米棒（H-TiO₂,灰黑色）. 将Pt纳米粒子（~ 1.9 nm）负载于此两种二氧化钛纳米棒上,制得Pt/TiO₂和Pt/H-TiO₂催化剂. XRD和XPS测试表明,氢处理TiO₂晶型没有变化,仍属金红石型,但增加了Ti-OH表面物种. 电化学测试表明,H-TiO₂载体能够增强氧在Pt表面的吸脱附能力,从而提高其甲醇电催化氧化活性,Pt/H-TiO₂电极甲醇氧化峰电流密度为Pt/TiO₂电极的1.6倍、Pt/C电极的2.1倍.     

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.     

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。     

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.     

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.     

Hydrothermal Syntheses of CuO,CuO/Cu2O,Cu2O,Cu2O/Cu and Cu Microcrystals Using Ionic Liquids

In this paper, CuO, CuO/Cu₂O, Cu₂O, Cu₂O/Cu and Cu microcrystals were synthesized via a hydrothermal method by mixing Cu(NO₃)₂·3H₂O and NaOH together in the presence of an ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate([BMIM]BF₄) or 1-butyl-3-methylimidazolium chloride([BMIM]Cl). The structures and the morphologies of the obtained products were characterized by means of X-ray diffractometer(XRD), field-emission scanning electron microscopy/energy-dispersive spectroscopy(FESEM/EDS), transmission electron microscopy/selected area electron diffraction(TEM/SAED) and Raman spectroscopy. The result of XRD indicates that Cu₂O and Cu microcrystals are cubic phase and the Raman spectra confirm the presence of carbon. The results of FESEM and TEM images show Cu₂O microcrystals as rule cubes of 2 μm in length and Cu particles of 5 μm in diameter. According to the difference between crystal structures, bi-component and single component products were synthesized by adjusting the reaction conditions. A possible formation mechanism of Cu₂O and Cu was proposed in[BMIM]BF₄.     

SO_2和H_2O对CeO_2/TiO_2/堇青石催化剂选择催化还原NO_x性能的影响

采用浸渍法制备了以堇青石为基底、氧化铈为活性组分的整体式脱硝催化剂CeO2/TiO2/堇青石催化剂。通过与商业钒基催化剂(V2O5-WO3/TiO2/堇青石)的对比研究发现,CeO2/TiO2/堇青石催化剂表现出了优良的抗硫抗水性能,经过30 h抗硫抗水实验,CeO2/TiO2/堇青石催化剂的氮氧化物转化率仍能保持在70%以上,仅下降了5%。BET、XRD、FT-IR和TG表征结果表明,在含硫含水气氛中反应时,CeO2/TiO2/堇青石和V2O5-WO3/TiO2/堇青石催化剂表面均有硫酸铵盐的生成,且前者的生成量明显低于后者。NH3-DRIFT分析结果表明,在含硫含水气氛中两种催化剂表面Brnsted酸性都被增强,而Lewis酸性有所减弱。进一步的XPS分析结果表明,烟气中的SO2+H2O会使催化剂表面Ce4+向Ce3+发生转化,从而导致化学吸附氧含量增加,这是CeO2/TiO2/堇青石催化剂具有优良抗硫抗水性能的重要原因。