WO2018064960A1 - 一种微波辅助碳模板法制备负载型纳米金属材料的方法 - Google Patents

一种微波辅助碳模板法制备负载型纳米金属材料的方法 Download PDF

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WO2018064960A1
WO2018064960A1 PCT/CN2017/104429 CN2017104429W WO2018064960A1 WO 2018064960 A1 WO2018064960 A1 WO 2018064960A1 CN 2017104429 W CN2017104429 W CN 2017104429W WO 2018064960 A1 WO2018064960 A1 WO 2018064960A1
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oxide
metal
nano metal
nano
preparing
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French (fr)
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姜兴茂
曹静远
仝雪
张忠南
冯健
童彦杰
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常州大学
武汉工程大学
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Definitions

  • the invention provides a microwave assisted carbon template method for preparing a supported nano metal oxide or nano metal material, and belongs to the technical field of nano material preparation.
  • Nanomaterials refer to solid materials composed of very fine grains with characteristic dimension dimensions on the order of nanometers ( ⁇ 100 nm). Nanomaterials have many properties that are not available in conventional materials, including optical properties, electromagnetic properties, thermodynamic properties, and quantum mechanical properties. Due to these properties, nanomaterials are widely used in lubrication, optoelectronics, magnetic recording, and catalysis. However, due to its high surface energy, the nanoparticles are easily agglomerated spontaneously, which greatly limits the nano-effect of nanomaterials and reduces their application fields and effects. Therefore, nanomaterials often require a carrier.
  • the porous material is a material composed of interconnected or closed voids.
  • the silica and alumina are ideal catalyst carriers, which can block the agglomeration of the supported particles and provide a reaction solution.
  • the transport channel promotes the diffusion of the generated material, and the large specific surface area contributes to the contact between the catalyst and the reactant, and is one of the indispensable materials in the modern industry.
  • the preparation of porous oxide supports is generally synthesized by a hard template method and a soft template method and is considered to be the most efficient method for synthesizing porous materials. Loaded nano metal or oxide materials have broad application prospects in industrial catalysis, water treatment and electrochemistry.
  • a direct dipping method is generally employed.
  • the direct impregnation method is to directly immerse the porous oxide support material in a metal salt solution, and then dry and heat-treat to obtain a porous oxide support-supported nano material.
  • the nickel nanoparticles are introduced into the alumina by an immersion reduction method to obtain a highly dispersed Alumina-supported nickel catalyst has broad application prospects in the field of methanation of carbon monoxide to synthetic artificial natural gas.
  • the impregnation method is widely used, but lacks effective regulation of the particle size, composition and distribution in the carrier.
  • the microwave-assisted carbon template method utilizes high-frequency microwave energy to generate a large amount of heat in a short time, thereby promoting various chemical reactions, and is a more effective energy utilization and heating method.
  • Microwave heating synthesis can greatly accelerate the movement and collision speed of reactive molecules, which is beneficial to the formation of a large number of crystal nuclei, can limit the increase of crystal grain size, and can synthesize smaller and more uniform nanometers than the crystals prepared by conventional methods. material.
  • microwave synthesis technology has been widely used in the preparation of nanomaterials.
  • the traditional methods for the synthesis of porous oxide-loaded nano-metal materials often have problems such as difficulty in controlling the size of the nanoparticles, poor dispersibility, high cost of the stencil agent, and serious post-treatment pollution.
  • conventional synthetic methods cannot be widely used in the preparation of various nanometals or oxides due to limitations in the preparation methods. Therefore, a simple and universal method for preparing porous oxide-supported nano-metal or metal oxide composites was developed, and the pore structure of the support and the size, composition, crystal phase and loading of the nanoparticles were controlled during the synthesis. Parameters such as quantity will definitely have a significant impetus for the wide application of such materials.
  • the object of the present invention is to develop a simple and universal method for preparing a porous oxide-supported nano metal oxide or nano metal material, which is widely applicable to the synthesis of supported nano metal or nano metal oxide.
  • the present invention utilizes a precursor of a saccharide, urea, oxide carrier, and a metal salt to form a homogeneous solution in water such that the metal salt is uniformly distributed in the mixed liquid.
  • the microwave is used to carbonize the sugar to obtain a carbon-coated oxide carrier and the nano metal, and the metal active component is uniformly distributed in the porous carbon, and then the high temperature treatment in the air to obtain the oxide carrier-supported nano metal oxide.
  • a porous carbon-supported nano metal oxide or nano metal material is obtained.
  • a microwave assisted carbon template method for preparing a supported nano metal oxide or nano metal material according to the following steps:
  • step b) the solution obtained in step a) is subjected to microwave treatment for 0.1 min to 60 min, and the power of microwave heating is 100 w to 50 kw, so that the sugar is dehydrated and carbonized to obtain a dark brown solid;
  • the dark brown solid obtained in the step b) is heat-treated at 200-1100 ° C for 0.5 h to 24 h in an air atmosphere to obtain a porous supported nano metal oxide material;
  • step c) The solid obtained in the step c) is heat-treated at 200 to 1100 ° C for 0.5 to 24 hours in a reducing atmosphere to obtain a porous metal oxide-supported nano metal/alloy material.
  • the precursor of the oxide carrier in the step (a) comprises a common silicon source, a common aluminum source, and other common metal salts; wherein the common silicon source comprises a silica sol, sodium silicate, or tetraethyl orthosilicate; the common aluminum source comprises an aluminum sol.
  • metal elements aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum isopropoxide; other common metal salts are one of metal nitrates, halides, hypochlorites, acetates, oxalates, phosphates or sulfates Or a salt of one or more different metal elements, the types of metal elements are: Mg, Pb, In, Sn, Sb, Zr, Nb, La, Ce, Ta, Mo, W, Re, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Pt, Pd, Ir, Ru, Rh, Y, Ba, Sr, La and Os.
  • the metal salt described in the step (a) is a salt of one or more different metal elements of a metal nitrate, a halide, a hypochlorite, an acetate, an oxalate, a phosphate or a sulfate.
  • the types of metal elements are: Mg, Al, Pb, In, Sn, Sb, Zr, Nb, La, Ce, Ta, Mo, W, Re, Ti, V, Cr, Mn, Fe, Co, Ni, Cu , Zn, Ag, Pt, Pd, Ir, Ru, Rh, Y, Ba, Sr, La and Os.
  • the sugar in the step (a) is one of glucose, fructose, sucrose, maltose, lactose, starch and dextrin.
  • the mass ratio of the sugar to the urea in the step (a) is from 20:1 to 1:60.
  • the mass ratio of the saccharide to the metal salt in the step (a) is from 100:1 to 1:10.
  • the mass ratio of the saccharide to the carrier oxide precursor in the step (a) is from 100:1 to 1:50.
  • the mass ratio of the sugar to the water in the step (a) is from 50:1 to 1:100.
  • the porous oxide carrier oxide being a single element oxide or a composite oxide
  • the single element oxide is one of oxides of the following elements
  • the composite oxide includes two types. Or oxides of two or more different elements: Si, Mg, Al, Pb, In, Sn, Sb, Zr, Nb, La, Ce, Ta, Mo, W, Re, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Pt, Pd, Ir, Ru, Rh, Y, Ba, Sr, La and Os.
  • the porous oxide support-loaded nano metal oxide obtained in the step (c) may be a single metal element oxide or a composite metal oxide, wherein the single metal oxide includes one of the oxides of the following elements.
  • the composite metal oxide includes oxides of two or more different metal elements: Mg, Al, Pb, In, Sn, Sb, Zr, Nb, La, Ce, Ta, Mo, W, Re, Ti , V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Pt, Pd, Ir, Ru, Rh, Y, Ba, Sr, La and Os.
  • the porous oxide carrier oxide being a single element oxide or a composite oxide
  • the single element oxide is one of the oxides of the following elements
  • the composite oxide includes two types. Or oxides of two or more different elements: Si, Mg, Al, Pb, In, Sn, Sb, Zr, Nb, La, Ce, Ta, Mo, W, Re, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Pt, Pd, Ir, Ru, Rh, Y, Ba, Sr, La and Os.
  • the porous oxide carrier-loaded nano metal material obtained in the step (d) may be a simple substance of a metal element or an alloy or an intermetallic compound of two or more different metal elements, wherein the metal element includes Mg, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, Pt, Pd, Ru, Os, Rh, Ir, Au, Ag, Pb, In, Sn, Sb, Zr, Nb, La, Ce, Ta, Mo, W, and Re.
  • the metal element includes Mg, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, Pt, Pd, Ru, Os, Rh, Ir, Au, Ag, Pb, In, Sn, Sb, Zr, Nb, La, Ce, Ta, Mo, W, and Re.
  • the reducing gas described in the step (d) is a mixed gas containing hydrogen or carbon monoxide in a volume fraction of 5% to 10%, and the equilibrium gas is nitrogen or argon.
  • the present invention utilizes a saccharide, urea, oxide carrier precursor and metal salt to form a homogeneous liquid in water such that the metal salt is evenly distributed in the mixed liquid. Then, by in-situ synthesis, the sugar is dehydrated and carbonized at a high temperature, and the metal component is uniformly distributed in the carbon template, and finally the oxide carrier-loaded nano metal is obtained by high-temperature heat treatment.
  • the invention can be used for loading a plurality of nano metal materials, and has a size of 2 to 1000 nm and high monodispersity. By adjusting the synthesis conditions, the composition, the crystal phase and the supporting amount of the nano metal can be controlled.
  • the pore size of the carrier can also be controlled by conditions such as raw material ratio, microwave heating power, time, and the like, and the pore size distribution is from 0.1 nm to 10 ⁇ m.
  • the invention has the advantages of simple synthesis route and low cost, and therefore has great application prospects in many aspects such as industrial catalysis, water treatment and electrochemistry.
  • Example 1 is an XRD chart of a silicon oxide-supported metal Ni obtained in Example 1.
  • Example 2 is an XRD chart of the alumina-supported metal Ni obtained in Example 2.
  • Example 3 is an XRD chart of cerium oxide-supported metal NiO obtained in Example 3.
  • Example 4 is an XRD chart of cerium oxide-supported metal NiO obtained in Example 4.
  • Fig. 5 is a TEM image of the silicon oxide-supported metal Ni obtained in Example 1.
  • Figure 6 is a TEM image of the alumina-supported metal Ni obtained in Example 2.
  • Figure 1 is an XRD pattern of a silicon-supported metal Ni. It can be seen that the nano-metal Ni is uniformly distributed in the carbon carrier, and Figure 5 is a TEM image of the silicon-supported metal Ni, which proves that the nano-metal Ni is consistent with the XRD result.
  • Example 2 Alumina supported nano Ni
  • FIG. 2 is an XRD pattern of alumina-loaded nano-metal Ni
  • FIG. 6 is a TEM image of alumina-loaded nano-metal Ni, which is consistent with the XRD results.
  • Figure 3 is an XRD pattern of the produced cerium oxide-supported metal NiO.
  • Synthetic raw materials fructose, urea, Ag(NO 3 ) 2 (silver nitrate)

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Abstract

一种微波辅助碳模板法制备负载型纳米金属材料的方法，属于纳米材料制备技术领域。利用糖类、尿素、氧化物载体的前驱体和金属盐在水中形成均相溶液，使得金属盐均匀分布在混合液体中。之后，利用微波加热使得糖类碳化得到碳包裹氧化物载体和纳米金属，同时金属活性组分均匀分布在多孔炭中，随后在空气中高温处理后，得到氧化物载体负载的纳米金属氧化物，接着在还原性气氛下高温热处理后，得到多孔炭负载纳米金属氧化物或纳米金属材料。通过改变原料配比、微波时长和功率等合成条件，可以得到担载量、粒径大小、晶相和组成同时可控的担载型纳米材料。整个工艺具有操作简单、绿色环保以及成本低廉等优点。

Description

一种微波辅助碳模板法制备负载型纳米金属材料的方法 技术领域
本发明提供了一种微波辅助碳模板法制备负载型纳米金属氧化物或纳米金属材料的方法，属于纳米材料制备技术领域。
背景技术
纳米材料是指由极细晶粒组成、特征维度尺寸在纳米数量级(～100nm)的固体材料。纳米材料拥有许多常规材料所不具备的性能，包括光学性能、电磁学性能、热力学性能、量子力学性能等，由于这些性能，纳米材料广泛应用于润滑、光电、磁记录、催化等领域。然而，由于其高表面能，纳米颗粒极易自发团聚，大大限制了纳米材料的纳米效应，降低了其应用领域及效果。因此纳米材料往往需要载体，多孔材料是一种由相互贯通或封闭的空洞构成网络结构的材料，氧化硅、氧化铝是较为理想的催化剂载体，既能阻碍所负载颗粒的团聚，提供反应溶液的输送通道，又促进了生成物质的扩散，大的比表面积有助于催化剂和反应物的接触，是现代工业中不可缺少的重要材料之一。多孔氧化物载体的制备一般是通过硬模板法和软模板法合成，被认为是合成多孔材料和最有效的方法。负载型纳米金属或氧化物材料在工业催化、水处理和电化学等诸多方面都具有广阔的应用前景。
在多孔材料担载纳米纳米金属或纳米金属氧化物的制备方法方面，普遍采用的是直接浸渍法。直接浸渍法是将多孔氧化物载体材料直接浸渍于金属盐溶液中，然后经干燥和热处理得到多孔氧化物载体负载的纳米材料。Dacheng Hu等[Hu D,Gao J,Ping Y,et al.Industrial&Engineering Chemistry Research,2012,51(13):4875-4886.]通过浸渍还原方法将镍纳米颗粒引入到氧化铝中，得到高度分散的氧化铝负载镍催化剂，其在一氧化碳甲烷化合成人造天然气领域有应用前景广阔。浸渍法应用广泛，但是对于纳米粒子的粒径、组分和在载体中的分布缺乏有效的调控。
微波辅助碳模板法是利用高频微波能，在很短时间内产生大量的热，从而促进各类化学反应的进行，是更有效的能量利用和加热方式。微波加热合成能大幅度加快反应分子的运动与碰撞速度，有利于晶核的大量形成，可限制晶体粒径的增加，能够合成出比常规方法所制备晶体的粒径更小、更均匀的纳米材料。目前，微波合成技术已广泛应用于纳米材料的制备。Peiro等分两步制备TiO2薄膜：第一步，将衬底浸入经微波辐射的TiO2 胶体溶液中，发现衬底上有TiO2晶体沉积；第二步，将上述处理的衬底浸入含Ti4+的水溶液中，并用微波辐射。实验发现，第二步制成的TiO2薄膜成长速度比第一步快，晶体结构完整，颗粒粒径分布在50～100nm之间[Peiro Ana M,Elena Vigil,et a1.Titanium(Ⅳ)oxide thin films obtained by a two-step-solution method.Thin Solid Films,2002，411:185]。Wang等以醋酸铜和氢氧化钠为原料，在乙醇溶剂中，通过微波辐射，成功合成平均粒径为4nm的CuO颗粒。颗粒形貌呈球形，产品的纯度高[Wang Hui,Xu Jinzhong,et a1.Preparation of CuO nanopar-ticles by microwave irradiation.J Cryst Growth,2002,244:88]。
总而言之，传统的多孔氧化物负载纳米金属材料的合成方法往往存在着纳米粒子尺寸不易控制，分散性差，模版剂成本高，后期处理污染严重等问题。此外，传统合成方法由于制备方法的限制不能够广泛运用于各种纳米金属或氧化物的制备。因此，开发一种简单普适的多孔氧化物负载纳米金属或金属氧化物复合材料的制备方法，并能够在合成过程中控制载体的孔道结构以及纳米粒子的尺寸、组分、晶相和担载量等参数，对于该类材料的广泛应用必将产生重大的推动作用。
发明内容
本发明的目的在于开发一种简单普适的多孔氧化物负载纳米金属氧化物或纳米金属材料的制备方法，该方法可广泛的适用于负载型纳米金属或纳米金属氧化物的合成。
本发明利用糖类、尿素、氧化物载体的前驱体和金属盐在水中形成均相溶液，使得金属盐均匀分布在混合液体中。之后，利用微波加热使得糖类碳化得到碳包裹氧化物载体和纳米金属，同时金属活性组分均匀分布在多孔炭中，随后在空气中高温处理后，得到氧化物载体负载的纳米金属氧化物，接着在还原性气氛下高温热处理后，得到多孔炭负载纳米金属氧化物或纳米金属材料。
本发明的具体实施步骤为：一种微波辅助碳模板法制备负载型纳米金属氧化物或纳米金属材料的方法，按照下述步骤进行：
a)将糖类、尿素、氧化物载体的前驱体和金属盐混合放在容器中，加入一定量的水，超声搅拌，使得混合固体完全融化，形成均匀的溶液；
b)将步骤a)中得到的溶液微波处理0.1min～60min，微波加热的功率为100w～50kw，使得糖类脱水碳化得到黑褐色固体；
c)将步骤b)中制得的黑褐色固体在空气氛围下，于200-1100℃下热处理0.5h-24h，得到多孔负载的纳米金属氧化物材料；
d)将步骤c)中得到的固体在还原性氛围下，于200～1100℃下热处理0.5h～24h，得到多孔氧化物载体负载的纳米金属/合金材料。
其中步骤(a)中氧化物载体的前驱体包括常用硅源、常用铝源、其他常用金属盐；其中常用硅源包含硅溶胶、硅酸钠、正硅酸乙酯；常用铝源包含铝溶胶、硫酸铝、氯化铝、硝酸铝、异丙醇铝；其他常用金属盐为金属硝酸盐、卤化物、次氯酸盐、醋酸盐、草酸盐、磷酸盐或硫酸盐中的一种或一种以上不同金属元素的盐，金属元素的种类有：Mg、Pb、In、Sn、Sb、Zr、Nb、La、Ce、Ta、Mo、W、Re、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ag、Pt、Pd、Ir、Ru、Rh、Y、Ba、Sr、La和Os。
其中步骤(a)中所述的金属盐为金属硝酸盐、卤化物、次氯酸盐、醋酸盐、草酸盐、磷酸盐或硫酸盐中的一种或一种以上不同金属元素的盐，金属元素的种类有：Mg、Al、Pb、In、Sn、Sb、Zr、Nb、La、Ce、Ta、Mo、W、Re、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ag、Pt、Pd、Ir、Ru、Rh、Y、Ba、Sr、La和Os。
其中步骤(a)中糖类为葡萄糖、果糖、蔗糖、麦芽糖、乳糖、淀粉和糊精中的一种。
其中步骤(a)中糖类与尿素的质量比为20:1～1:60。
步骤(a)中糖类与金属盐的质量比为100:1～1:10。
步骤(a)中糖类与载体氧化物前驱体的质量比为100:1～1:50。
步骤(a)中糖类与水的质量比为50:1～1:100。
其中所述的步骤(c)得到多孔氧化物载体氧化物是单元素氧化物或是复合氧化物，其中单元素氧化物为下列元素的氧化物中的一种，而复合氧化物则包括两种或两种以上不同元素的氧化物：Si、Mg、Al、Pb、In、Sn、Sb、Zr、Nb、La、Ce、Ta、Mo、W、Re、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ag、Pt、Pd、Ir、Ru、Rh、Y、Ba、Sr、La和Os。
其中所述的步骤(c)得到的多孔氧化物载体负载纳米金属氧化物，可以是单金属元素氧化物也可以是复合金属氧化物，其中单金属氧化物包括下列元素的氧化物中的一种，而复合金属氧化物则包括两种或两种以上不同金属元素的氧化物：Mg、Al、Pb、In、Sn、Sb、Zr、Nb、La、Ce、Ta、Mo、W、Re、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ag、Pt、Pd、Ir、Ru、Rh、Y、Ba、Sr、La和Os。
其中所述的步骤(d)得到多孔氧化物载体氧化物是单元素氧化物或是复合氧化物，其中单元素氧化物为下列元素的氧化物中的一种，而复合氧化物则包括两种或两种以上不同元素的氧化物：Si、Mg、Al、Pb、In、Sn、Sb、Zr、Nb、La、Ce、Ta、Mo、W、 Re、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ag、Pt、Pd、Ir、Ru、Rh、Y、Ba、Sr、La和Os。
其中所述的步骤(d)得到的多孔氧化物载体负载纳米金属材料，可以是一种金属元素的单质也可以是两种及以上不同金属元素的合金或金属间化合物，其中金属元素包括Mg、Al、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Nb、Mo、Pt、Pd、Ru、Os、Rh、Ir、Au、Ag、Pb、In、Sn、Sb、Zr、Nb、La、Ce、Ta、Mo、W和Re。
步骤(d)中所述的还原性气体为含氢气或一氧化碳体积分数为5％～10％的混合气，平衡气为氮气或氩气。
本发明利用糖类、尿素、氧化物载体前驱体和金属盐在水中形成均相液体，使得金属盐均匀分布在混合液体中。之后，利用原位合成的方法，在高温下使得糖类脱水碳化，同时金属组分均匀分布在碳模板中，最后通过高温热处理得到氧化物载体负载纳米金属。本发明可以用于负载众多纳米金属材料，其尺寸为2～1000nm且单分散性高，通过调节合成条件，可以控制纳米金属的组成、晶相以及担载量等。此外，载体的孔道尺寸也可以通过原料配比、微波加热功率、时间等条件进行控制，孔径分布从0.1nm～10μm。此外，本发明还具有合成路线简单和成本低廉等优势，因此在工业催化、水处理和电化学等诸多方面拥有巨大的应用前景。
附图说明
图1为实施例1制得的氧化硅负载金属Ni的XRD图。
图2为实施例2制得的氧化铝负载金属Ni的XRD图。
图3为实施例3制得的氧化镧负载金属NiO的XRD图。
图4为实施例4制得的氧化铈负载金属NiO的XRD图。
图5为实施例1制得的氧化硅负载金属Ni的TEM图。
图6为实施例2制得的氧化铝负载金属Ni的TEM图。
具体实施方式
下面结合具体实施例对本发明做进一步说明，但本发明的保护范围不限于此。
实施例1：氧化硅负载纳米Ni
合成原料：葡萄糖、尿素、硅溶胶、水、Ni(NO3)2`6H2O(硝酸镍)
(1)称取1.5g葡萄糖、2.5g尿素、2g硅溶胶、5g水和0.9g Ni(NO3)2·9H2O于一个100mL烧杯中，超声搅拌10min直至烧杯中药品溶解。
(2)将(1)中所述熔融液体取出，放入微波中加热，加热功率为800w，加热3min得到黑褐色膨松固体。
(3)用研钵将(2)中得到的样品研碎，并放与坩埚中，在500℃下，空气中焙烧5h，得到氧化硅负载的纳米氧化镍。
(4)在550℃下，5％H2/N2条件下热处理4h，得到氧化硅负载纳米金属镍，XRD测试显示Ni粒径大小为5nm。
图1为氧化硅负载金属Ni的XRD图，图中可见纳米金属Ni均匀分布在碳载体中，图5为氧化硅负载金属Ni的TEM图，证明纳米金属Ni与XRD结果相符。
实施例2：氧化铝负载纳米Ni
合成原料：葡萄糖、尿素、铝溶胶、水、Ni(NO3)2`6H2O(硝酸镍)
(1)称取1.5g葡萄糖、2.5g尿素、1g铝溶胶、5g水和0.9g Ni(NO3)2·9H2O于一个100mL烧杯中，超声搅拌10min直至烧杯中药品溶解。
(2)将(1)中所述熔液取出，放入微波中加热，加热功率为700w，加热10min得到黑褐色膨松固体。
(3)用研钵将(2)中得到的样品研碎，并放与坩埚中，在500℃下，空气中焙烧5h，得到氧化铝负载的纳米氧化镍。
(4)在650℃下，5％H2/N2条件下热处理4h，得到氧化铝负载纳米金属镍，XRD测试显示Ni粒径大小为10nm。
图2为氧化铝负载纳米金属Ni的XRD图，图6为氧化铝负载纳米金属Ni的TEM图，与XRD结果相符。
实施例3：氧化镧负载纳米NiO
合成原料：葡萄糖、尿素、硝酸镧、水、Ni(NO3)2`6H2O(硝酸镍)
(1)称取1.5g葡萄糖、2.5g尿素0.42g硝酸镧、5g水和0.2g Ni(NO3)2·9H2O于一个100mL烧杯中，超声搅拌10min直至烧杯中药品溶解。
(2)将(1)中所述熔融液体取出，放入微波中加热，加热功率为700w，加热5min得到黑褐色膨松固体。
(3)用研钵将(2)中得到的样品研碎，并放与坩埚中，在500℃下，空气中焙烧5h，得到氧化镧负载的纳米氧化镍。
图3为制得的氧化镧负载金属NiO的XRD图。
实施例4：氧化铈载纳米NiO
合成原料：葡萄糖、尿素、硝酸铈、水、Ni(NO3)2`6H2O(硝酸镍)
(1)称取1.5g葡萄糖、2.5g尿素0.42g硝酸铈、5g水和0.2g Ni(NO3)2·9H2O于一个100mL烧杯中，超声搅拌10min直至烧杯中药品溶解。
(2)将(1)中所述熔融液体取出，放入微波中加热，加热功率为700w，加热5min得到黑褐色膨松固体。
(3)用研钵将(2)中得到的样品研碎，并放与坩埚中，在500℃下，空气中焙烧5h，得到氧化铈负载的纳米氧化镍。
图4为制得的氧化铈负载金属NiO的XRD图。
实验例4：氧化硅负载纳米Ag
合成原料：果糖、尿素、Ag(NO3)2(硝酸银)
(1)称取1g果糖、60g尿素、0.1g Ag(NO3)2、5g水、2g硅溶胶于一个200mL烧杯中，超声搅拌10min直至烧杯中药品溶解。
(2)将(1)中所述熔融液体取出，放入微波中加热，加热功率为500w，加热3min得到黑褐色膨松固体。
(3)用研钵将(2)中得到的样品研碎，并放与坩埚中，在500℃下，空气中焙烧5h，得到氧化硅负载的纳米银。
实验例6：氧化铝负载纳米Pd
合成原料：葡萄糖、尿素、Pd(NO3)2·2H2O(硝酸钯)
(1)称取50g葡萄糖、2.5g尿素、1g水、0.5g铝溶胶和0.03g Pd(NO3)2·2H2O于一个200mL烧杯中，超声搅拌10min直至烧杯中药品溶解。
(2)将(1)中所述熔融液体取出，放入微波中加热，加热功率为200w，加热60min得到黑褐色膨松固体。
(3)用研钵将(2)中得到的样品研碎，并放与坩埚中，在500℃下，空气中焙烧5h，得到氧化铝负载的纳米氧化钯。
(4)在300℃下，5％H2/N2条件下热处理4h，得到氧化铝负载纳米金属钯。
实验例7：氧化硅负载纳米Fe2O3
合成原料：乳糖、尿素、Fe(NO3)2·9H2O(硝酸铁)
(1)称取50g乳糖和5g尿素、5g水、2g硅溶胶和0.5g Fe(NO3)2·9H2O于一个200mL 烧杯中，超声搅拌10min直至烧杯中药品溶解。
(2)将(1)中所述熔融液体取出，放入微波中加热，加热功率为50kw，加热0.1min得到黑褐色膨松固体。
(3)用研钵将(2)中得到的样品研碎，并放与坩埚中，在600℃下，空气中焙烧5h，得到氧化硅负载的三氧化二铁。
实验例8：氧化硅负载纳米CuO
合成原料：果糖、尿素、Cu(NO3)2
(1)称取1g果糖、60g尿素、10g Cu(NO3)2、50g水、50g硅溶胶于一个200mL烧杯中，超声搅拌10min直至烧杯中药品溶解。
(2)将(1)中所述熔融液体取出，放入微波中加热，加热功率为500w，加热30min得到黑褐色膨松固体。
(3)用研钵将(2)中得到的样品研碎，并放与坩埚中，在500℃下，空气中焙烧12h，得到氧化硅负载的纳米CuO。

Claims (10)

  1. 一种微波辅助碳模板法制备负载型纳米金属氧化物或纳米金属材料的方法，其特征在于按照下述步骤进行：
    a)将糖类、尿素、氧化物载体的前驱体和金属盐混合放在容器中，加入一定量的水，超声搅拌，使得混合固体完全融化，形成均匀的溶液；
    b)将步骤a)中得到的溶液微波处理0.1min～60min，微波加热的功率为100w～50kw，使得糖类脱水碳化得到黑褐色固体；
    c)将步骤b)中制得的黑褐色固体在空气氛围下，于200-1100℃下热处理0.5h-24h，得到多孔负载的纳米金属氧化物材料；
    d)将步骤c)中得到的固体在还原性氛围下，于200～1100℃下热处理0.5h～24h，得到多孔氧化物载体负载的纳米金属/合金材料。
  2. 根据权利要求1所述的一种微波辅助碳模板法制备负载型纳米金属氧化物或纳米金属材料的方法，其特征在于其中步骤(a)中氧化物载体的前驱体包括常用硅源、常用铝源、其他常用金属盐；其中常用硅源包含硅溶胶、硅酸钠、正硅酸乙酯；常用铝源包含铝溶胶、硫酸铝、氯化铝、硝酸铝、异丙醇铝；其他常用金属盐为金属硝酸盐、卤化物、次氯酸盐、醋酸盐、草酸盐、磷酸盐或硫酸盐中的一种或一种以上不同金属元素的盐，金属元素的种类有：Mg、Pb、In、Sn、Sb、Zr、Nb、La、Ce、Ta、Mo、W、Re、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ag、Pt、Pd、Ir、Ru、Rh、Y、Ba、Sr、La和Os。
  3. 根据权利要求1所述的一种微波辅助碳模板法制备负载型纳米金属氧化物或纳米金属材料的方法，其特征在于其中步骤(a)中所述的金属盐为金属硝酸盐、卤化物、次氯酸盐、醋酸盐、草酸盐、磷酸盐或硫酸盐中的一种或一种以上不同金属元素的盐，金属元素的种类有：Mg、Al、Pb、In、Sn、Sb、Zr、Nb、La、Ce、Ta、Mo、W、Re、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ag、Pt、Pd、Ir、Ru、Rh、Y、Ba、Sr、La和Os。
  4. 根据权利要求1所述的一种微波辅助碳模板法制备负载型纳米金属氧化物或纳米金属材料的方法，其特征在于其中步骤(a)中糖类为葡萄糖、果糖、蔗糖、麦芽糖、乳糖、淀粉，甲基纤维素和糊精中的一种。
  5. 根据权利要求1所述的一种微波辅助碳模板法制备负载型纳米金属氧化物或纳米金属材料的方法，其特征在于其中步骤(a)中糖类与尿素的质量比为20:1～1:60；步骤(a)中糖类与金属盐的质量比为100:1～1:10；步骤(a)中糖类与载体氧化物前驱体的质量比为100:1～1:50；步骤(a)中糖类与水的质量比为50:1～1:100。
  6. 根据权利要求1所述的一种微波辅助碳模板法制备负载型纳米金属氧化物或纳米金属材料的方法，步骤(d)中所述的还原性气体为含氢气或一氧化碳体积分数为5％～10％的混合气，平衡气为氮气或氩气。
  7. 根据权利要求1所述的一种微波辅助碳模板法制备负载型纳米金属氧化物或纳米金属材料的方 法，其特征在于其中所述的步骤(c)得到多孔氧化物载体氧化物是单元素氧化物或是复合氧化物，其中单元素氧化物为下列元素的氧化物中的一种，而复合氧化物则包括两种或两种以上不同元素的氧化物：Si、Mg、Al、Pb、In、Sn、Sb、Zr、Nb、La、Ce、Ta、Mo、W、Re、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ag、Pt、Pd、Ir、Ru、Rh、Y、Ba、Sr、La和Os。
  8. 根据权利要求1所述的一种微波辅助碳模板法制备负载型纳米金属氧化物或纳米金属材料的方法，其特征在于其中所述的步骤(c)得到纳米金属氧化物是单金属元素氧化物或是复合金属氧化物，其中单金属氧化物为下列元素的氧化物中的一种，而复合金属氧化物则包括两种或两种以上不同金属元素的氧化物：Mg、Al、Pb、In、Sn、Sb、Zr、Nb、La、Ce、Ta、Mo、W、Re、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ag、Pt、Pd、Ir、Ru、Rh、Y、Ba、Sr、La和Os。
  9. 根据权利要求1所述的一种微波辅助碳模板法制备负载型纳米金属氧化物或纳米金属材料的方法，其特征在于其中所述的步骤(d)得到多孔氧化物载体氧化物是单元素氧化物或是复合氧化物，其中单元素氧化物为下列元素的氧化物中的一种，而复合氧化物则包括两种或两种以上不同元素的氧化物：Si、Mg、Al、Pb、In、Sn、Sb、Zr、Nb、La、Ce、Ta、Mo、W、Re、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ag、Pt、Pd、Ir、Ru、Rh、Y、Ba、Sr、La和Os。
  10. 根据权利要求1所述的一种微波辅助碳模板法制备负载型纳米金属氧化物或纳米金属材料的方法，其特征在于其中所述的步骤(d)得到的纳米金属可以是一种金属元素的单质也可以是两种及以上不同金属元素的合金或金属间化合物，其中金属元素包括Mg、Al、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Nb、Mo、Pt、Pd、Ru、Os、Rh、Ir、Au、Ag、Pb、In、Sn、Sb、Zr、Nb、La、Ce、Ta、Mo、W或Re。
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