WO2020082410A1 - 一种负载型双金属核壳结构催化剂及其制备方法 - Google Patents

一种负载型双金属核壳结构催化剂及其制备方法 Download PDF

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WO2020082410A1
WO2020082410A1 PCT/CN2018/113555 CN2018113555W WO2020082410A1 WO 2020082410 A1 WO2020082410 A1 WO 2020082410A1 CN 2018113555 W CN2018113555 W CN 2018113555W WO 2020082410 A1 WO2020082410 A1 WO 2020082410A1
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core
catalyst
shell
pdm
shell structure
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French (fr)
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李殿卿
马瑞
贺宇飞
冯拥军
冯俊婷
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北京化工大学
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Priority to US16/493,275 priority Critical patent/US10913052B1/en
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Definitions

  • the invention belongs to the field of catalyst preparation, and particularly relates to a supported bimetallic core-shell catalyst and a preparation method thereof.
  • Bimetallic catalysts have the characteristics of composition and adjustable structure due to the synergy between two metals (including geometric effects and electronic effects), and are widely used in selective hydrogenation, oxidation, hydrogenolysis and reforming reactions.
  • the bimetallic catalyst can be divided into alloy structure, heterostructure and core-shell structure according to the distribution of the two metals.
  • the bimetallic core-shell structure due to the difference in core-shell composition, makes this type of material more versatile, and the composition is highly variable.
  • the core-shell structure has its unique chemical properties: electron transfer between the core layer and the shell layer, the lattice strain of the surface metal atoms and the full exposure of the active metal on the surface.
  • the core-shell structure M @ N (M and N each represents a metal) of a single metal shell is less stable, and it is difficult to maintain the structure stability under harsh reaction conditions.
  • the bimetallic core-shell structure with the synthetic shell layer as the bimetallic alloy and the core as the single metal can not only exert the advantages of the core-shell structure, but also take advantage of the stability characteristics of the alloy, which is of great significance for improving the performance of the bimetallic catalytic material. .
  • the controllable preparation of such materials is still challenging. It has been reported in recent years that the method of epitaxial growth of seed crystals has been used to prepare supported core-shell structures.
  • the supported-core-shell structure has shown high research value in the field of heterogeneous catalysis, and has been radiated to the fields of electrocatalysis, photocatalysis, and optical devices.
  • This type of structure preparation method has the disadvantages of cumbersome reaction conditions, difficult to operate, high preparation cost, and species residue. Therefore, the controllable preparation of supported core-shell bimetallic catalysts and the application of such catalysts in heterogeneous catalytic reactions need to be further developed.
  • the purpose of the present invention is to provide a supported bimetallic core-shell structure catalyst, and another object is to provide a preparation method of the supported bimetallic core-shell structure catalyst.
  • the catalyst is used in petrochemical and fine chemicals. At present, it has been found that it has good application effect in selective hydrogenation of acetylene and anthraquinone.
  • the supported bimetallic core-shell structure catalyst provided by the present invention is expressed as M @ PdM / ZT, in which the active metal particles M @ PdM are core-shell structures, M is the core, and the diameter is 5-15 nm, and M represents the metals Ag and Pt , Au, Ir; PdM alloy is the shell layer, the thickness of the shell layer is 1-10nm; ZT is the carrier, ZT is hydrotalcite (Mg 2 Al-LDH), alumina (Al 2 O 3 ), dioxide One of silicon (SiO 2 );
  • the preparation method of the supported bimetallic core-shell structure catalyst provided by the present invention has the following steps
  • the M is one of Ag, Pt, Au and Ir;
  • the M salt is AgNO 3 , HPtCl 6 , Pt (C 5 H 7 O 2 ) 2 , H 2 IrCl 6 ⁇ 6H 2 O, Ir (C 5 One of H 7 O 2 ) 3 and HAuCl 4 ⁇ 4H 2 O;
  • the Pd salts are PdCl 2 , Pd (NO 3 ) 2 , Pd (C 5 H 7 O 2 ) 2 , Pd (CH 3 COO ) One of 2 ;
  • the reducing solution is a mixture of reducing agent and deionized water, wherein the mass percentage of water is 0-20%;
  • the reducing agent is: ethylene glycol, isopropyl alcohol , N, N-dimethylacetamide, N, N-dimethylformamide, glyceraldehyde.
  • FIG. 1 is an electron micrograph of Ag @ PdAg / Mg 2 Al-LDH prepared in Example 1. It can be seen that the metal particles of the active component in the supported catalyst are uniformly dispersed on the hydrotalcite carrier, and the metal particles are intact and uniform in size. The average particle size is 15.6 nm.
  • Figure 2 is the X-ray energy spectrum (EDX) of the metal particles in the Ag @ PdAg / Mg 2 Al-LDH catalyst prepared in Example 1 and the line scan results of metal Pd and Ag. Comparison of the distribution of the elements Pd and Ag can be seen, Ag is distributed throughout the metal particles and Pd is concentrated on the surface of the metal particles, so it can be determined that the metal particles of the active component of the catalyst are the core-shell structure of PdAg coated on the surface of Ag. In addition, it can be seen from the line scan results of the element Pd in FIG. 2 that the thickness of the PdAg alloy shell layer is 4 nm, and the core diameter is 8 nm.
  • EDX X-ray energy spectrum
  • FIG. 3 is an X-ray photoelectron spectrum of the Pd element of the Ag @ PdAg / Mg 2 Al-LDH catalyst prepared in Example 1.
  • FIG. 4 is a graph showing the selectivity of the target product ethylene with temperature during the selective hydrogenation of acetylene in the Ag @ PdAg / Mg 2 Al-LDH catalyst prepared in Example 1.
  • FIG. It can be seen from the figure that the catalyst has an ethylene selectivity higher than 95% in the temperature range of 30-100 ° C.
  • FIG. 5 is a graph showing the change of acetylene conversion rate and ethylene selectivity with time in the selective hydrogenation reaction of acetylene of the Ag @ PdAg / Mg 2 Al-LDH catalyst prepared in Example 1.
  • FIG. It can be seen from the figure that the catalyst does not deactivate after 50 hours of reaction, and the conversion rate of acetylene has remained above 96%.
  • the ethylene selectivity shows a similar trend. After a long period of reaction, the catalyst selectivity remains above 93%.
  • Example 6 is an electron micrograph of the Ag @ PdAg / Mg 2 Al-LDH catalyst prepared in Example 1 after 48 hours of selective hydrogenation of acetylene. It can be seen from the photo that after a long time of reaction, the metal particles have not agglomerated, and the metal particles of the active component are uniformly dispersed on the surface of the hydrotalcite carrier.
  • FIG. 7 is a scanning transmission electron microscope (STEM) photograph of metal particles of the Au @ PdAu / SiO 2 catalyst prepared in Example 2.
  • STEM scanning transmission electron microscope
  • the bulk of the metal particles is Au, that is, the metal particles have a core-shell structure with Au as the core and PdAu as the shell, and the thickness of the shell layer is about 2 nm.
  • Example 8 is a graph showing the change in the hydrogenation efficiency of the Ag @ PdAg / Mg 2 Al-LDH catalyst prepared in Example 1 and the Au @ PdAu / SiO 2 catalyst prepared in Example 2 in the anthraquinone hydrogenation reaction. It can be seen from the figure that the initial hydrogenation efficiency of both catalysts can reach 13.9g / L. Moreover, after 300 min of reaction, the hydrogenation efficiency of the catalyst was kept above 14.2 g / L, indicating that the bimetallic core-shell structure catalyst has excellent stability in this reaction.
  • FIG. 9 is a graph showing the variation of the effective anthraquinone selectivity with time in the anthraquinone hydrogenation reaction of the Ag @ PdAg / Mg 2 Al-LDH catalyst prepared in Example 1 and the Au @ PdAu / SiO 2 catalyst prepared in Example 2. It can be seen from the figure that after the reaction of the core-shell structure catalyst for 5h, the effective anthraquinone selectivity remains above 95%.
  • the beneficial effects of the present invention are: by using a one-step synthesis method, a carrier, a metal salt and a reducing agent solution are mixed to synthesize a M @ PdM / ZT catalyst in one step, wherein the active metal particles M @ PdM have a core-shell structure and the shell layer is composed of PdM alloy.
  • the dynamic behavior of the reduction of the two metal ions can be adjusted to achieve the construction of the core-shell structure; by controlling the concentration of metal ions, the composition of the active metal particles and the thickness of the shell can be adjusted.
  • the method is simple and versatile. Not only can the active metal reaction sites be fully exposed, but the construction of the surface alloy can also fully exert the synergy between the two metals.
  • the bimetallic core-shell mechanism catalyst prepared by this method exhibits excellent catalyst selectivity and stability in both acetylene selective hydrogenation and anthraquinone hydrogenation reactions.
  • Figure 1 is an electron micrograph of the Ag @ PdAg / Mg 2 Al-LDH catalyst in Example 1.
  • FIG. 2 is a line scan spectrum of X-ray Pd and Ag of metal particles of Ag @ PdAg / Mg 2 Al-LDH catalyst in Example 1.
  • FIG. 2 is a line scan spectrum of X-ray Pd and Ag of metal particles of Ag @ PdAg / Mg 2 Al-LDH catalyst in Example 1.
  • FIG. 3 is an X-ray photoelectron spectrogram of Ag @ PdAg / Mg 2 Al-LDH catalyst metal Pd in Example 1.
  • FIG. 3 is an X-ray photoelectron spectrogram of Ag @ PdAg / Mg 2 Al-LDH catalyst metal Pd in Example 1.
  • FIG. 4 is a graph showing the variation of ethylene selectivity with temperature of the Ag @ PdAg / Mg 2 Al-LDH catalyst in the selective hydrogenation of acetylene in Example 1.
  • FIG. 4 is a graph showing the variation of ethylene selectivity with temperature of the Ag @ PdAg / Mg 2 Al-LDH catalyst in the selective hydrogenation of acetylene in Example 1.
  • FIG. 5 is a graph showing the variation of acetylene conversion rate and ethylene selectivity with time in the selective hydrogenation of acetylene of the Ag @ PdAg / Mg 2 Al-LDH catalyst in Example 1.
  • FIG. 5 is a graph showing the variation of acetylene conversion rate and ethylene selectivity with time in the selective hydrogenation of acetylene of the Ag @ PdAg / Mg 2 Al-LDH catalyst in Example 1.
  • Example 6 is an electron micrograph of the Ag @ PdAg / Mg 2 Al-LDH catalyst in Example 1 after selective hydrogenation of acetylene for 48 h.
  • FIG. 7 is a scanning transmission electron microscope photograph of Au @ PdAu / SiO 2 catalyst metal particles in Example 2.
  • Example 8 is a graph showing the hydrogenation efficiency of Ag @ PdAg / Mg 2 Al-LDH in Example 1 and the Au @ PdAu / SiO 2 catalyst in Example 2 in the hydrogenation reaction of anthraquinone with time.
  • Example 9 is a graph showing the variation of the effective anthraquinone selectivity with time in the Ag @ PdAg / Mg 2 Al-LDH in Example 1 and the Au @ PdAu / SiO 2 catalyst in Example 2 in the anthraquinone hydrogenation reaction.
  • the evaluation device is the WFS-3015 micro-reaction bed of Tianjin Xianquan Company.
  • the operation steps are as follows:
  • the temperature of the reaction bed was raised to 150 ° C to pretreat the catalyst with nitrogen for 1 hour, and the nitrogen flow rate was 50 ml / min.
  • the reaction feed gas namely nitrogen, ethylene acetylene mixed gas and hydrogen
  • flow rate is 111, 55.5, 1.0mL / min; the ethylene acetylene mixed gas acetylene percentage content is 0.947%, the hydryne ratio is about 2.
  • the reaction temperature was controlled to 100 ° C, the reaction space velocity was 10050h -1 , and the relative pressure of the reaction system was 0.4MPa.
  • the concentration of the reactants and products was analyzed by online gas chromatography, the capillary column specification was 0.53 ⁇ 50mm, and the detector was a hydrogen flame detector. And use the normalization method for data processing.
  • the acetylene conversion rate and ethylene selectivity of the catalyst at 100 °C are shown in Table 1.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Comparative example Conversion rate of acetylene (%) 100 94 87 100 100 86 Ethylene selectivity (%) 94 91 100 74 91 72
  • the comparative sample is a PdPtAg / Mg 2 Al-LDH catalyst obtained according to the Chinese patent CN 103977794B, which was applied for in this laboratory.
  • the catalyst is dedicated to the selective hydrogenation of acetylene.
  • the evaluation device is a polytetrafluoroethylene liner reactor with a magnetic stirring and heating device. 25 mg of catalyst and 60 mL of anthraquinone working solution (concentration of 100 g / L anthraquinone working solution consist of 100 g of 2-ethylanthraquinone, 1 , 3,5-trimethylbenzene and 400mL of trioctyl phosphate) added to the reactor and closed, hydrogen gas was introduced into the reactor through a steel bottle to replace the air in the reactor, repeat 5 times. The reaction kettle was heated to 50 ° C, and hydrogen gas was introduced to make the pressure reach 0.3MPa, and the stirring speed was adjusted to 1200r / min to start timing. After 1.5 hours of reaction, a reaction sample was collected from the reaction gas outlet valve to evaluate the activity and selectivity and calculate the H 2 O 2 yield. The H 2 O 2 yield and space-time yield of the catalyst are shown in Table 2.
  • the comparative sample is a Pd / Al 2 O 3 catalyst for anthraquinone hydrogenation reaction obtained according to Chinese patent CN 103172097A. This patent is applied by this laboratory. This catalyst is dedicated to the anthraquinone hydrogenation reaction.

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Abstract

一种负载型双金属核壳结构催化剂及其制备方法，所采用的制备方法是将载体、金属盐和还原剂溶液混合，一步法合成M@PdM/ZT核壳结构催化剂。该催化剂的活性金属颗粒M@PdM为核壳结构，金属M为内核，M代表金属Ag、Pt、Au、Ir中的一种；壳层为PdM合金；ZT表示载体，Mg 2Al-LDH、Al 2O 3、SiO 2中的一种。基于金属离子还原电势的不同，在材料合成过程中通过改变温度和反应时间调控两种金属离子还原的动力学行为，实现核壳结构的构筑；通过金属离子浓度和比例的调控，实现壳层合金的组成和厚度可控制备。该双金属核壳结构催化剂用于乙炔选择性加氢反应和蒽醌加氢反应具有较好的应用效果。

Description

一种负载型双金属核壳结构催化剂及其制备方法 技术领域
本发明属于催化剂制备领域，具体涉及负载型双金属核壳催化剂及其制备方法。
背景技术
作为能源转化的基础，多相催化在国民经济中占有举足轻重的地位，而新型高效的负载型催化剂一直是推动多相催化技术发展的重要作用力。双金属催化剂由于两种金属间的协同作用(包括几何效应和电子效应)使其具有组成、结构可调的特点，广泛应用于选择性加氢、氧化、氢解以及重整等反应中。
对于双金属催化剂，按照两种金属的分布情况可以分为合金结构、异质结构、核壳结构。双金属核壳结构，由于核层-壳层组成的不同使得该类材料组成更多元，组成可调变性强。相比于合金结构，核壳结构有其独特的化学性质：核层-壳层之间的电子转移，表面金属原子的晶格应变以及活性金属在表面的充分暴露等。然而，单一金属壳层的核壳结构M@N(M和N各代表一种金属)稳定性较差，在苛刻的反应条件下很难保持结构稳定。因此设计合成壳层为双金属合金，核为单一金属的双金属核壳结构，一方面能发挥核壳结构的优势，同时可利用合金的稳定性特点，对于提高双金属催化材料性能具有重要意义。但是，该类材料的可控制备仍具挑战。近年来利用晶种外延生长的方法制备负载型核壳结构已有报道。文献Meng Min,Fang Zhicheng,Zhang Chao,Su Hongyang,He Rong,Zhang Renpeng,Li Hongliang,Li Zhi-Yuan,Wu Xiaojun,Ma Chao,Zeng Jie,Nano Letters,2016,16,3036以Pd立方块作为晶种，十六烷基三甲基氯化铵作为封端剂，以葡萄糖为还原剂，通过对Au，Cu离子还原动力学的调控，成功制备了Pd@AuCu核壳结构。Vismadeb Mazumder,Chi Maiofang,Karren L.More,Sun Shouheng,JACS,2010,132,7848中利用两步法，在表面活性剂存在的条件下，在Pd纳米颗粒表面生长FePt合金，最终得到了Pd@PtFe纳米颗粒。然而，外延生长法存在制备方法繁琐、表面活性剂残留覆盖活性位点等缺点。因此，设计简便可行的一步法，在无表面活性剂和保护剂条件下制备M@NM双金属核壳结构仍是纳米材料领域研究的难点之一。
综上所述，负载型-核壳结构由于其独特的结构特点在多相催化领域表现出较高的研究价值，并辐射至电催化、光催化以及光学器件等领域，但现有文献报道的该类结构制备方法存在反应条件繁琐不易操作、制备成本高、物种残留等缺点。因此，负载型核壳双金属催化剂的可控制备，以及该类催化剂在多相催化反应的应用研究尚需进一步开展。
发明内容
本发明的目的是为了提供一种负载型双金属核壳结构催化剂，另一目的是提供该类负载型双金属核壳结构催化剂的制备方法。该催化剂用于石油化工和精细化工中。目前发现用于乙炔选择性加氢反应和蒽醌加氢反应具有较好的应用效果。
本发明所提供的负载型双金属核壳结构催化剂，表示为M@PdM/ZT，其中活性金属颗粒M@PdM为核壳结构，M为内核，直径为5-15nm，M代表金属Ag、Pt、Au、Ir中的一种；PdM合金为壳层，壳层厚度为1-10nm；ZT表示载体，ZT是水滑石(Mg 2Al-LDH)、氧化铝(Al 2O 3)、二氧化硅(SiO 2)中的一种；
本发明所提供的负载型双金属核壳结构催化剂的制备方法，具备步骤如下
A.将M盐和Pd盐加入到还原性溶液中超声4-5min得到混合盐溶液；其中M和Pd离子总浓度为0.01-20mmol/L，M：Pd离子的摩尔比为0.1-10；
所述的M为Ag、Pt、Au、Ir中的一种；M盐为AgNO 3、HPtCl 6、Pt(C 5H 7O 2) 2、H 2IrCl 6·6H 2O、Ir(C 5H 7O 2) 3、HAuCl 4·4H 2O中的一种；所述的Pd盐为PdCl 2、Pd(NO 3) 2、Pd(C 5H 7O 2) 2、Pd(CH 3COO) 2中的一种；所述的还原性溶液是还原剂与去离子水的混合物，其中水的质量百分含量为0-20％；所述的还原剂为：乙二醇、异丙醇、N，N-二甲基乙酰胺、N，N-二甲基甲酰胺、甘油醛中的一种。
B.将上述混合盐溶液于40-50℃加热搅拌10-30min，加入载体，继续搅拌10-20min，升温至100-160℃，保持该温度0.5-24h得到黑色沉淀的悬浊液，降至室温，离心，洗涤，干燥得到灰色或黑色粉末；经表征证明为M@PdM/ZT催化剂；其活性组分金属颗粒为核壳结构，其中M为核，PdM合金为壳层。所述的载体为氧化铝(Al 2O 3)、二氧化硅(SiO 2)、水滑石(Mg 2Al-LDH)。
图1为实施例1制备的Ag@PdAg/Mg 2Al-LDH的电镜照片，可以看出负载型催化剂中活性组分金属颗粒均匀分散在水滑石载体上，金属颗粒晶型完好，尺寸均一，平均粒径为15.6nm。
图2为实施例1制备的Ag@PdAg/Mg 2Al-LDH催化剂中金属颗粒的X-射线能谱(EDX)金属Pd和Ag的线扫结果，对比元素Pd和Ag的分布可以看出，Ag分布于整个金属颗粒而Pd集中分布在金属颗粒表面，因此可以判定该催化剂活性组分金属颗粒是PdAg包覆于Ag表面的核壳结构。此外从图2中元素Pd的线扫结果可以看出，PdAg合金壳层厚度为4nm，内核直径为8nm。
图3为实施例1制备的Ag@PdAg/Mg 2Al-LDH催化剂Pd元素的X-射线光电子能谱图。相比于单金属，Pd电子结合能的偏移表明制备的催化剂金属颗粒表面PdAg合金的形成。
图4为实施例1制备的Ag@PdAg/Mg 2Al-LDH催化剂在乙炔选择性加氢反应中，目标产物乙烯选择性随温度变化曲线。从图中可以看出，该催化剂在30-100℃温度范围内乙烯选择性都高于95％。
图5为实施例1制备的Ag@PdAg/Mg 2Al-LDH催化剂在乙炔选择性加氢反应中，乙炔转化率、乙烯选择性随时间变化曲线。从图中可以看出，催化剂在反应50h后并没有出现失活的现象，乙炔转化率一直保持96％以上。乙烯选择性表现出类似的趋势，在长时间反应后，催化剂选择性依然维持在93％以上。
图6为实施例1制备的Ag@PdAg/Mg 2Al-LDH催化剂在乙炔选择性加氢反应48h后的电镜照片。从照片中可以看出，经过长时间的反应催化剂并没有发生金属颗粒团聚的现象，活性组分金属颗粒均匀分散在水滑石载体表面。
图7为实施例2制备的Au@PdAu/SiO 2催化剂的金属颗粒的扫描透射电镜(STEM)照片。从照片中可以看出Au@PdAu金属颗粒尺寸约为15nm。金属颗粒体相和表面的亮度不同(STEM照片的亮度由金属原子的原子序数决定的，原子序数大，亮度强)，金属颗粒的表面亮度低于中心部分，说明金属Pd集中分布于金属颗粒的表面。此外，通过量取晶格条纹可知，该金属颗粒的体相为Au，即该金属颗粒是由Au为内核PdAu为壳的核壳结构，且壳层厚度约为2nm。
图8为实施例1制备的Ag@PdAg/Mg 2Al-LDH催化剂和实施例2制备的Au@PdAu/SiO 2催化剂在蒽醌加氢反应中氢化效率变化曲线。从图中可以看出，两个催化剂初始氢化效率均可到达13.9g/L。并且，在反应300min后，催化剂的氢化效率均保持在14.2g/L以上，表明双金属核壳结构催化剂在该反应中具有优异的稳定性。
图9为实施例1制备的Ag@PdAg/Mg 2Al-LDH催化剂和实施例2制备的Au@PdAu/SiO 2催化剂在蒽醌加氢反应中有效蒽醌选择性随时间变化曲线。从图中可以看出，核壳结构催化剂在反应5h以后，有效蒽醌选择性依然保持在95％以上。
本发明的有益效果是：通过使用一步合成法，将载体、金属盐和还原剂溶液混合，一步合成M@PdM/ZT催化剂，其中活性金属颗粒M@PdM为核壳结构，壳层组成为PdM合金。通过调控温度和反应时间调控两种金属离子还原的动力学行为，实现核壳结构的构筑；通过控制金属离子浓度调控活性金属颗粒组成和壳层厚度。该方法过程简单，通用性强，不仅可以使活性金属反应位点充分暴露，表面合金的构筑还可以充分发挥两种金属间的协同作用。该方法制备的双金属核壳机构催化剂在乙炔选择性加氢和蒽醌加氢反应中都表现出了优异的催化剂选择性和稳定性。
附图说明
图1为实施例1中Ag@PdAg/Mg 2Al-LDH催化剂的电镜照片。
图2为实施例1中Ag@PdAg/Mg 2Al-LDH催化剂金属颗粒X-射线Pd和Ag的线扫谱图。
图3为实施例1中Ag@PdAg/Mg 2Al-LDH催化剂金属Pd的X-射线光电子能谱图。
图4为实施例1中Ag@PdAg/Mg 2Al-LDH催化剂在乙炔选择性加氢反应中产物乙烯选择性随温度变化曲线。
图5为实施例1中Ag@PdAg/Mg 2Al-LDH催化剂在乙炔选择性加氢反应中乙炔转化率、乙烯选择性随时间变化曲线。
图6为实施例1中Ag@PdAg/Mg 2Al-LDH催化剂在乙炔选择性加氢反应48h后的电镜照片。
图7为实施例2中Au@PdAu/SiO 2催化剂金属颗粒的扫描透射电镜照片。
图8为实施例1中Ag@PdAg/Mg 2Al-LDH和实施例2中Au@PdAu/SiO 2催化剂在蒽醌加氢反应中氢化效率随时间变化曲线。
图9为实施例1中Ag@PdAg/Mg 2Al-LDH和实施例2中Au@PdAu/SiO 2催化剂在蒽醌加氢反应中有效蒽醌选择性随时间变化曲线。
具体实施方式：
以下结合附图实施例对本发明作进一步详细描述
实施例1
0.008mmol Pd(C 5H 7O 2) 2，0.08mmol的AgNO 3加入到100mL的N，N-二甲基甲酰胺中，超声5min得到混合盐溶液。将上述混合溶液装于烧瓶中置于油浴锅上50℃加热搅拌10min，加入1g Mg 2Al-LDH粉末，继续搅拌10min，之后升温至130℃，保温2h，得到黑色沉淀的悬浊液，降至室温，离心，洗涤，干燥得到黑色粉末，经过表征证明其为Ag@PdAg/Mg 2Al-LDH催化剂，且金属颗粒为核壳结构，壳层PdAg为合金。
实施例2
将0.01mmol Pd(CH 3COO) 2，0.04mmol的HAuCl 4·4H 2O加入到100ml的乙二醇水溶液中(其中水的质量分数为20％)，搅拌，超声5min得到混合盐溶液。将上述混合溶液装于烧瓶中置于油浴锅上，50℃加热搅拌0.5h，加入0.5g无定型二氧化硅粉末(SiO 2)，继续搅拌10min，之后升温至110℃，在该温度下反应12h，得到黑色沉淀的悬浊液，降至室温，离心，洗涤，干燥得到黑色粉末，经过表征证明其为Au@PdAu/SiO 2催化剂，且金属颗粒为核壳结构，壳层PdAu为合金。
实施例3
将0.002mmol Pd(NO 3) 2，0.06mmol的AgNO 3加入到100ml的N,N-二甲基甲酰胺水溶液中(其中水的质量分数为10％)；搅拌，超声5min得到混合盐溶液。将上述混合溶液装于烧瓶中置于油浴锅上40℃加热搅拌1h，加入1g氧化铝粉末，继续搅拌10min，之后升温至130℃，在该温度下反应2h，得到黑色沉淀的悬浊液，降至室温，离心，洗涤，干燥得到灰色粉末。经过表征证明其为Ag@PdAg/Al 2O 3催化剂，且金属颗粒为核壳结构，壳层PdAg为合金。
实施例4
将0.005mmol Ir(C 5H 7O 2) 3，0.001mmol的PdCl 2加入到100ml的异丙醇水溶液中(水的质量分数为10％)，搅拌，超声5min得到混合盐溶液。将上述混合溶液装于烧瓶中置于油浴锅上40℃加热搅拌0.5h，加入2g水滑石(Mg 2Al-LDH)粉末，继续搅拌10min，之后升温至100℃，在该温度下反应1h，得到黑色沉淀的悬浊液，降至室温，离心，洗涤，干燥得到灰色粉末。经过表征证明其为Ir@PdIr/Mg 2Al-LDH催化剂，且金属颗粒为核壳结构，壳层PdIr为合金。
实施例5
将0.01mmol Pd(CH 3COO) 2，0.004mmol的HPtCl 6加入到100ml的N,N-二甲基乙酰胺溶液中，搅拌，超声5min得到混合盐溶液。将上述混合溶液装于烧瓶中置于油浴锅上45℃加热搅拌0.5h，加入2g氧化铝粉末，继续搅拌10min，之后升温至160℃，在该温度下反应12h，得到黑色沉淀的悬浊液，降至室温，离心，洗涤，干燥得到黑色粉末。经过表征证明其为Pt@PdPt/Al 2O 3催化剂，且金属颗粒为核壳结构，壳层PdPt为合金。
应用例1：
将实施例1-5催化剂与对比例样品进行乙炔选择性加氢反应性能评价
评价装置为天津先权公司的WFS-3015型微型反应床，操作步骤如下：
分别称取0.1g催化剂样品，并与1.9g石英砂(40-80目)充分混合，装于石英反应管中。反应开始前，先将反应床温度升到150℃通氮气对催化剂进行预处理1小时，氮气流速为50ml/min。预处理结束后，待反应床温度降至室温，通反应原料气，即氮气、乙烯乙炔混合气、氢气，流量分别为111、55.5、1.0mL/min；乙烯乙炔混合气乙炔的百分含量为0.947％，氢炔比约为2。控制反应温度为100℃，反应空速为10050h -1，反应体系的相对压力为0.4MPa。反应物与产物的浓度通过在线气相色谱进行分析，毛细管柱规格为0.53×50mm，检测器为氢焰检测器。并采用归一化法进行数据处理。催化剂在100℃条件下的乙炔转化率和乙烯选择 性结果见表1
表1
催化剂样品 实施例1 实施例2 实施例3 实施例4 实施例5 对比例
乙炔转化率(％) 100 94 87 100 100 86
乙烯选择性(％) 94 91 100 74 91 72
其中对比例样品是根据中国专利CN 103977794B得到的PdPtAg/Mg 2Al-LDH催化剂，该专利是本研究室申请的，该催化剂是专用于乙炔选择性加氢反应。
应用例2：
将实施例1-5催化剂与对比例样品应用于蒽醌加氢反应进行性能评价，具体步骤如下：
评价装置为带有磁力搅拌和加热装置的聚四氟乙烯内胆反应釜，将25mg催化剂和60mL蒽醌工作液(浓度为100g/L的蒽醌工作液由100g 2-乙基蒽醌、1,3,5-三甲苯和400mL磷酸三辛酯组成)加入到反应釜并封闭，通过钢瓶向反应釜中通入氢气以置换反应釜中的空气，重复5次。将反应釜升温至50℃，并通入氢气，使压力达到0.3MPa，搅拌转速调至1200r/min后开始计时。反应1.5h后，从反应气出口阀采集反应样品进行活性和选择性评价并计算H 2O 2产率。催化剂的H 2O 2产率和时空收率见表2。
表2
Figure PCTCN2018113555-appb-000001
其中对比例样品是根据中国专利CN 103172097A得到的蒽醌加氢反应用Pd/Al 2O 3催化剂，该专利是本实验室申请的，该催化剂专用于蒽醌加氢反应。

Claims (2)

  1. 一种负载型双金属核壳结构催化剂的制备方法，具备步骤如下：
    A.将M盐和Pd盐加入到还原性溶液中超声4-5min得到混合盐溶液；所述的M为Ag、Pt、Au、Ir中的一种；M盐为AgNO 3、HPtCl 6、Pt(C 5H 7O 2) 2、H 2IrCl 6·6H 2O、Ir(C 5H 7O 2) 3、HAuCl 4·4H 2O中的一种；所述的Pd盐为PdCl 2、Pd(NO 3) 2、Pd(C 5H 7O 2) 2、Pd(CH 3COO) 2中的一种；还原性溶液是由还原剂与去离子水的混合物，其中水的质量百分含量为0-20％，所述的还原剂为：乙二醇、异丙醇、N，N-二甲基乙酰胺、N，N-二甲基甲酰胺、甘油醛中的一种；所述的混合盐溶液中M离子和Pd离子总浓度为0.01-20mmol/L，M:Pd离子的摩尔比为0.1-10；
    B.将上述混合盐溶液于40-50℃加热搅拌10-30min，加入载体，继续搅拌10-20min，升温至100-160℃，保持该温度0.5-24h得到有黑色沉淀的悬浊液，降至室温，离心，洗涤，干燥得到灰色或黑色粉末；经表征证明为M@PdM/ZT催化剂；其活性组分金属颗粒M@PdM为核壳结构，其中M为核，PdM合金为壳层；所述的载体为Al 2O 3、SiO 2、Mg 2Al-LDH水滑石中的一种。
  2. 一种根据权利要求1所述的方法制备的负载型双金属核壳结构催化剂，该催化剂表示为M@PdM/ZT，其中活性金属颗粒M@PdM为核壳结构，M为内核，直径为5-15nm，M代表金属Ag、Pt、Au、Ir中的一种；PdM合金为壳层，壳层厚度为1-10nm；ZT表示载体，ZT是水滑石(Mg 2Al-LDH)、氧化铝(Al 2O 3)、二氧化硅(SiO 2)中的一种。
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