甲醇水相重整制氢原位还原糠醛制备糠醇

基于在雷尼镍催化剂作用下,甲醇水相重整产氢和糠醛液相加氢两反应的反应条件(温度、压力、液相)相近,研究了不需要外部提供氢源的情况下,液相原位还原糠醛的可行性。通过反应温度、反应物配比和催化剂用量的优化实现了水相制氢与液相加氢二个反应较好的耦合,在反应温度120℃、反应压力0.8MPa和水、甲醇、糠醛的体积比为25:125:5的条件下,原位加氢产物糠醇的选择性优于传统的液相加氢还原法,为糠醛选择性加氢提供了一条新的技术路线。     

Morphology and activity relationships of macroporous CuO-ZnO-ZrO_2 catalysts for methanol synthesis from CO_2 hydrogenation

A series of macroporous CuO-ZnO-Zr0_2(CZZ) catalysts with different Zn/Zr ratios were successfully prepared by template method and characterized by X-ray diffraction(XRD),N_2 adsorption,reactive N_2O adsorption,scanning electron microscopy(SEM),H_2 temperature-programmed reduction(H_2-TPR),and transmission electron microscopy(TEM).The activity of the catalysts was tested for methanol synthesis from CO_2 hydrogenation.It is found that the increase in the Zn/Zr ratio could lead to the sintering of the catalysts,destroying the macroporous structure integrity.The macroporous CZZ catalysts own lower Zn/Zr ratio,exhibiting a better morphology and activity.For comparison,the conventional nonporous CZZ catalysts were also investigated.The results show that the CZZ catalysts with macroporous structure own smaller particles,higher CO_2 conversion,and CH_3OH yield.It reveals that the macroporous structure could inhibit the growth of the particle size,and the special porous structure is favorable for diffusion and penetration of CO_2,which could improve the catalytic activities.     

Influence of rare earth promoters on the performance of Ni/Mg（Al）O catalysts for hydrogenation and steam reforming of toluene

CeO₂-, La₂O₃-, and ZrO₂-promoted Ni/Mg(Al)O catalysts synthesized by hydrotalcite-type precursors have been investigated with respect to catalytic activity and carbon formation in the hydrogenation and steam reforming of toluene as a model tar compound. X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) specific surface area and H₂-temperature programmed reduction (TPR) were used to observe the characteristics of the prepared catalysts. The carbon formation and its amount on the used catalysts were examined by transmission electron microscope (TEM), scanning electron microscope (SEM) and thermogravimetric (TG). The trend of catalytic activity as derived from the experimental results followed the order: Ni-Ce>Ni-Las>Ni-Zr>Ni. The catalyst modified with CeO₂ exhibited the highest catalytic performance and had good carbon resistance in the hydrogenation and steam reforming of toluene. A toluene conversion of 96.8%, a CH₄ yield of 45.2% and a CO yield of 50.4% have been achieved. The addition of promoters led to better dispersion of nickel species and higher interaction nickel-support, which were favorable for increasing the catalytic activity and effectively preventing carbon formation.     

喷雾干燥法制备碳载铂钴镍合金催化剂及其甲醇催化氧化性能研究

本文以氯铂酸、氯化镍和硝酸钴为原料,XC-72炭黑为载体,通过雾化干燥法结合煅烧还原制备碳载铂基（PtCo Ni）分散性好的多元合金纳米粒子催化剂。重点研究表面经过改性的炭黑对合金纳米粒子形成和分散的影响规律,研究碳载PtCoNi（原子比为1:1:1）合金纳米粒子的甲醇催化氧化活性、抗CO中毒能力和耐久性,以及不同原子比对催化氧化甲醇活性和抗CO中毒能力的影响规律。研究结果表明,采用表面改性后的炭黑作为载体,制备的碳载铂基（PtCoNi）催化剂为合金纳米粒子,且纳米粒子在炭黑表面分散均匀,粒径分布在1-4nm,平均粒径为2.3nm;与商用的Pt/C催化剂相比,PtCoNi/C（原子比为1:1:1）催化剂具有更高的甲醇催化氧化活性、耐久性和抗CO中毒性;不同原子比铂基多元催化剂在催化氧化甲醇活性上的顺序为：PtCoNi/C>Pt3CoNi/C>Pt5CoNi/C,抗CO中毒性顺序为：PtCoNi/C>Pt3CoNi/C>Pt5CoNi/C。     

贵金属催化剂在石油化工中的应用

根据反应类型总结了贵金属在石油化工如催化重整反应、加氢催化反应、氧化反应、脱氢催化、异构化反应中的应用。对比分析了不同研究方法得到的共性成果及存在的问题,并对未来贵金属催化剂在石油化工中的应用做了展望。     

Preparation and catalytic activity of CO-resistant catalyst core-shell Au@Pt/C for methanol oxidation

Au@Pt core-shell nanoparticles were successfully synthesized by a successive reduction method and then assembled on Vulcan XC-72 carbon surface.Furthermore,its composition,morphology,structure,and activity towards methanol oxidation were characterized by UV-vis spectrometry,transmission electron microscopy (TEM),high-resolution TEM (HRTEM),X-ray diffraction (XRD),X-ray photoelectron spectroscopy (XPS),and cyclic voltammetry (CV).Results reveal that Au@Pt/C catalyst has better activity towards methanol oxidation than the pure platinum prepared under the same conditions.When the atomic ratio of Au to Pt in the prepared Au@Pt/C catalyst is 1∶2,this catalyst exhibits best electrocatalytic activity towards methanol oxidation in acidic media,and the peak current density on this catalyst is ～2.0times higher than that on Pt/C catalyst.The better catalytic activity of Au@Pt/C results from its better resistance to toxic CO than Pt/C because the CO oxidation on Au@Pt/C is 60 mV more negative than the case on Pt/C.     

BaO对单Pd催化剂净化甲醇燃料车尾气性能的影响

利用FIB/SEM切片、XRD、TEM和EDX、EELS等先进分析技术对微球模板法所制备的Au/Ag泡沫材料的微观结构、形貌、成分及成分分布等进行了细致的研究.结果表明:由微球状Au/Ag球壳堆积而成的泡沫材料中微球直径约8 μm,微球壁厚200～1200 nm; Au/Ag泡沫材料的球壳可细分为3层,内层和外层为Au/Ag合金的微粒,中间主要是非晶碳层,夹杂有少量的Au/Ag微粒;Au/Ag泡沫材料的骨架由单个空心球壳组成,球壳之间通过接触点的金属镀层连接在一起;球壳上有小孔状结构,是在热分解法去除聚苯乙烯微球模板对形成的;球壳壁厚分布不均匀,少数球壳有塌陷、变形、破裂等现象.这些详细的分析有助于改进工艺,提高Au/Ag泡沫材料的制备质量.     

超临界CO2沉积技术制备负载钌炭催化剂

以氯化钌为活性前驱体,活性炭为载体,采用超临界CO2沉积技术制备了负载钌/炭催化剂,以葡萄糖催化加氢反应考察了催化剂的活性,研究了助溶剂种类,助溶剂用量,超临界压力对催化剂活性的影响,并用SEM、XRD、XPS对催化剂表面的形貌、晶形及钌分布情况进行了表征.结果表明:超临界CO2沉积技术可有效提高负载钌炭催化剂的活性,在实验范围内,当助溶剂为甲醇,用量为2 ml,超临界CO2压力为12.0 MPa时制得催化剂的活性最佳,其催化活性是传统水浸渍方法制得样品的1.48倍;钌在催化剂中以无定型的非晶形式存在,钌在活性炭表面均匀分布,超临界沉积技术进一步增强了活性组分钌和载体间的相互作用.     

Catalytic behaviour and surface properties of supported lanthana

This paper deals with the role of dispersed lanthana as an active phase in several catalytic reactions: CO hydrogenation, CO oxidation, and oxidative dimerization of methane.

Characterization of the prepared catalysts indicates that lanthana can be effectively dispersed on silica and on ceria. While in the case of silica-supported catalysts lanthana appears at the surface, leading to an almost full coverage for loadings higher than 40%, in the case of ceria-based systems, lanthana forms a solid solution with the support.

In all the reactions studied, the presence of lanthana can be related to significant changes in the catalytic properties of the bare supports. Thus, the selectivity towards the total oxidation products observed on pure ceria is decreased, and the low activity shown by silica is enhanced. For the CO+H₂ reaction, the addition of lanthana also generates upgraded products.     

稀土在直接甲醇燃料电池铂基催化剂中的应用及研究进展

直接甲醇燃料电池(DMFC)以其高效、低污染的特点而备受关注。铂基电催化剂被认为是DMFC阳极的有效催化剂。但由于在甲醇氧化过程中铂的活性中心容易被产生的中间产物如CO等吸附和堵塞,导致催化活性降低,稳定性差,严重制约了直接甲醇燃料电池推广应用。稀土元素由于其4f轨道独特的电子结构和相应的镧系收缩效应,在铂基电催化剂中可有效提高铂催化剂的活性和耐久性。本文简要总结近年来稀土氧化物作为铂基电催化剂的助催化剂、碳材料掺杂改性剂和载体在甲醇氧化反应中的催化活性和抗CO中毒能力应用研究,以及铂-稀土金属(Pt-RE)纳米合金催化剂对DMFC长期运行稳定性的影响;并对稀土元素在铂基电催化剂中的应用发展提出了展望。     

硅钨酸修饰多晶铂电极及其电催化性能

通过循环伏安扫描制备了硅钨酸修饰多晶铂电极，在电极制备过程中发现，SiW12在Pt电极表面的氢区发生了氧化-还原反应，而在氧区使电极表面含氧粒子的吸附增加。通过循环伏安和恒电位I-t曲线研究了该修饰电极在硫酸溶液中的电化学行为和对甲醇氧化的电催化作用。研究结果表明：硅钨酸修饰多晶铂电极提高了甲醇氧化的催化活性和抗CO中毒性。     

Ti/nano-TiO2-Pt复合电极催化甲醇氧化的研究

采用溶胶-凝胶法(sol-gel)制备纳米TiO2(Ti/nano-TiO2)膜电极,再用电沉积法在纳米TiO2膜上修饰Pt微粒,制成Ti/nano-TiO2-Pt复合电极.用循环伏安法研究了纯Pt丝电极和Ti/nano-TiO2-Pt电极对甲醇氧化的电催化活性以及稳定性.结果表明:对甲醇氧化,复合电极比Pt丝电极具有更高的催化活性,且对甲醇氧化中间产物CO的吸附量少,因而不易中毒;复合电极载铂量达到一定值时,电极具有最强的催化活性.     

喷雾干燥法制备铂镍合金三维纳米骨架材料及增强甲醇氧化性能研究

本文以氯铂酸氨和氯化镍为原料,氯化铵作为造孔剂,通过雾化干燥法结合煅烧还原制备铂镍合金三维纳米骨架材料,该新型材料可增强催化甲醇氧化性能。重点研究了前驱体中加入氯化铵和不加入对铂镍合金三维纳米骨架形成的影响规律,研究不同结构的铂镍合金三维纳米骨架材料对催化氧化甲醇活性和稳定性的影响规律。研究结果表明,通过加入适量的氯化铵作为造孔剂,制备的铂镍合金为单项固溶体结构(面心立方结构),由弯曲纳米线交织组成三维纳米骨架材料,纳米线直径小于10 nm,纳米孔10 nm左右;与商用Pt黑和不加入氯化铵制备的铂镍合金纳米材料相比,PtNi合金三维纳米骨架材料具有更高的甲醇催化氧化活性(611.4 mA.mg_^-1Pt),分别是商用Pt黑的3.58倍(170.8 mA.mg_^-1Pt)和PtNi合金纳米材料(不加氯化铵)的1.36倍(448.8 mA.mg_^-1Pt);在催化甲醇氧化性能稳定性上,PtNi合金三维纳米骨架材料表现出最好的稳定性,稳定性顺序为：PtNi合金三维纳米骨架材料 > PtNi合金纳米材料(不加氯化铵)> 商用Pt黑。此外,本文对该方法进行了扩展,成功的制备了铂镍钴铜钌铱钯(PtNiCoCuRuIrPd)高熵合金三维纳米骨架材料。     

K+-enhanced electrocatalytic CO2 reduction to multicarbon products in strong acid

Electrocatalytic CO2 reduction reaction(CO2RR)has been regarded as a highly effective strategy to produce valuable fuels and feedstocks,contributing to achievin...     

热处理对Pt纳米线电催化性能的影响

采用阳极氧化铝(AAO)模板法电化学沉积制备了Pt纳米线催化剂,并进行了热处理。通过X射线衍射(XRD)、扫描电子显微镜(SEM)和电化学测试对热处理前后Pt纳米线催化剂的晶体结构、形貌和电催化性能进行了表征,并与商业碳载铂(Pt/C)做对比。SEM照片表明制备了表面粗糙的Pt纳米线。循环伏安法(CV)和计时电流曲线表明,Pt纳米线较Pt/C催化活性高,退火后Pt纳米线更利于甲醇氧化,且稳定性更好。旋转圆盘电极(RDE)测试研究发现,未经热处理的Pt纳米线催化剂氧还原反应(ORR)极化曲线的半波电势相对Pt/C有正移,有更大的极限扩散电流,利于氧还原反应的发生。     

RuH2 (PPh3)4 在催化有机反应中的应用

介绍了RuH2(PPh3)4 (1)在催化有机反应中的应用进展 .含有Ru-H键的结构简单配合物1能催化氢转移反应(异构化、氧化反应和还原反应)、碳碳键形成反应和氰基三键的亲核加成反应;其催化的反应具有条件温和、效率高和环境友好的特点,因而具有潜在的工业应用价值和"一石多能"的催化方法论意义.     

铱的氯桥双核配合物作为均相催化剂在有机合成中的应用

铱的氯桥双核配合物—1,5-环辛二烯氯化铱二聚体[Ir(COD)Cl]2由于具有独特的催化性质,已作为均相催化剂,广泛应用于各类有机合成反应进行重要药品和精细化工产品的制备。这些反应包括烷基化反应,氢化反应,氧化反应及环加成反应。[Ir(COD)Cl]2催化剂具有适用底物范围广、原料易得,对映选择性高的优点。本文对[Ir(COD)Cl]2催化的反应类型、应用和相关的反应机理进行介绍和总结。     

Ru-doped phosphorene for electrochemical ammonia synthesis

The electrochemical ammonia synthesis has attracted increasing attention due to its energy saving characteristics.However,developing novel electrocatalysts and their mechanism remain great challenges.Here,several transition metal(TM) atoms doped on phosphorene were studied as N_2 fixation electrocatalysts by using density functional theory(DFT) calculations.The results demonstrate that single Ru atom doped phosphorene shows an excellent catalytic activity for ammonia synthesis via the enzymatic pattern.A small overpotential of 0.696 V is achieved for this process.The effect of oxidation in the catalyst was also discussed in our work.Oxidation deactivates the catalyst,which should be avoided in the experiment.Our outcomes offer a novel perspective for single-atom catalytic ammonia synthesis with phosphorene as a substrate.     

Synthesis of biomorphic hierarchical CeO2 microtube with enhanced catalytic activity

A biomorphic CeO₂ microtube with multiple-pore structure was fabricated by using the cotton as biotemplate, through cerium nitrate solution infiltration and thermal decomposition. Field emission scanning electron microscope (FESEM), powder X-ray diffraction (XRD), transmission electron microscope (TEM), N₂ adsorption–desorption isotherms, temperature-programmed reduction (TPR) and CO oxidation were used to characterize the samples. The results indicated that the synthesized products were composed of crystallites with grain size about 9 nm and exhibited a fibrous morphology similar to the original template and possessed a specific surface area (BET) of 62.3 m²/g. Compared with the conventional CeO₂ particles, the synthesized materials showed a superior catalytic activity for CO oxidation. For the synthesized fibrous CeO₂, the CO conversion at 320 °C was above 90% and a 100% CO conversion was obtained at 410 °C.     

Theoretical investigation of the CO oxidation on Al<Subscript>12</Subscript>Zr Cluster

Equilibrium geometries of Al₁₂Zr cluster were systematically studied on the basis of density functional theory with generalized gradient approximation. To gain insights into high catalytic activity we use the CO oxidation as a benchmark probe. In Al–Zr bimetallic clusters, Zr site is the catalytically active centre, the adsorption of CO and O₂ on the same site respectively (single-site mechanism), a Langmuir-Hinshelwood (LH) mechanism is proposed, which proceed via two steps, CO + O₂ → CO₂ + O and CO + O → CO₂. Two CO oxidation mechanisms of two CO₂ molecules as product have been simulated. For the later mechanism, the key step is the O–O bond scission in the OCOO* intermediate, which is significantly accelerated due to the attack of the neighboring CO molecule. The calculated barriers for the later reactions are lower compared with the former reaction. Detailed reaction paths corresponding to this case are calculated. Our study suggests that the CO oxidation catalyzed by Al₁₂Zr cluster is likely to occur at the room temperature.