铝改性介孔二氧化硅泡沫载体材料合成及其DBT加氢脱硫性能

介孔二氧化硅泡沫(MCFs)材料具有超大的三维球形孔结构、超大孔容(1.0–2.4 cm3/g)、高比表面(1000 m2/g)、孔径可调范围较广(24–50 nm)且球形孔道之间通过窗口(9–22 nm)联结,因此具有优良的传质性能,能够促进加氢脱硫反应.但是,与传统的微孔分子筛相比,该纯硅类介孔材料酸性较弱,不利于一些酸催化反应;因此,对纯硅材料进行金属改性以增加其酸性,从而促进催化剂的催化活性.而一般对纯硅类介孔材料采用Al,Ti,Zr等金属,铝改性主要是为纯硅载体提供酸性,而钛锆改性则是为了调变活性金属以及促进金属的分散,从而提高催化剂的加氢脱硫活性.因此,我们主要采用后改性方法,以P123为微乳液体系中的表面活性剂,TEOS为硅源,TMB为扩孔剂,异丙醇铝为铝源,成功合成了一系列Si/Al比不同的介孔二氧化硅泡沫材料.通过改变异丙醇铝的加入量,成功合成了系列Si/Al比(x)的NiMo/Al-MCFs(x)(x=10,20,30,40和50)催化剂.对所合成的载体及相应的催化剂通过SAXS,N2吸附脱附,SEM,Py-FTIR,UV-Vis,H2-TPR,NH3-TPD,HRTEM,Raman及27Al MAS NMR等表征手段进行分析,并在高压加氢微反装置上对相应的NiMo负载型催化剂进行DBT HDS活性评价,系统分析了不同硅铝比对催化剂DBT HDS反应活性的影响.SAXS和SEM表征结果表明,Al后改性并没有破坏载体材料的结构;27Al MAS NMR表征结果表明,后改性法能成功把Al掺杂进纯硅材料的骨架中.催化剂UV-Vis和Raman表征结果表明,当Si/Al比为20时,NiMo/Al-MCFs(20)催化剂Mo物种的带隙能量最大,且氧化钼的平均粒径较小,Mo物种在该催化剂中的分散度较好;H2-TPR分析结果表明,NiMo/Al-MCFs(20)催化剂还原温度较低,最易还原.Py-FTIR结果表明,随着Al加入量的增大,其酸性逐渐增大,当Si/Al比为20时酸性达到最大,继续增加Al的加入量,其酸性不再增加;此外,NiMo/Al-MCFs(20)的硫化度最高,且其MoS2的堆垛层数较低.负载活性金属后制备了NiMo/Al-MCFs(x)催化剂,将其应用于DBT加氢脱硫反应,并与传统NiMo/γ-Al2O3催化剂加氢脱硫反应活性作对比.研究发现,所制备的NiMo/Al-MCFs(x)系列催化剂由于具有较大孔径、比表面积及孔容和较强的酸性,因而其DBT HDS活性明显高于传统的工业NiMo/γ-Al2O3催化剂,且催化剂活性在硅铝比达到20时最大,最高可达96%,因此它作为加氢脱硫催化剂载体具有很大的应用前景.     

Asymmetric transfer hydrogenation over Ru-TsDPEN catalysts supported on siliceous mesocellular foam

A siliceous mesocellular foam-immobilized Ru-TsDPEN complex exhibited excellent catalytic reactivity, enantioselectivity and reusability in the asymmetric transfer hydrogenation of an imine and ketones.     

Adsorption of CO2 on mesocellular siliceous foam iteratively functionalized with dendrimers

Melamine-type dendrimers are grafted to mesocellular siliceous foam (MCF) with ultralarge mesopores by stepwise alternating treatments of the substrate with 2,4,6-trichlorotriazine and ethylenediamine. MCF grafted dendrimers up to 4th generation are prepared and characterized. Very high organic loadings (55 wt% at the 4th generation) are achieved, with half of the initial substrate mesopores volume remaining unoccupied—leaving room for the rapid ingress and egress of small gas molecules. The product materials possess relatively high thermal stability—their decomposition starts at around 300 °C. Adsorption measurements suggest that only the primary amine groups of these melamine type structures are active for CO₂ chemisorption. The CO₂ adsorption capacities of these adsorbents are improved relative to the unfunctionalized MCF, especially when considered on a wt% substrate basis.     

Highly dispersed palladium nanoparticles on mesocellular foam: an efficient and recyclable heterogeneous catalyst for alcohol oxidation

Palladium nanoparticles immobilized on amino-functionalized mesocellular foam constitute an efficient catalyst for the aerobic oxidation of primary and secondary alcohols to their corresponding carbonyl compounds in high to excellent yields. An exceptionally high TON of 365?000 was reached for the oxidation of 1-phenylethanol under solvent-free reaction conditions. The catalyst can be recycled many times with retained activity as shown by the identical rate curves of the first and fifth runs.     

Small Pd nanoparticles supported in large pores of mesocellular foam: an excellent catalyst for racemization of amines

Highly dispersed palladium nanoparticles (1–2 nm) supported in large‐pore mesocellular foam (MCF; 29 nm) were synthesized. The Pd‐nanocatalyst/MCF system was characterized by transmission electron microscopy (TEM), powder X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS). The performance of the Pd nanocatalyst obtained was examined for amine racemization. The Pd nanocatalyst showed higher activity and selectivity toward racemization of (S)‐1‐phenylethyl amine than any other amine racemization catalyst reported so far and it could be reused several times. Our data from TEM and XRD suggest a restructuring of the Pd nanocatalyst from amorphous to crystalline and an increase in Pd nanocatalyst size during the racemization reaction. This led to an unexpected increase of activity after the first use. The Pd nanocatalyst obtained can be integrated with other resolving processes of racemic organic compounds to increase the yield of chiral organic products.     

Palladium nanoclusters supported on propylurea-modified siliceous mesocellular foam for coupling and hydrogenation reactions

This paper describes the synthesis, characterization and applications of palladium (Pd) nanoparticles supported on siliceous mesocellular foam (MCF). Pd nanoparticles of 2-3 nm and 4-6 nm were used in reactions involving molecular hydrogen (such as hydrogenation of double bonds and reductive amination), transfer hydrogenation of ketones and epoxides, and coupling reactions (such as Heck and Suzuki reactions). They successfully catalyzed all these reactions with excellent yield and selectivity. This heterogeneous catalyst was easily recovered by filtration, and recycled several times without any significant loss in activity and selectivity. The palladium leaching in the reactions was determined to be much less than the FDA-approved limit of 5 ppm. Furthermore, the catalyst can be stored and handled under normal atmospheric conditions. This immobilized catalyst allows for ease of recovery/reuse and minimization of waste generation, which are of great interest in the development of green chemical processes.     

Rhodium nanoparticles entrapped in boehmite nanofibers: recyclable catalyst for arene hydrogenation under mild conditions

A new recyclable rhodium catalyst was synthesized by a simple procedure from readily available reagents, which showed high activities in the hydrogenation of various arenes under 1 atm H2 at room temperature.     

Palladium nanoparticles entrapped in aluminum hydroxide: dual catalyst for alkene hydrogenation and aerobic alcohol oxidation

[reaction: see text] A new aluminum hydroxide-supported palladium catalyst (1) made by a one-pot synthesis through nanoparticle generation and gelation shows a dual catalytic activity for olefinic hydrogenation and aerobic alcohol oxidation.     

Siliceous mesocellular foam for high-performance liquid chromatography: Effect of morphology and pore structure

Spherical siliceous mesocellular foam (MCF) particles with an average particle size of 4.8 μm have been successfully prepared. These spherical particles were tailored in pore sizes and surface areas. They were functionalized with C₈ or C₁₈ groups, and applied towards reversed phase high-performance liquid chromatography (HPLC) column separations. Their high surface areas gave rise to very good retention characteristics, as illustrated in the separation of a series of alkylbenzene solutes with increasing chain length. The highly interconnected porous structure and ultralarge pore size of MCF allowed the columns to be used at high flow rates without much loss in column efficiency. The column efficiency and peak symmetry were further improved by eliminating the micropores of the stationary phase. The reversed phase column packed with C₁₈-modified spherical MCF particles provided for excellent separation of different deoxynucleosides, illustrating the broad applicability of these materials due to their controlled pore size.     

Polyoxometalate-modified carbon nanotubes: new catalyst support for methanol electro-oxidation

A new catalyst support, polyoxometalate-modified carbon nanotubes, is presented in this paper through the chemisorption between polyoxometalate and carbon. Pt and Pt-Ru nanoparticles were electrochemically deposited on polyoxometalate-modified carbon nanotubes electrodes, and their electrocatalytic properties for methanol electro-oxidation are investigated in detail. Due to the unique electrical properties of carbon nanotubes and the excellent redox properties and the high protonic conductivity of polyoxometalate, for the similar deposition charge of Pt and Pt-Ru catalysts, 1.4 times larger exchange current density, 1.5 times higher specific activity, and better cycle stabilities can be obtained at polyoxometalate-modified carbon nanotube electrodes as compared to the electrodes without polyoxometalate modification. These results show that polyoxometalate-modified carbon nanotubes as a new catalyst support have good potential application in direct methanol fuel cells.     

Effect of TMB/P123 ratios on physicochemical properties of mesocellular foam carbon (MCF-C) as catalyst for ethanol dehydrogenation

The preparation of mesocellular foam carbon catalysts with different ratios of 1,3,5-trimethyl benzene (TMB)/P123 is represented for investigation in catalytic activity via ethanol dehydrogenation to acetaldehyde. The TMB was used as a swelling agent and P123 acted as template-structuring. The physicochemical properties of synthesized catalysts were determined using Brunauer-Emmett-Teller (BET) surface area analysis, transmission electron microscopy (TEM), scanning electron microscopy (SEM)–energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Fourier transform infrared (FT-IR), thermogravimetric analysis (TGA), ammonia temperature-programmed desorption (NH₃-TPD), and carbon dioxide temperature-programmed desorption (CO₂-TPD). The evidence suggested that various ratios of TMB/P123 can differently control the mesostructure including the pore size, specific surface area, and pore volume. Particularly, MCF-C 3.5 catalyst (TMB/P123 of 3.5) enhanced the catalytic via ethanol dehydrogenation. Interestingly, effectively controllable pore structure of catalysts is beneficial for the desorption of selective product such as acetaldehyde leading to remarkably increased yield of acetaldehyde. Furthermore, the MCF-C 3.5 evidently exhibited outstanding stability at temperature of 400 °C for 12 h. Thus, it can be reasonably selected the ratio of TMB/P123 as 3.5, which is dominantly facilitated either high diffusion of reactant or high stability without losing of the traditional structure compared with other ratios of TMB/P123.     

有序介孔碳材料负载铂纳米粒子：用于硝基苯及其衍生物液相催化氢化的高效催化剂

介孔碳材料由于具有规整的孔道结构、表面疏水性、化学惰性、大的比表面积和大的孔体积等特点,在催化领域的应用备受关注,不仅可以直接用作催化剂,还可以作为催化剂载体负载金属活性中心并用于催化反应.介孔碳材料作为载体用于加氢反应已有报道,并且其催化活性明显优于活性炭材料.有序介孔碳材料的代表之一CMK-3可以经过SBA-15翻模合成.采用浸渍法将氯铂酸负载到CMK-3载体上,经过甲酸钠还原制得质量分数为5%的Pt/CMK-3催化剂.小角XRD谱表明CMK-3保留了p6mm对称性,介孔结构完好;从广角XRD谱可以看出,金属铂粒子的衍射峰比较宽,说明铂纳米粒子分散比较均匀. CO化学吸附和透射电镜(TEM)的表征结果进一步证明铂纳米粒子分散得比较均匀,平均粒子大小约为2.5 nm (CO化学吸附), EDX结果表明铂的实际担载量为4.7%.将Pt/CMK-3催化剂用于硝基苯及其衍生物的液相加氢反应中,发现溶剂对反应结果具有很大的影响.首先参考以前的工作,选用水和乙醇体积比9：1的混合溶液为溶剂.在298 K和4 MPa氢气条件下,50 mg催化剂可以将21 mmol硝基苯在10 min内转化98.4%,产物苯胺的选择性高于99%;活性明显高于商品化Pt/C催化剂(相同条件下转化率为88.7%).在此基础上,把Pt/CMK-3催化剂用于含有不同取代基的硝基苯衍生物的液相催化加氢反应,含有吸电子基团如氯取代的硝基苯衍生物转化率为(21.4%–77.7%);苯环上含有给电子基团如甲基时,硝基甲苯加氢反应的转化率为(83.3%–98.0%);而给电子能力更大的基团如甲氧基取代的硝基苯衍生物的转化率却并不高.一方面是由于电子效应导致氯取代的硝基苯衍生物活性偏低,另一方面是由于空间位阻导致邻位取代的硝基苯衍生物活性相对其它位置取代的衍生物转化率偏低.考虑到部分反应物在混合溶剂中溶解度较低,可能导致加氢反应过程受到影响,从而影响反应结果,所以又选用无水乙醇溶剂进行了比较.首先仍用50 mg催化剂于硝基苯催化加氢反应,发现在乙醇溶剂中,21 mmol硝基苯在5 min内可以完全转化;当把硝基苯的量增加到5倍时,转化率为22.2%,苯胺选择性高于99%.因此,在乙醇溶剂中将催化剂用量减半,结果在5 min内21 mmol硝基苯衍生物均完全转化为对应的芳香胺化合物;除了硝基氯苯发生脱氯副反应外,其它衍生物选择性都很高.为了更好地区分不同取代基硝基苯衍生物的加氢活性,将2-氯硝基苯和2-甲基硝基苯的用量增大至105 mmol,反应过程中保持氢气压力恒为4 MPa,并使反应在5 min后中止,此时测得2-氯硝基苯催化加氢的TOF值为28.3 s–1,而2-甲基硝基苯的TOF值高达43.8 s–1. X射线光电子能谱(XPS)显示Pt/CMK-3表面含有带一定正电的铂物种,推测此物种有助于吸附硝基的氧原子,从而活化底物,促进加氢反应的顺利进行.最后还考察了Pt/CMK-3催化剂在硝基苯加氢中的循环使用性能,发现催化剂可以循环使用至少14次,活性没有任何下降.对反应滤液进行ICP分析,发现滤液中并没有铂离子流失;对使用过的催化剂进行透射电镜表征也没有观察到铂粒子聚集现象,说明催化剂的稳定性良好.     

Highly fluorescent rhodamine B nanoparticles entrapped in hybrid glasses

Rhodamine B (RB) nanoparticles entrapped in hybrid glasses show enhanced fluorescent emission (approximately 220-fold larger than that of single RB molecules) thanks to the configuration control of the self-assembled aggregates that form the supramolecular architecture of the nanoparticles. The fluorescence performance reported in this work is around 1 order of magnitude larger than that recently reported for fluorescent Nile Red nanoparticles. The fluorescence enhancement results from the use of a highly efficient fluorescent dye such RB and the formation of larger nanoparticles. Note that the later implies the presence of a large number of emitting centers involved in the fluorescence emission.     

Cyclodextrin nanosponges: a potential catalyst and catalyst support for synthesis of xanthenes

The nanoporous framework of a cyclodextrin nanosponge was used as catalyst for accelerating the one-pot, three-component reaction of dimedone, aldehyde, and phenols for synthesis of xanthene derivatives. Moreover, the nanocavities of cyclodextrin nanosponges were exploited for immobilization of heteropolyacids through the wet impregnation method. This catalyst exhibited superior catalytic performance compared to the bare cyclodextrin nanosponge. Despite the good catalytic activity, the leaching of the catalytic species did not allow efficient recovery and reusability. To circumvent this problem, the cyclodextrin nanosponge was amine-functionalized prior to heteropolyacid immobilization. The results proved that the amine functionalities had an effective role in preserving the catalytic species and improving the reusability through decreasing the leaching time. This catalyst was used for synthesis of a variety of xanthenes in aqueous media. The catalytic amount of catalyst afforded the desired product in excellent yields and with a relatively short reaction time. The results suggested cyclodextrin nanosponge-based catalysts as potential candidates for promoting chemical reactions.     

Unique catalysis of Ni-Al hydrotalcite derived catalyst in CO_2 methanation: cooperative effect between Ni nanoparticles and a basic support

Ni-Al hydrotalcite derived catalyst （Ni-Al2O3-HT） exhibited a narrow Ni particle-size distribution with an average particle size of 4.0 nm. Methanation of CO2 over this catalyst initiated at 225℃ and reached 82.5% CO2 conversion with 99.5% CH4 selectivity at 350℃, which was much better than its impregnated counterpart. Characterizations by means of CO2 microcalorimetry and 27 Al NMR indicated that large amount of strong basic sites existed on Ni-Al2O3-HT, originated from the formation of Ni-O-Al structure. The existence of strong basic sites facilitated the activation of CO2 and consequently promoted the activity. The combination of highly dispersed Ni with strong basic support led to its unique and high efficiency for this reaction.

Keywords     

Unique catalysis of Ni-Al hydrotalcite derived catalyst in CO2 methanation: cooperative effect between Ni nanoparticles and a basic support

Ni-Al hydrotalcite derived catalyst (Ni-Al₂O₃-HT) exhibited a narrow Ni particle-size distribution with an average particle size of 4.0 nm. Methanation of CO₂ over this catalyst initiated at 225 °C and reached 82.5% CO₂ conversion with 99.5% CH₄ selectivity at 350 °C, which was much better than its impregnated counterpart. Characterizations by means of CO₂ microcalorimetry and ²⁷Al NMR indicated that large amount of strong basic sites existed on Ni-Al₂O₃-HT, originated from the formation of Ni-O-Al structure. The existence of strong basic sites facilitated the activation of CO₂ and consequently promoted the activity. The combination of highly dispersed Ni with strong basic support led to its unique and high efficiency for this reaction.     

Gold nanoparticles supported on cellulose aerogel as a new efficient catalyst for epoxidation of styrene

A new efficient heterogeneous catalyst was introduced for the epoxidation of styrene. The catalyst was obtained from deposition of gold nanoparticles on the cellulose aerogel. The catalyst was characterized with XRD, TGA, EDX, BET, FAAS and SEM. High yield and excellent selectivity were achieved for the epoxidation of styrene in solvent-free conditions at room temperature using H₂O₂ as a green oxidant during 1 h. The reaction has some advantages such as solvent-free and mild reaction conditions, low catalyst loading, high yield, excellent selectivity, green oxidant and short reaction duration. In addition, the catalyst is recyclable and applicable for six times without decrease in yield.     

Colloidal cobalt nanoparticles: a highly active and reusable Pauson-Khand catalyst

A new Pauson-Khand catalyst based on colloidal cobalt nanoparticles has been developed; the catalyst is highly effective for many intra- and inter-molecular Pauson-Khand reactions and can be recycled and reused many times without losing catalytic activity.