金核/铂壳纳米粒子的光化学合成及电催化活性

在含不同摩尔比的Au(Ⅲ)和Pt(Ⅳ)离子的PEG(聚乙二醇)-丙酮溶液中,采用光化学共还原法合成了一组Au@Pt复合纳米粒子,并以炭黑分别对其负载制成Au@Pt/C催化剂。借助于UV-Vis、TEM和HR-TEM的表征,证实复合纳米粒子为球形的核/壳结构;分别以XPS、EDS和电化学方法分析了复合粒子的化学状态、结构特点和Au@Pt/C催化剂的催化性质。结果表明,不同Au:Pt摩尔比的Au@Pt/C催化剂对甲醇氧化反应具有良好的催化活性和稳定性,其中Au:Pt=1:1时形成的Au@Pt/C催化剂电催化活性最高,约为商品Pt/C催化剂的4倍。简要讨论了核/壳结构产生高催化活性的主要原因。     

Enhanced catalytic performance for selective oxidation of propene with O_2 over bimetallic Au-Cu/SiO_2 catalysts

Au-Cu bimetallic nanoparticles with uniform size,shape,and compositions were synthesized by wet chemistry method,and then the Au-Cu/SiO_2 catalyst supported on SiO_2 was prepared.Meanwhile,their catalytic activity for the selective oxidation of propene to acrolein using O_2 as an oxidant was evaluated.The bimetallic catalyst shows a significantly enhanced catalytic performance comparing with Au and Cu monometallic catalysts.Characterization of the materials and kinetic study was conducted to explore the cooperating mechanism of Au and Cu for improving the catalytic activity of the bimetallic catalyst.Cu component can segregate to the alloy surface and the Au-Cu alloy transferred to Au-CuO core/shell structure after annealing during the preparation process.Based on the Mars-van Krevelen mechanism for the selective oxidation of propene over the prepared catalysts,the coexistence of CuO can promote the adsorption and activation of O_2.Meanwhile,the electrons transfer from Au to Cu in the catalyst can facilitate the adsorptions of both oxygen on CuO sites and propene on Au sites.The combined effects of the above two aspects result in the high catalytic activity of the Au-Cu/SiO_2 catalyst for selective oxidation of propene to acrolein,compared to the Au/SiO_2 and CuO/SiO_2 catalysts.     

Au/CuMn催化剂对于C3H8还原NO催化性能的研究

以沉积-沉淀法制备了系列Au/CuMn催化剂,并对催化剂进行了XRD和XPS等表征,研究了Au负载量和催化剂焙烧温度对Au/CuMn催化剂性能的影响。实验结果显示,60℃烘干、Au理论负载量为3%的催化剂性能最佳,在50℃的反应条件下,NO的转化率达到72.4%,但催化剂失活较快。XPS分析显示,催化剂表面的Au3+与吸附氧物种Oads.是反应的活性中心,反应过程中催化剂表面氧化态Au3+与Oads.物种部分被还原,可能是催化剂失活的重要原因。另外,反应后在催化剂表面生成的亚硝酸盐、硝酸盐和碳酸盐等物种,覆盖了活性中心,也是导致催化剂失活的原因之一。     

制备条件对Au/AC催化分解臭氧性能的影响

研究了活性炭负载的金催化剂(Au/AC)对低浓度臭氧的催化分解性能,考察了前驱体溶液pH值、干燥方式、焙烧温度等制备条件对催化剂活性的影响,以及空速对臭氧分解率的影响。结果表明,在金前驱体溶液pH值为10、经微波辐射干燥、200℃氢气还原制备的催化剂,金颗粒在活性炭表面的分布更加均匀,尺寸更小,具有更高的催化活性。在室温、相对湿度45%和空速72000h-1时,对浓度为50mg/m3臭氧的分解率保持在90%以上(在2400min内)。N2吸附-脱附和XPS表征结果表明,活性炭载金催化剂在催化分解臭氧后,比表面积和孔体积略有下降;Au4f的XPS峰虽稍向高能方向移动,但仍保持催化活性;活性炭表面碳含量显著下降而氧含量大幅增加,说明活性炭上负载的Au在自身催化分解臭氧的同时,还起到了促进臭氧与单质碳反应的作用。     

Analysis of the Active Au Species on Au/α-Fe2O3 Catalyst

采用沉积沉淀法制备了CO低温氧化 Au/α-Fe2O3催化剂,利用 X 射线衍射(XRD)、X 射线光电子能谱(XPS)、BET 比表面测定、程序升温还原(H2-TPR)等表征技术,对比了制备过程 pH 值的微小变化、焙烧及光线照射对催化剂结构及催化性能的影响,探明了 Au/α-Fe2O3催化剂的活性物种。结果表明,110 ℃处理的 Au/α-Fe2O3催化剂表面同时存在 Au3+、Au0以及过渡态 Auδ+(0<δ<1),它们对 CO 氧化的活性顺序为 Au3+>Auδ+>Au0;pH 值为 8 条件下制备的催化剂 Au3+含量高、比表面积大,催化性能最好;高温焙烧使氧化态金还原的同时也使载体比表面积严重缩小,催化活性显著下降;紫外线照射可以引起 Au3+的逐渐还原以及 Au0 颗粒的生长,其催化失活作用弱于高温焙烧。     

Effects of Ce-Doping on the Structure and NH3-SCR Activity of Fe/Beta Catalyst

用标准的离子交换法制备了Fe/Beta分子筛SCR催化剂,并将其涂覆在蜂窝陶瓷载体上进行氮氧化物转化率的性能评价。分子筛和Ce掺杂分子筛的结构采用如电感耦合等离子体原子发射光谱（ICP-AES）,低温N2吸附,X射线衍射（XRD）仪,扫描电子显微镜（SEM）,NH3程序升温脱附（NH3-TPD）和H2程序升温还原（H2-TPR）等进行表征。结果表明,不论催化剂是在新鲜状态还是经过水热/硫老化后,采用更好的沸石结构的Fe-Beta分子筛结构及铈掺杂的催化剂都具有更宽的NOx转化温度窗口。由实验结果可知,较大的比表面积、均匀的小颗粒分子筛、规则的沸石骨架以及表面分散的不饱和的Ce4+对NH3-SCR的性能均有促进作用。     

碳载金铂双金属催化剂催化活性研究

采用KBH4做还原剂、PVP做保护剂,化学法一步合成Au-Pt合金纳米粒子,应用UV-Vis、TEM、XRD等手段对其进行了表征.将所合成的合金纳米粒子负载在碳黑上,获得Au-Pt双金属碳载催化剂,应用循环伏安法(CV)检测了催化剂对甲醇的电催化氧化活性.研究表明,Au-Pt/C催化剂的催化活性明显高于Pt/C的,说明...     

New gold catalysts for liquid phase oxidation

A pre-requisite for good catalytic activity with supported gold is that the metal is present as nanoparticles, but no suitable method for depositing gold on carbon as nanoparticles has previously been reported. The deposition precipitation method which has been used successfully for catalyst preparation with other supports, produces large aggregates with carbon. It is now shown, however, that pre-reduced gold sol is a satisfactory method for preparing gold on carbon catalysts as long as an appropriate choice of sol is made. In this paper the activity of gold on carbon catalysts prepared in a number of different ways is compared in a standardized liquid phase organic oxidation reaction. The activity for Au/C catalysts prepared by the sol method can show a two-fold increase compared with a similar catalyst prepared by deposition precipitation.     

Catalytic performance and kinetics of Au/γ-Al_2O_3 catalysts for low-temperature combustion of light alcohols

Au/γ-Al2O3 catalysts were prepared by deposition-precipitation method for the catalytic combustion of low concentration alcohol streams(methanol,ethanol,iso-propanol and n-propanol).The catalysts were characterized by X-ray photoelectron spectroscopy(XPS),X-ray diffractometry(XRD) and energy dispersive X-ray micro analysis(EDS) techniques.The XPS results showed that there was only Au0 on the surface of catalysts.The XRD patterns showed that Au was presumably highly dispersed over γ-Al2O3.The temperatures for complete conversion of methanol,ethanol,iso-propanol and n-propanol with concentration of 2.0 g/m3 were 60,155,170 and 137 ℃,respectively,but they were completely mineralized into CO2 and H2O at 60,220,260 and 217 ℃ respectively over the optimized catalyst.The activity of the catalyst was stable in 130 h.The kinetics for the catalytic methanol elimination followed quasi-first order reaction expressed as r=0.652 8c0+0.084 2.The value of apparent activation energy is 54.7 kJ/mol in the range of reaction temperature.     

Support effects in the selective gas phase hydrogenation ofp-chloronitrobenzene over gold

The catalytic continuous gas phase hydrogenation of p-chloronitrobenzene (P=1 atm;T=423 K) has been investigated over a series of oxide (Al₂O₃, TiO₂, Fe₂O₃ and CeO₂) supported Au (1 mol %) catalysts. The application of two catalyst synthesis routes,i.e. impregnation (IMP) and deposition-precipitation (DP), has been considered where the DP route generated smaller mean Au particle sizes (1.5-2.8 nm) compared with the IMP preparation (3.5-9.0 nm). The catalysts have been characterised in terms H2 chemisorption and BET area measurements where the formation of metallic Au post-activation has been verified by diffuse reflectance UV-Vis, XRD and HRTEM analyses.p-Chloroaniline was generated as the sole reaction product over all the Au catalysts with no evidence of C-Cl and/or C-NO₂ bond scission and/or aromatic ring reduction. The specific hydrogenation rate increased with decreasing Au particle size (from 9 to 3 nm), regardless of the nature of the support. This response extends to a reference Au/TiO₂ catalyst provided by the World Gold Council. A decrease in specific rate is in evidence for smaller particles (< 2 nm) and can be attributed to a quantum size effect. The results presented establish the basis for the design and development of a versatile catalytic system for the clean continuous production of high value amino compounds under mild reaction conditions.     

The activation of supported Au catalysts prepared by impregnation

In this study, Au/TiO₂, Au/γ-Al₂O₃, and Au/C catalysts were prepared by an incipient-wetness impregnation method. The CO oxidation activity after different pretreatment was analyzed. Two pretreatments are found possible to activate these catalysts for CO oxidation: (i) high-temperature hydrogen reduction and (ii) aqueous base treatment using NH3(aq). The high-temperature hydrogen reduction is effective for Au/TiO₂ and Au/C, but not Au/Al₂O₃. The base treatment is effective for Au/Al₂O₃ and Au/TiO₂, but not Au/C. Small Au particles of ca. 2 nm size were observed in activated Au catalysts from both pretreatments; however, the high-temperature H₂ reduction procedure also resulted in large Au particles of ca. 25 nm size which makes it a less efficient pretreatment than the base treatment. The activated Au/TiO₂ catalysts show comparable turnover frequency as the Au/TiO₂ catalyst prepared by a deposition precipitation method. The effective pretreatments were found to be accompanied by a reduced acidity, which is measured by the pH of aqueous catalyst suspension. Reasons for such activation are discussed.     

Au/Co_3O_4的制备、表征及加氢催化性能研究

采用化学浸渍法制备出Au/Co_3O_4纳米复合材料,用透射电子显微镜(TEM)、X射线能谱(EDS)和X射线粉末衍射(XRD)等对其结构和组成进行了表征,并考察了其在对硝基苯酚加氢反应中的催化性能。表征结果表明,Au纳米粒子很好地分散在Co_3O_4载体上。催化性能测试表明,Au/Co_3O_4纳米复合材料对于对硝基苯酚加氢反应表现出优异的催化活性,TOF值为5.01 min~(-1);此外,催化剂经过5次循环仍然保持优异的催化性能。     

PAN/PANI/rGO/Au复合纤维的制备及其催化、原位SERS监测性能研究

负载型贵金属纳米催化剂是提高贵金属催化剂利用率,降低经济成本的一种有效途径,也是一种新型的有潜力的表面增强拉曼光谱(SERS)的基底材料。本文首先利用静电纺丝技术构建了还原的氧化石墨烯(rGO)增强的聚丙烯腈/聚苯胺复合纤维(PAN/PANI/rGO),然后采用原位还原的方法在其表面生长金纳米颗粒得到了PAN/PANI/rGO/Au复合纤维,通过SEM, FTIR, XRD, XPS, Raman和UV-Vis光谱等手段对复合纤维进行了结构和形貌表征,最后以NaBH₄还原四硝基苯酚(4-NP)为模型,研究了复合纤维的催化性能和原位SERS检测该催化还原反应的过程,并将其与同种方法制备的PAN/PANI/GO/Au和PAN/PANI/Au复合纤维进行比较。结果表明,rGO增强的PAN/PANI/rGO/Au复合纤维具有优于PAN/PANI/GO/Au和PAN/PANI/Au复合纤维的催化活性、原位增强拉曼检测的能力和循环性能。     

Ag/Au-decorated Fe3O4/SiO2 composite nanospheres for catalytic applications

Noble metal particles in nanoscale (Au, Ag, Pt, etc.) have attracted intensive research interest due to their promising catalysis properties. However, the practical applications of these nanoparticle catalysts are always jeopardized by two problems. One is the difficulty in recovering the used nanoparticles and the other arises from the low catalytic efficiency due to the aggregation of the nanoparticles. In this work, Ag/Au nanoparticles were distributed onto spherical superparamagnetic carriers (SSCNs), which were fabricated through a facile oil-in-DEG emulsion route. The Ag/Au nanoparticles were attached onto the SSCNs by two steps. The Au seeds were attached onto the silica surface through electrostatic attraction first, and the Ag nanoparticles were grown on the basis of the Au seeds. The obtained Ag/Au–SSCN composite nanospheres demonstrated promising catalytic properties, which could also be recycled very easily by using a magnet.     

Ru/Mn-Ce/TiO2及Ru/TiO2催化剂对丁二酸的催化湿式氧化研究

采用浸渍法制备了2个系列的Ru／Mn-Ce/TiO2及Ru/TiO2催化剂,并用XRD、TEM、BET等方法对催化剂进行表征。在T=270℃和Po2=1．5MPa条件下,在间歇式反应釜中对丁二酸进行降解实验。结果表明60min内丁二酸降解的总有机碳(TOC)去除率为80％～99．8％;在钌含量相同的情况下,Ru／Mn-Ce／TiO2催化剂的催化活性高于Ru/TiO2催化剂;Ru含量较低的情况下,Mn、Ce对提高催化活性有很大作用,但Ru含量增加时Mn、Ce的作用减弱;氢还原的温度对Ru/TiO2系列催化剂的催化氧化活性有明显影响,500℃还原钌所得催化剂对丁二酸的催化氧化活性优于350℃。     

Adsorption of small molecules on gold single crystal surfaces

Much more work has been carried out on supported gold catalysts (also called “real” catalysts) than on gold single crystal surfaces. However, for fundamental understanding of catalysis by gold, well-defined gold surfaces and controlled conditions using the surface science approach may provide useful information concerning reaction mechanisms and the nature of active centers. This paper presents a brief overview on the work carried out regarding adsorption of several small molecules on gold surfaces from 2004, date of the last review on gold surface science [R. Meyer, C. Lemire, S.K. Shaikhutdinov and H. Freund,Gold Bull., 2004, 37, 72], until recently. Both experimental and theoretical results are discussed. A large difference between the flat Au(111), by far the most studied surface, and stepped/kinked surfaces, is found, demonstrating the importance of low-coordinated Au atoms for high catalytic activity.     

Au/Ni双金属纳米颗粒的制备及其催化制氢活性

采用化学共还原法制备了聚乙烯吡咯烷酮(PVP)保护的Au/Ni双金属纳米颗粒,采用UV-Vis、TEM对所合成的纳米颗粒进行了表征,研究了双金属纳米颗粒的化学组成对其催化水解Na BH4制氢活性的影响。结果表明:所制备的Au/Ni双金属纳米颗粒的平均粒径为2.9~4.2 nm,Au/Ni双金属纳米颗粒的催化活性高于Au和Ni单金属纳米颗粒的活性,Au50Ni50双金属纳米颗粒的催化活性最高,30℃时其催化活性数值达到550 mol-H2·h-1·mol-M-1。XPS和密度泛函理论(DFT)的结果都表明:Au/Ni双金属纳米颗粒优异的催化性能可归因于电荷转移效应,Ni原子与Au原子之间发生的电子转移使得Au原子带负电而Ni原子带正电,荷电的Au和Ni原子成为催化反应的活性中心。Au50Ni50双金属纳米颗粒催化水解Na BH4制氢的活化能为61.9 k J/mol。     

Selective catalytic reduction of NO with propene over Au/CeO2/Al2O3 catalysts

Selective catalytic reduction of NO by propene under an oxygen-rich atmosphere has been investigated over Au/ CeO₂, Au/CeO₂/Al₂O₃ and Au/Al₂O₃ catalysts prepared by deposition-precipitation. The results demonstrated that Au/16%CeO₂/Al₂O₃ had good low-temperature activity, selectivity towards N₂ and stability, which is superior to that of Pt/Al₂O₃. It was also found that adding 2% water vapour to the feed stream enhanced the NO conversions at low temperatures while the presence of 20 ppm SO₂ increased NO conversions at higher temperatures. It is particularly interesting that under the simultaneous presence of 2% water vapour and 20 ppm SO₂, the NO conversions to N₂ were significantly increased and the temperature window was widened significantly. The catalysts were characterized by Xray diffraction (XRD), high resolution transmission electron microscopy coupled with energy dispersive X-ray spectroscopy (HRTEM-EDX) and temperatureprogrammed reduction (H2-TPR) techniques. Both XRD and HRTEM revealed that CeO₂ was highly dispersed on the alumina support, and HRTEM combined with EDX showed that gold particles were preferentially deposited on those highly dispersed CeO₂ particles. The gold deposition made CeO₂ more reducible and interaction between gold and those highly dispersed CeO₂ particles became stronger than that with the bulk CeO₂, and this interaction is probably responsible for the superior catalytic performance of the Au/CeO₂/Al₂O₃.     

挥发性有机物催化燃烧用贵金属催化剂的研究进展

催化燃烧技术是目前处理挥发性有机物(VOCs)废气最有效技术之一。贵金属催化剂因具有高活性和稳定性,广泛应用于挥发性有机物催化氧化反应中。综述了近年来国内外VOCs用贵金属催化剂研究进展,阐述了Pd、Pt和Au等不同贵金属活性组分的种类、制备方法、颗粒尺寸、协同效应,以及载体性质和载体-活性金属的作用等对催化剂性能的影响,最后,对贵金属催化剂的研究方向进行了展望。     

A Novel internally heated Au/TiO2 carbon-carbon composite structured reactor for low-temperature CO oxidation

A compact, internally heated, catalytic reactor is demonstrated for the low-temperature oxidation of carbon monoxide. Carbon nanofibres were grown on carbon felt and used as a support material for Au/TiO₂ catalysts. The carbon composite plays two roles; as a support material for the catalyst and for providing heat to the reaction by the Joule effect. The internal heating offers a stable reactor system with quick temperature response at relatively low energy input. Comparison between external and internal heating shows higher conversion of CO in the low-temperature range when using internal heating. The Au/TiO₂ catalyst supported on the carbon-carbon composite shows good stability at 250°C.