微乳法制备纳米催化剂研究进展

微乳法作为制备纳米微粒的有效方法,具有操作简单、制备粒子尺寸均匀、颗粒大小及形状可控等优点,在纳米催化剂制备领域具有广阔的应用前景。综述了近年来采用微乳法制备纳米催化剂的研究状况,尤其是对利用微乳法制备金属纳米粒子、金属氧化物及负载型金属催化剂进行了综述。     

负载型纳米钌催化剂的制备方法及应用

负载型纳米金属催化剂在化学工业中发挥着重要作用。纳米金属颗粒的结构、组成、形貌以及与载体的相互作用影响负载型纳米金属催化剂的催化活性和稳定性,而纳米金属催化剂的物化性质与催化剂的制备方法密切相关。与其他贵金属相比,负载型纳米钌催化剂对芳环加氢具有很高的催化活性,在化工材料、制药以及有机液体储氢等领域具有较为广泛的应用。综述了负载型纳米钌催化剂的基本制备方法及应用,为今后研究工作提供了参考。     

介孔碳材料及其负载金属催化剂的制备及应用研究进展

介孔碳材料具有较高比表面积、均一可控纳米孔分布和可调节的表面化学性能,在催化领域具有重要应用前景.综述了介孔碳材料及其负载金属催化剂的制备方法及催化应用进展.     

镝离子掺杂纳米二氧化钛空心球的合成及其光化学性能

以钛酸四丁酯为钛源,利用水热制备的纳米碳球为模板,通过超声辅助法合成了不同镝掺杂量的二氧化钛空心球。通过XRD、SEM、TEM、EDX、UV-Vis和荧光光谱对其形貌和光谱性质进行了表征,并讨论了镝掺杂前后对产物结构形貌的影响。研究结果表明,利用碳球为模板制备的镝掺杂的二氧化钛球尺寸可控且在430 nm附近发出宽而强的蓝光。     

纳米或多孔氧化铬粒子制备的研究进展

综述了近年来国内外纳米或多孔氧化铬的制备方法,即气相法、固相法和液相法（主要包括热分解法、沉淀法、溶胶-凝胶法、水热合成法、模板法、溶液燃烧法、超声化学法等）;讨论了各制备方法对粒子表面形貌、粒径尺寸或孔结构、晶相结构等的影响;展望了今后对这类纳米或多孔材料研究与应用的发展方向。在诸多制备方法中,模板法或其与其他方法的联用法是制备规整形貌、有序孔结构、均匀粒径分布、高热稳定性氧化铬的较为适宜的方法。模板法有望发展成为高效实用的催化剂制备技术。     

Pd负载电纺碳纳米纤维的制备及其催化活性

Pd纳米粒子负载的碳纳米纤维是催化Sonogahira偶合反应的良好催化剂,其高长径比使之易于从反应混合物中过滤分离;金属纳米粒子与碳纤维间的强相瓦作用使其具有良好的多次重复使用性.通过电纺丝技术和碳化技术制备了Pd金属纳米粒子负载的电纺碳纳米纤维,透射电镜观察显示最终碳化温度及在该温度下的停留时间是影响钯纳米粒子尺寸及其在纤维中分布的主要因素.并通过所得复合纳米纤维对Sonogahira偶合反应的催化活性研究,发现475～575℃这一温度范围是制备具有良好催化活性的金属钯纳米粒子负载的碳纳米纤维的最佳的碳化温度段.     

新型碳负载纳米钯催化的芳基末端炔烃的合成研究

以新型纳米多孔碳为载体,负载钯纳米颗粒,制备出了一种新型的负载型纳米催化剂。该催化剂具有较高的催化活性,能够在室温条件下实现芳基末端炔烃的合成,并且催化剂在重复回收四次之后,催化活性和结构都没有发生明显的变化。     

氧化铈合成与改性及在催化领域的应用

氧化铈催化剂已经在催化领域被广泛研究与应用。本文讨论了氧化铈的合成技术对形貌、尺寸与性能的影响，通过不同温度与碱浓度制备的三种不同形貌的氧化铈来探讨形貌对催化活性的影响。不同的二氧化铈纳米形貌表面氧缺陷浓度的变化被认为与晶体层选择性暴露在不同纳米结构中有关，催化活性顺序为：棒>立方体>颗粒。CeO₂的形貌不仅对纯CeO₂催化剂的催化性能具有巨大影响，对铈负载催化剂也具有很大影响，但氧化铈形貌对铈负载催化剂的催化行为是特定于情况的。不同的负载物与不同的氧化铈形貌复合后的催化性能主要由活性位点，表面氧空位，金属-载体相互作用、污染物降解过程等多方面共同决定。本文还介绍了氧化铈复合催化剂在臭氧催化、催化降解挥发性有机物及光催化领域的优势与进展。     

碳包裹非贵金属催化剂的制备及其在催化加氢中的应用

实现非贵金属催化剂在加氢反应中的广泛应用对工业催化领域具有重要意义,新型碳包裹非贵金属催化剂因其优异的结构稳定性和催化加氢性能而备受关注。本文综述了近年来碳包裹非贵金属催化剂及其制备方法的研究进展,归纳总结了不同制备方法对碳包裹结构的影响以及其优缺点,并介绍了碳包裹非贵金属催化剂在硝基类芳烃、羰基类芳烃、苯酚、喹啉加氢以及费托合成等加氢反应中的催化性能以及稳定性表现。文中提出：目前该催化剂亟需解决的问题是实现金属粒子尺寸以及碳壳结构的可控调变,今后的一个研究方向是进一步探索能够简便调节催化剂结构并且经济可行的制备方法。     

超声技术在贵金属纳米催化剂制备中的应用

贵金属纳米催化剂由于其特殊的物理化学性质,在工业生产、燃料电池、光催化等领域都有良好的前景。贵金属纳米催化剂的催化活性与其结构、形貌、尺寸密切相关。超声技术由于声空化特有的还原、分散作用,可用于可控形貌的纳米粒子的合成。综述了超声方法制备不同结构的贵金属纳米催化剂的研究进展。     

活性炭负载金属催化剂的研究进展

活性炭作为一种优良的催化剂载体被广泛应用于催化领域,其经酸碱预处理或氧化预处理后表面可负载一种或多种金属催化剂,是优化各种金属催化剂性能的有效方法之一。为给今后活性炭载体催化剂的研发提供一些参考和方向,从单一金属催化剂负载和复合金属催化剂负载的制备、催化活性及应用着手,对近年来新制备的活性炭负载金属催化剂进行综述。     

A new system design for the preparation of copper/activated carbon catalyst by metal-organic chemical vapor deposition method

A metal-organic chemical vapor deposition (MOCVD) technique was used to prepare heterogeneous metallic catalyst supported on activated carbon. A new system design was built to achieve higher metal loading within a shorter preparation time. In the optimization of system parameters, higher metal loading can be achieved by using longer deposition time, optimum carrier gas flow rate, higher operating temperature of either evaporation zone or a deposition zone or a smaller amount of porous support. Several techniques were carried out to characterize the catalyst such as physisorption, X-ray diffraction, inductively coupled plasma—optical emission spectroscopy and scanning electronic microscopy assisted with the Energy dispersive X-ray spectroscopy (SEM-EDX). It was found that the BET specific surface area and total adsorption volume of the prepared catalysts were reduced after metal deposition, due to the formation of the deposited copper onto the porous media both externally and internally. The morphology of the cylindrical Cu/AC was analyzed by SEM-EDX. The results show that the metal was deposited with a reasonably uniform distribution onto the inner part of the porous support.     

Graphene as catalyst support: The influences of carbon additives and catalyst preparation methods on the performance of PEM fuel cells

The reduction of the platinum amount for efficient PEM (polymer electrolyte membrane) fuel cells was achieved by the use of graphene/carbon composites as catalyst support. The influences of the carbon support type and also of the catalyst preparation method on the fuel cell performance were investigated with electrochemical, spectroscopic and microscopic techniques. Using pure graphene supports the final catalyst layer consists of a dense and well orientated roof tile structure which causes strong mass transport limitations for fuels and products. Thus the catalysts efficiency and finally the fuel cell performance were reduced. The addition of different carbon additives like carbon black particles or multi-walled carbon nanotubes (MWCNT) destroys this structure and forms a porous layer which is very efficient for the mass transport. The network structure of the catalyst layer and therefore the performance depends on the amount and on the morphology of the carbon additives. Due to optimizing these parameters the platinum amount could be reduced by 37% compared to a commercial standard system.     

直接甲醇燃料电池中碳基载体材料的研究进展

甲醇氧化电催化剂是决定直接甲醇燃料电池（direct methanol fuel cells, DMFCs）性能、寿命与成本的关键。为获得高功率密度和低生产成本的DMFCs,设计合成具有组成、结构、形貌可控的阳极催化剂备受关注。阳极催化剂的颗粒尺寸、粒径分布、形貌结构、稳定性、分散性以及催化活性都和负载它的载体息息相关,而碳基载体材料由于其优异的性能被广泛应用于DMFCs领域。本文分别介绍了酸性环境和碱性环境中甲醇氧化反应的机理,然后对不同形式的碳基载体材料,例如炭黑、介孔碳、碳纳米材料、氧功能化碳、杂原子掺杂碳、以及金属氧化物改性碳作为催化剂载体在DMFCs领域中的应用进行了综述,最后对DMFCs的发展趋势进行了展望。     

Platinum embedded within carbon nanospheres for shape selective liquid phase hydrogenation

Reactant shape selective catalysis occurs when substrates of different sizes and shapes are consumed at different rates over catalysts that combine molecular sieving transport processes with reaction. By contrast the same substrates react at nearly equivalent rates over catalysts that have large, open pores that do not induce any form of molecular sieving. Here we describe the design and synthesis of reactant shape selective catalysts for liquid phase hydrogenation reactions. Using an emulsion polymerization of furfuryl alcohol, we have made catalysts that consist of microporous carbon nanospheres within which are embedded platinum nanoparticles. The porosity of the carbon spheres was found to be a key parameter affecting catalyst activity and selectivity; porosity was varied by adding pore forming agents, such as polyethylene glycol with different molecular weights, during synthesis, or by mild oxidation of the as-synthesized catalyst using carbon dioxide. In addition to increasing porosity to reduce mass transfer limitations, a synthesis of smaller carbon spheres (<200 nm) was devised to reduce the micropore diffusion length. Decreasing the particle size of the catalyst by adjusting the surfactant composition during polymerization, improved the effectiveness factor by approximately one order of magnitude making it as active as a comparable standard metal catalyst.     

Performance of CoMoS catalysts supported on nanoporous carbon in the hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene

A new type of nanoporous carbon with a large surface area and mesoporosity was prepared and used as a support for a hydrodesulfurization (HDS) catalyst. The overall activity of CoMoS catalysts for the HDS of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) is affected by the type of support used for preparing the catalyst and decreases in the order of CoMo/(nanoporous carbon)>CoMo/(activated carbon)>CoMo/Al₂O₃. The surface area of activated carbon is the largest among these three types of supports but is significantly lowered after metal loading during the preparation of the catalyst. On the other hand, the surface areas of the other two supports are largely preserved after metal loading. The intrinsic activity of the catalysts, estimated by dividing the overall HDS rate by the amount of NO adsorbed on the catalyst, shows a trend that is different from that for the overall activity, and follows the order of CoMo/(nanoporous carbon)≈CoMo/Al₂O₃>CoMo/(activated carbon). The low intrinsic activity of CoMo/(activated carbon) compared to that of the other two catalysts, particularly in the case of 4,6-DMDBT HDS, is obtained because the diffusion of reactants into the catalyst pores is significantly limited. This is not observed with other catalysts supported on nanoporous carbon and alumina. From the results of this study, we conclude that nanoporous carbon is a promising support for HDS catalysts, compared to conventional supports such as alumina and activated carbon, because it has a large surface area and a high mesoporosity, both of which are beneficial to the preparation of highly dispersed metal catalysts without significant pore blocking due to the dispersed metal particles.     

钌炭催化剂的制备及其在芳环加氢反应中的应用

芳环加氢反应是最重要的合成反应之一,钌炭催化剂在芳环加氢反应中具有优异的催化性能。综述钌炭催化剂的制备方法和载体性质对钌炭催化剂的影响以及钌炭催化剂在苯、苯甲酸和对苯二甲酸二甲酯等芳环加氢反应中的应用进展。负载型钌炭催化剂的制备方法主要有浸渍法、沉淀法和升华法,超声辅助浸渍法可将大部分钌纳米粒子引入到炭载体的孔道内部,得到限域型负载钌炭催化剂。而镶嵌式钌炭催化剂主要是指通过原位炭化的方法将钌粒子部分镶嵌在炭的孔壁上,一步得到钌炭催化剂,其制备方法主要有软模板剂法和硬模板剂法。除制备方法外,炭的骨架结构、表面性质及氮掺杂对钌炭催化剂的性能影响也较大。镶嵌式钌炭催化剂具有钌纳米粒子和炭载体之间的相互作用强、催化剂抗流失及烧结性能好,在芳环加氢反应中表现出卓越的催化性能和稳定性。随着新制备技术的出现,新型镶嵌式钌炭催化剂将可能实现产业化。     

加氢处理催化剂制备技术研究进展

从过渡金属硫化物催化剂活性相理论出发,认为在加氢催化剂制备过程中保证活性组分的适度分散和金属-载体之间适度的相互作用能提高加氢催化剂的性能。本文针对加氢处理催化剂的制备技术,综述了添加有机助剂、平衡吸附法、浆液浸渍法等浸渍改进技术以及水热沉积法、原位晶化法、化学气相沉积法等新型的制备技术,并介绍了相关的国内外研究进展。分析指出有机助剂能与载体、金属作用,进而改变金属在载体表面的存在形态,有利于高活性CoMoS相的生成;水热沉积法和原位晶化法能够使活性组分在载体上均匀吸附沉积,从而实现活性组分在载体上的分散,并形成堆积程度更高的高活性Ⅱ型活性中心。     

CFC-115加氢脱氯制HFC-125 Pd/C催化剂制备研究

以商品化活性炭为载体、贵金属Pd为活性组分,采用浸渍法制备了一系列Pd/C催化剂.在常压固定床微型反应器中,以CFC-115加氢脱氯生产臭氧消耗物质(ODS)替代品HFC-125为目标反应,评价了催化剂的性能.详细考察了载体预处理硝酸浓度、载体粒径、Pd源前驱体及溶剂等制备条件对其催化性能的影响.在研究的范围内,采用粉末活性炭为载体,Pd(NO_3)_2为Pd源,甲醇为溶剂制备的催化剂具有最好的催化性能.     

负载固相的铑基催化剂应用于烯烃氢甲酰化反应的研究进展

负载固相的催化剂因其简便的分离循环操作以及可观的催化性能而广受关注,但存在反应活性较差、金属流失量较大、催化剂制备成本较高等问题。本文首先从不同负载材料的角度综述了近年来该类催化剂最新的研究进展,主要探讨了载体的表面性质、催化剂的制备方法、膦配体等对催化性能的影响;最后介绍了新型的单原子催化剂所取得的突破性进展。分析表明：具有"类均相"特点的多孔有机聚合物的催化活性很好,而超支化聚合物功能化的磁性纳米催化剂的稳定性更佳。另外还对负载型铑催化剂未来的研究方向进行了展望：需要进一步加深对多孔有机聚合物的化学结构的理解,以便对其更好地表征;借助一些先进的表征技术如高角环状暗场扫描透射电镜和密度泛函理论的计算来深入研究载体结构对单原子催化剂的催化性能的影响。