Wheat flour-derived N-doped mesoporous carbon extrudes as an efficient support for Au catalyst in acetylene hydrochlorination

We recently reported an N‐doped mesoporous carbon(N‐MC)extrudate,with major quaternary N species,prepared by a cheap and convenient method through direct carbonization of wheat flour with silica,which has excellent catalytic performance in acetylene hydrochlorination.Herein,we examined the activity of Au supported on N‐MC(Au/N‐MC)and compared it with that of Au supported on nitrogen‐free mesoporous carbon(Au/MC).The acetylene conversion of Au/N‐MC was 50%at 180°C with an acetylene space velocity of 600 h–1 and VHCl/VC2H2 of 1.1,which was double the activity of Au/MC(25%).The introduced nitrogen atoms acted as anchor sites that stabilized the Au3+species and inhibited the reduction of Au3+to Au0 during the preparation of Au/N‐MC catalysts.

Study on Chemisorption, Catalytic Behavior, and Stability of Supported Au Catalyst for the Propylene Epoxidation Reaction

The supported Au/TiO2 and Au/TiO2-SiO2 catalysts were prepared by deposition precipitation method. The TPD study reveals that propylene oxide competes with propylene to be adsorbed on the same adsorptive center-Ti^n＋ site on the surface of the catalyst and that the adisorbing capacity of the catalyst for propylene oxide is larger than that for propylene. Catalytic behavior for propylene epoxidation with H2 and O2 was tested in a micro-reactor. Under typical conditions, the selectivity for propylene oxide is over 87%. The TG curves show that PO successive oxidation cause carbon deposition on the active center and deactivation of the Au catalysts. Because the amounts of Tin＋ site decrease significantly, and consequently the separation between Ti^n＋ sites increases, the Au/TiO2-SiO2 catalyst is more stable than Au/TiO2.

Kinetics and mechanistic insights into the active sites of Au catalysts for selective propylene oxidation

Identification of the catalytically active sites emerges as the prerequisite for an atomic-level comprehensive understanding and further rational design of highly efficient catalysts.Here,we demonstrate a kinetics strategy to identify the active sites of Au catalyst for the disentanglement of geometric and electronic effects on the selective oxidation of propylene to acrolein.Both the Ti-containing titanium-silicalite-1(TS-1)and Ti-free silicalite-1(S-1)were employed as supports to immobilize Au catalysts,which were investigated by a combination of multiple characterization,kinetics analysis,crystal structure modelling.The Au(111)sites are identified as the main active site for acrolein formation,while their electronic effects are highly relevant to the presence or absence of Ti.Moreover,propylene epoxide(PO)formation mainly involves the co-participation of Au and Ti sites,the proximity between Au and Ti sites is found to have less influences on PO formation in a certain distance.In comparison,acrolein is very likely to generate over Au(111)sites via the hydrogen-assisted O_(2) activation to oxygenated species for its oxidizing propylene.The insights gained here could guide the design and preparation of Au catalysts for selective propylene oxidation.

Au/Cu-Co催化剂上甘油选择性氧化制二羟基丙酮的研究

二羟基丙酮(DHA)是甘油选择性氧化的高附加值产物,在农业、医药等领域具有重要的应用价值。本文以溶胶-凝胶法和硬模板法制备的CuO和Cu-Co金属氧化物复合材料为载体并负载金制备了催化剂,研究了其在非碱性条件下催化甘油氧化为二羟基丙酮的性能。活性评价结果表明,Au/Cu_(0.75)Co_(0.25)催化剂具有最高的催化活性,表现出了良好的选择性,在最佳的反应条件下,甘油转化率为69.0%,DHA选择性为99.7%,催化剂较高的活性可能是由于Co的加入增强了Au与载体之间的相互作用,使得电子云密度更容易向Au发生偏移从而形成更多的Au^(0)物种并且提高了Au的颗粒分散度,Au^(0)的增加有利于形成更多的晶格氧物种O_(latt),从而增强了甘油的活化和转化,更小的Au粒径也有利于催化剂上甘油的吸附和活化,从而促进了DHA的生成。

气氛环境下Au/CeO_(2)催化剂烧结行为的原位电镜研究

气氛环境下原位研究催化剂的烧结行为,能够为理解催化剂在预处理以及反应条件下的烧结机理和高稳定催化剂的设计提供重要的实验依据。本文以Au/CeO_(2)模型纳米催化剂为研究对象,利用环境透射电子显微镜原位观察其在O_(2)与CO气氛下的高温动态烧结过程。实验发现,负载在CeO_(2)上的Au纳米颗粒在O_(2)与CO气氛环境中表现出不同的烧结行为,其在O_(2)气氛下具有较高的烧结速度,同时存在颗粒迁移与聚集长大(particle migration and coalescence,PMC)和奥斯特瓦尔德熟化(Ostwald ripening,OR)两种烧结过程;在CO气氛下烧结速度较慢,烧结过程以OR为主。对比不同气氛环境下烧结后催化剂的表面结构可知,CO增加了CeO_(2)表面台阶的数量以及表面氧空位浓度,增强了载体对Au颗粒的锚定作用,从而提升Au/CeO_(2)催化剂的稳定性。

醋酸乙酯在Pd/Au表面的形成机理研究

采用密度泛函理论研究了醋酸乙烯合成过程中关键副产物醋酸乙酯在Pd/Au(100)及Pd/Au(111)表面的形成机理,从微观层面揭示Pd/Au(100)及Pd/Au(111)表面不同Pd原子数、Pd/Au原子构型对醋酸乙酯形成的影响。研究结果表明,Pd/Au(100)和Pd/Au(111)表面邻位Pd活性位构型最有利于醋酸乙酯的生成,而随着Pd/Au表面Pd原子数的增加,生成醋酸乙酯的反应活性逐渐降低,团簇Pd活性位(Pd原子数大于等于4)可以有效抑制醋酸乙酯的生成。该机理为开发高选择性Pd/Au催化剂、抑制醋酸乙酯副产物生成提供了理论依据。

乙烯气相法制醋酸乙烯Pd-Au催化剂研究进展

醋酸乙烯(VAc)是重要的化工原料,具有良好的应用价值。随着光伏行业的迅速发展以及环保要求的提升,我国对高品质醋酸乙烯(即乙烯气相法醋酸乙烯)的需求逐年增加,开发高催化活性、高目标产物选择性、高稳定性以及低成本的乙烯气相法制醋酸乙烯Pd-Au催化剂具有重要意义。首先,综述了乙烯气相法制醋酸乙烯催化剂的发展,概述了Pd-Au催化剂的载体、活性组分以及醋酸钾助剂的作用,分析了乙烯气相法制醋酸乙烯的两种反应机理和Pd-Au催化剂的失活原因,阐述了由浸渍法制得蛋壳型Pd-Au催化剂的制备过程。然后,总结了研究者为进一步提高催化性能、降低催化剂成本在催化剂改进方面的研究成果,包括载体改性和异型化,以及活性组分的浸渍、陈化、还原、水洗及干燥等步骤的改进。最后,提出了未来乙烯气相法醋酸乙烯催化剂的研究方向。

Surface pits stabilized Au catalyst for low-temperature CO oxidation

Development of active and stable catalysts for low-temperature CO oxidation has long been regarded as a hot topic.In this contribution,we used CeO_(2) with high-density surface pits as support to prepare an active and stable Au/CeO_(2) catalyst by an adsorption-deposition method.The obtained 0.05 wt%Au/CeO_(2)-TD(where TD represents thermal decomposition)can maintain its activity at 80℃ for more than 20 h or even after calcination at 800℃ for 2 h.The characterization results showed that the high-density surface pits on CeO_(2)-TD play a decisive role in the stabilization of Au and enhancement of the redox property.This work may provide a new strategy to improve the stability of supported metal catalysts by a simple and conventional method.

Performant Au hydrogenation catalyst cooperated with Cu-doped Al_(2)O_(3) for selective conversion of furfural to furfuryl alcohol at ambient pressure

Catalytic hydrogenation of furfural to furfuryl alcohol is an important upgrading process for valorization of biomass-derived furanyl platform molecules.However,selective hydrogenation of a,b-unsaturated aldehydes like furfural to the corresponding alcohols at ambient pressure remains challenging in sustainable chemistry.Till date heterogeneous Au hydrogenation catalyst has been scarcely reported for this reaction due to the low reactivity of Au for H_(2)dissociation.In this work,we showed that Au nanoparticles(loading:0.2 wt%)with a mean size of about 3 nm supported on Cu-doped Al_(2)O_(3)can efficiently hydrogenate furfural to furfuryl alcohol in liquid phase at ambient pressure.We demonstrated that doping a small amount of Cu(2 mol%)to g-Al_(2)O_(3)may modify the Lewis acidity-basicity of Al_(2)O_(3)and simultaneously induce the presence of sufficient Cu^(+) species on surface,which facilitated the hydrogen transfer from i-PrOH to furfural.Moreover,we observed an enhanced reactivity of Au toward molecular H_(2)via cooperation with the Lewis acidic-basic Cu_(2)O-Al_(2)O_(3)support.Hence,100%yield to furfuryl alcohol with a productivity of 0.98 g_(FA),h^(-1),g^(-1)_(cat.)at 120C and 0.1 MPa H_(2)can be obtained.The prepared Au/Cu-Al_(2)O_(3)catalyst was found reusable and was effective to the concentrated furfural solution,as well as several typical unsaturated aldehydes.

Au负载催化剂应用于水煤气变换制氢反应的研究进展

水煤气变换反应是目前广泛应用于制氢的方法,应用于水煤气变换反应的催化剂成为了重要的研究热点.我们在简述传统水煤气变换催化剂的基础上,重点介绍了Au负载型催化剂应用于水煤气变换反应的相关文献,针对Au负载型催化剂的载体种类、制备方法以及催化剂活性机理做出了详细分析.强调了影响水煤气变换反应催化剂的重点参数及Au负载型催化剂的发展趋势,以便为提高催化剂催化活性、设计Au负载催化剂并应用在水煤气变换反应中的研究者提供必要的参考信息.

Au/FeO_x-TiO_2 as an efficient catalyst for the selective hydrogenation of phthalic anhydride to phthalide

Au/FeOx-TiO2,prepared by deposition-precipitation method,is an efficient and stable catalyst for the liquid phase selective hydrogenation of phthalic anhydride to phthalide under mild reaction conditions.

Rational construction of metal–base synergetic sites on Au/Mg-beta catalyst for selective aerobic oxidation of 5-hydroxymethylfurfural

The selective aerobic oxidation of biomass-derived 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid (FDCA, a potential renewable substitution of fossil-based terephthalic acid to produce polyethylene 2,5-furandicarboxylate plastic) is an appealing transformation for constructing eco-friendly and sustainable chemical processes. Au supported catalysts have showed encouraging performances for this well-received conversion, whose catalytic behavior was greatly affected by the adopted support derived from the existence of metal-support interactions. Herein, a series of Mg-Beta zeolites were hydrothermally synthesized via developed structural reconstruction, which were employed as basic supports for Au catalysts to construct bifunctional catalysts. The relationship between structure (Au particle size, basicity within zeolites and Auδ+ contents) and FDCA yield was concretely established. The conclusion was made that the utilization of Mg-Beta zeolites with strong basicity as the support could not only improve the FDCA yield but also decrease the amount of additional base. Furthermore, the possible reaction mechanism was also proposed via tracking time-dependent variations of corresponding organics and controlled experiment. This work provides some guidance for rationally designing multifunctional catalysts in the view of integrating metal catalysts with metallosilicate zeolites, which was beneficial to the catalytic upgrading of organic compounds with multiple functional groups.

Base-free aerobic oxidation of glycerol on TiO_2-supported bimetallic Au–Pt catalysts

The aerobic oxidation of glycerol provides an economically viable route to glyceraldehyde, dihydroxyacetone and glyceric acid with versatile applications, for which monometallic Pt, Au and Pd and bimetallic Au-Pt, Au- Pd and Pt-Pd catalysts on TiO2 were examined under base-free conditions. Pt exhibited a superior activity relative to Pd, and Au-Pd and Pt-Pd while Au was essentially inactive. The presence of Au on the Au-Pt/TiO2 catalysts led to their higher activities （normalized per Pt atom） in a wide range of Au/Pt atomic ratios （i.e. 1/3-7/1 ）, and the one with the Au/Pt ratio of 3/1 exhibited the highest activity. Such promoting effect is ascribed to the increased electron density on Pt via the electron transfer from Au to Pt, as characterized by the temperature-programmed desorption of CO and infra-red spectroscopy for CO adsorption. Meanwhile, the presence of Au on Au-Pt/TiO2, most like due to the observed electron transfer, changed the product selectivity, and facilitated the oxidation of the secondary hydroxyl groups in glycerol, leading to the favorable formation of dihydroxyacetone over glyceraldehyde and glyceric acid that were derived from the oxidation of the primary hydroxyl groups. The synergetic effect between Au and Pt demonstrates the feasibility in the efficient oxidation of glycerol to the targeted products, for example, by rational tuning of the electronic properties of metal catalysts.

Catalytic activity of Au/Fe-PILC and Au/Fe-oxide catalysts for catalytic combustion of formaldehyde

Iron polymeric hydroxygroups pillared clays(Fe-PILC) were prepared by Na+-montmorillonite with iron pillaring agent. 2.01Au/Fe-PILC catalyst was obtained by deposited-precipitation(DP) method. 2.52Au/Fe-oxide catalyst was prepared by co-precipitation method. The catalytic activity of these catalysts was measured by catalytic combustion of formaldehyde. The catalyst of 2.01Au/Fe-PILC exhibits the high catalytic activity. The catalytic combustion reaction of formaldehyde proceeds at considerable rates at 20 ℃ and complete burn-off of formaldehyde is achieved at 120 ℃. The structure of catalysts,the valence state of gold and the size of gold particles were investigated by means of X-ray powder diffractometry,X-ray photoelectron spectroscopy and transmission electron microscopy. The results show that gold atoms with partially positive charge exist in the catalyst and play an important role in the catalytic activity. In addition,nano-sized,well-dispersed gold particles and good adsorption properties of support are necessary to obtain high activity Au catalysts for catalytic combustion of formaldehyde.

Synthesis of Ni@Au Core-shell Nanoparticles and Its Applications in Ullmann Reaction as a Synergistic Catalyst

The Ni@Au core-shell nanoparticles had been successfully synthesized from aqueous solution by one-step route at room temperature. The Ni@Au nanoparticles can be an excellent catalyst for Ullmann reaction. The advantage of Ni@Au is that the catalyst does not need additional reducing agents. The Au shell can effectively protect the Ni core from oxidation. The Ni core and Au shell have both composited in structure and cooperated in function.

Au和Ag修饰TNTAs阵列及光电催化甘油转化研究

通过阳极氧化法制备TiO_(2)纳米管阵列(TNTAs),管径是60 nm和管长是5.4μm。进一步利用电沉积法制备了Au和Ag修饰的TNTAs/Au和TNTAs/Ag纳米管阵列。评价了负载不同Au和Ag含量对光阳极光电催化转化甘油耦合产氢耦合的影响。结果表明,负载Au和Ag的TNTAs可将甘油光电催化转化为甘油醛(GLD)、二羟基丙酮(DHA)等高附加值产品并协同产氢。TNTAs/Au(0.08 mmol/L)和TNTAs/Ag(0.04 mmol/L)的催化性能最高,其产氢速率分别为213.8,198.1μmol•cm^(-2)•h^(-1),甘油转化率为4.6%、4.4%,DHA的选择性为15.4%、15.3%。样品的最佳性能归功于金属纳米颗粒的等离子共振效应,即金属作为电子陷阱有效地聚集了光激发的电子,TiO_(2)导带中的电子被转移到金属上,防止了光生电子-空穴对的复合,有效地提高了TiO_(2)纳米管阵列的催化性能。

用于CO氧化的Au催化剂载体研究进展

负载型金(Au)纳米催化剂对CO氧化反应过程具有较高的催化活性,而其负载载体的物化性质对Au催化活性的提升有显著影响。系统地总结了几种常见的Au催化剂载体(活性载体:TiO_(2)、CeO_(2)以及Co_(3)O_(4);惰性载体:SiO_(2)和Al_(2)O_(3))在协调Au催化氧化CO过程中的催化性能及相关的作用机制,重点分析了各载体对催化性能的影响,对负载型Au催化剂载体的选择及设计提供指导,并对未来Au催化剂的发展方向做了展望。

Liquid Phase Hydrogenation of <i>p</i>-Chloronitrobenzene on Au-Pd/TiO₂Catalysts: Effects of Reduction Methods

The effects of palladium addition and the reduction methods on Au/TiO2 were investigated. Pd was loaded on TiO2 firstly by incipient-wetness impregnation, Au was then loaded by deposition-precipitation method. The nominal loadings of Au and Pd were 1 wt% and 0.01 wt%. The bimetallic catalysts were reduced by heating at 453 K, by flowing H2 at 423 K, or by NaBH4 at 298 K. The catalysts were characterized by ICP, XRD, TEM, HRTEM, TPR and XPS. Hydrogenation of p-chloronitrobenzene was carried out at 1.2 MPa H2 pressure and 353 K. The results showed that even adding very small amount of Pd could enhance activity and selectivity of p-chloroaniline significantly. Pd and Au formed alloy and Pd could donate partial electron to Au. Pd metal on the surface of alloy could adsorb hydrogen and enhanced the activity. The pretreatment methods did not change particle size significantly, all were below 4 nm. The sample reduced by NaBH4 could have higher concentration of Au0 and sustain small Au particle size, resulting in high activity.

Study on Au/Al_2O_3 catalysts for low-temperature CO oxidation in situ FT-IR

Au/Al2O3 catalyst was prepared by a modified anion impregnation method and investigated with respect to its initial activity and stability for low-temperature CO oxidation.The activity changes of the catalyst were examined after separate treatment in CO＋O2 or CO2 ＋O2 .Furthermore,in situ FT-IR studies were performed to investigate the species on the surface when CO or CO＋O2 or CO2 ＋O2 was selected separately as adsorption gas.The results showed that Au/Al2O3 catalyst exhibited very high initial activity,but the catalytic activity was found to decrease gradually during CO oxidation with time on stream.And also,the activity of the catalyst declined after treatment in CO＋O2 or CO2 ＋O2 .The formation and accumulation of carbonate-like species during CO oxidation or treatment in CO＋O2 or CO2 ＋O2 might be mainly responsible for the activity decrease,which was reversible.