技术领域technical field
本发明属于催化剂制备技术领域，特别涉及一种高分散负载型贵金属纳米粒子及其制备方法。The invention belongs to the technical field of catalyst preparation, and in particular relates to a highly dispersed loaded noble metal nano particle and a preparation method thereof.
背景技术Background technique
负载型贵金属催化剂因其特有的高活性、稳定性以及重复利用性，得到越来越多学者们的重视和关注。目前最为常见的制备负载型贵金属催化剂的方法有：浸渍法、沉淀沉积法和化学还原法等。浸渍法，即把活性组分浸渍在载体表面上，然后进行后续处理。该方法操作简单，是最为传统的合成负载型催化剂的方法。具体的合成过程为：对载体进行预处理、预活化；然后用活性组分的盐溶液浸泡载体，使载体充分、均匀的吸收活性组分；最后用化学还原剂温和还原或使用氢气在一定温度下焙烧还原，最终得到负载型贵金属催化剂。但该方法的缺点是不易控制贵金属颗粒的粒子大小；活性组分粒子容易团聚，分散程度差等。沉淀沉积法的具体合成方法如下：首先把载体和金属盐溶液一同加入到反应容器中，然后滴加一定浓度的碱溶液(如NaOH或LiOH溶液)，到一定pH值后停止滴加，取出混合液进行干燥。干燥后的固体先后进行加热焙烧、还原活化等过程，最终生成负载型的贵金属催化剂。该方法的缺点是不易控制具体沉淀的位置；重复性较差；易在溶液中直接成核而非在载体表面上；生成的粒子颗粒大、大小不均一、分散度差。化学还原的方法首先要选好恰当的化学还原剂(如柠檬酸、硼氢化钠等)。制备过程为：首先把金属盐溶液和载体一起放入反应器中，随后加入一定量的化学还原剂，在无需加热焙烧的情况下，可温和的得到负载型催化剂。此方法对载体几乎没有要求，且金属的流失相对较少。但是还原剂一定要恰当匹配：若使用过强的还原剂，制备出的贵金属粒子尺寸无法控制，出现严重的团聚现象。因此，开发一种通用的、简便的、粒径可控的高分散负载型贵金属纳米粒子仍然是一项具有挑战性的目标。Supported noble metal catalysts have attracted more and more attention and attention from scholars because of their unique high activity, stability and reusability. At present, the most common methods for preparing supported noble metal catalysts are: impregnation method, precipitation deposition method and chemical reduction method. The impregnation method is to impregnate the active component on the surface of the carrier, and then carry out subsequent treatment. This method is simple to operate and is the most traditional method for synthesizing supported catalysts. The specific synthesis process is: pretreatment and preactivation of the carrier; then soaking the carrier with the salt solution of the active component to make the carrier fully and uniformly absorb the active component; Lower calcining and reduction, and finally a supported noble metal catalyst is obtained. However, the disadvantage of this method is that it is not easy to control the particle size of the precious metal particles; the active component particles are easy to agglomerate and the degree of dispersion is poor. The specific synthesis method of the precipitation deposition method is as follows: first, add the carrier and the metal salt solution into the reaction vessel together, then dropwise add a certain concentration of alkali solution (such as NaOH or LiOH solution), stop the dropwise addition after reaching a certain pH value, take out the mixed liquid to dry. The dried solid undergoes processes such as heating, roasting, reduction and activation, and finally produces a supported noble metal catalyst. The disadvantage of this method is that it is not easy to control the specific precipitation position; the repeatability is poor; it is easy to nucleate directly in the solution instead of on the surface of the carrier; the generated particles are large, uneven in size and poor in dispersion. The chemical reduction method must first select an appropriate chemical reducing agent (such as citric acid, sodium borohydride, etc.). The preparation process is as follows: first put the metal salt solution and the carrier into the reactor, and then add a certain amount of chemical reducing agent to obtain the supported catalyst gently without heating and roasting. This method requires little carrier and relatively little metal loss. However, the reducing agent must be properly matched: if the reducing agent is too strong, the size of the prepared noble metal particles cannot be controlled, and serious agglomeration will occur. Therefore, the development of a versatile, facile, and size-controllable highly dispersed loaded noble metal nanoparticles remains a challenging goal.
此外，层状双羟基金属氢氧化物(LDHs)材料，也称为类水滑石，是一类阴离子层状材料，其分子式为[M2+1-xM3+x(OH)2](An-x/n)·mH2O。LDHs其层板由二价和三价金属阳离子组成，作为催化剂载体或者催化剂前体被广泛应用在催化领域。Furthermore, layered double metal hydroxide hydroxides (LDHs) materials, also known as hydrotalcites, are a class of anionic layered materials with the molecular formula [M2+1-x M3+x (OH)2 ]( An−x/n )·mH2 O. LDHs, whose laminates are composed of divalent and trivalent metal cations, are widely used in the field of catalysis as catalyst supports or catalyst precursors.
发明内容Contents of the invention
本发明的目的在于提供一种新型高分散负载型贵金属纳米粒子制备方法，解决了传统负载型贵金属催化剂的制备方法繁琐、周期长、制备环境不绿色环保、粒径不可控的问题。本发明通过在层板中引入Fe2+离子合成出含Fe2+的LDHs，利用层板结构中Fe2+的还原性可还原高价态贵金属离子，通过调控Fe2+与贵金属离子的比例制备得到粒径可控的高分散负载型贵金属纳米粒子。该方法高分散负载型贵金属纳米粒子制备方法无需外加任何还原剂，工艺过程简单、绿色节能、应用前景广泛。The purpose of the present invention is to provide a novel preparation method of highly dispersed supported noble metal nanoparticles, which solves the problems of cumbersome preparation methods, long cycle, unenvironmental preparation environment and uncontrollable particle size of traditional supported noble metal catalysts. The present invention synthesizes Fe2+ -containing LDHs by introducing Fe2+ ions into the laminate, utilizes the reducibility of Fe2+ in the laminate structure to reduce high-valence noble metal ions, and prepares by adjusting the ratio of Fe2+ to noble metal ions Highly dispersed loaded noble metal nanoparticles with controllable particle size are obtained. The preparation method of the highly dispersed loaded noble metal nanoparticles does not need any additional reducing agent, and the process is simple, green and energy-saving, and has broad application prospects.
一种高分散负载型贵金属纳米粒子，通过共沉淀法制备出含Fe2+的LDHs，利用层板结构中Fe2+的还原性还原吸附在LDHs表面的高价氧化态的贵金属离子，得到高分散负载型贵金属纳米粒子，其中，贵金属纳米粒子的粒径大小为0.5～3nm，贵金属的质量百分含量为0.1～2％。A kind of highly dispersed and loaded noble metal nanoparticles. Fe2+ -containing LDHs were prepared by co-precipitation method, and the high-valent oxidation state noble metal ions adsorbed on the surface of LDHs were reduced by the reduction of Fe2+ in the laminate structure to obtain highly dispersed Loaded noble metal nanoparticles, wherein the particle size of the noble metal nanoparticles is 0.5-3nm, and the mass percentage of the noble metal is 0.1-2%.
一种高分散负载型贵金属纳米粒子的制备方法，包括以下步骤：A preparation method of highly dispersed loaded noble metal nanoparticles, comprising the following steps:
1)配制二价金属硝酸盐、氯化亚铁、贵金属的盐或酸的混合溶液，其中，控制二价金属硝酸盐的浓度为0.4～0.55mol/L，控制氯化亚铁的浓度为0.1～0.25mol/L；控制贵金属的盐或酸的浓度为0.5～5mmol/L；1) Prepare a mixed solution of divalent metal nitrate, ferrous chloride, noble metal salt or acid, wherein the concentration of divalent metal nitrate is controlled to be 0.4-0.55mol/L, and the concentration of ferrous chloride is controlled to be 0.1 ～0.25mol/L; control the concentration of precious metal salt or acid to 0.5～5mmol/L;
2)配制氢氧化钠和碳酸钠的碱溶液，控制NaOH的浓度为1～2mol/L，Na2CO3的浓度为0.2～0.8mol/L；2) Prepare the alkali solution of sodium hydroxide and sodium carbonate, control the concentration ofNaOH to be 1-2mol/L, and the concentration ofNa2CO3 to be 0.2-0.8mol/L;
3)在氧气气氛下，将步骤2)的碱溶液逐滴加入步骤1)的混合溶液中，直到体系中的pH值达到9～11，30～60℃晶化8～16h后将反应液离心，洗涤至中性，于40～80℃烘箱中干燥得到高分散负载型贵金属纳米粒子。3) Under an oxygen atmosphere, add the alkali solution in step 2) dropwise to the mixed solution in step 1) until the pH value in the system reaches 9-11, crystallize at 30-60°C for 8-16 hours, and then centrifuge the reaction solution , washed until neutral, and dried in an oven at 40-80° C. to obtain highly dispersed and loaded noble metal nanoparticles.
优选的，步骤1)中的所述二价金属硝酸盐为硝酸镁、硝酸钴、硝酸镍和硝酸锌中的任意一种或者二种。Preferably, the divalent metal nitrate in step 1) is any one or two of magnesium nitrate, cobalt nitrate, nickel nitrate and zinc nitrate.
优选的，步骤1)中的贵金属的酸或盐为H2PtCl6，HAuCl4，RuCl3或H2PdCl4中的任意一种。Preferably, the acid or salt of the noble metal in step 1) is any one of H2 PtCl6 , HAuCl4 , RuCl3 or H2 PdCl4 .
对得到的高分散负载型贵金属纳米粒子进行结构表征。由透射电镜(TEM)图可以发现催化剂粒径小，分布均匀；由X-射线光电子能谱(XPS)谱图可以看出，贵金属离子已经被完全还原成零价态的贵金属纳米粒子。The structure of the obtained highly dispersed supported noble metal nanoparticles was characterized. From the transmission electron microscope (TEM) picture, it can be found that the particle size of the catalyst is small and the distribution is uniform; from the X-ray photoelectron spectroscopy (XPS) spectrum, it can be seen that the noble metal ions have been completely reduced to zero-valent noble metal nanoparticles.
本发明的优点在于：The advantages of the present invention are:
1)通过合成含Fe(II)的LDHs载体，利用其自身还原性成功还原贵金属离子为零价态的贵金属纳米粒子，方法简便且节能环保；1) By synthesizing Fe(II)-containing LDHs carrier, using its own reducing property to successfully reduce noble metal ions to zero-valent noble metal nanoparticles, the method is simple, energy-saving and environmentally friendly;
2)利用载体组成可调控性，通过改变Fe(II)的比例，有效地调控贵金属纳米粒子的粒径；2) Utilizing the controllability of the carrier composition, the particle size of noble metal nanoparticles can be effectively regulated by changing the ratio of Fe(II);
3)此载体原位还原方法可用于还原不同种类的贵金属，具有广泛的普适性。3) This carrier in situ reduction method can be used to reduce different kinds of noble metals, and has wide applicability.
附图说明Description of drawings
图1为实施例1制备的负载纳米铂催化剂的XRD谱图。Fig. 1 is the XRD spectrogram of the loaded nano-platinum catalyst prepared in Example 1.
图2为实施例1制备的负载纳米铂催化剂的TEM谱图。Fig. 2 is the TEM spectrogram of the loaded nano-platinum catalyst prepared in Example 1.
图3为实施例1制备的负载纳米铂催化剂的SEM谱图。Fig. 3 is the SEM spectrogram of the loaded nano-platinum catalyst prepared in Example 1.
图4为实施例1制备的负载纳米铂催化剂的XPS谱图。Fig. 4 is the XPS spectrogram of the loaded nano-platinum catalyst prepared in Example 1.
图5为实施例2制备的负载纳米金催化剂的TEM谱图。Fig. 5 is the TEM spectrogram of the loaded nano-gold catalyst prepared in Example 2.
图6为实施例2制备的负载纳米金催化剂的XPS谱图。Fig. 6 is the XPS spectrogram of the loaded nano-gold catalyst prepared in Example 2.
具体实施方式detailed description
下面通过具体实施例对本发明进行说明，但本发明并不局限于此。The present invention will be described below through specific examples, but the present invention is not limited thereto.
实施例1Example 1
将6.41g的Mg(NO3)2·6H2O、1.66g的FeCl2·6H2O、量取2mL的19.3mmol/L的H2PtCl6溶液加入到50mL的除去二氧化碳的去离子水中，记为溶液甲。将6.0g的NaOH和7.4g的Na2CO3加入到100ml的除去二氧化碳的去离子水中，记为溶液乙。在氧气气氛下，将溶液乙逐滴加入到溶液甲中，直到体系中的PH值达到11，然后在氧气气氛中，40℃晶化15h后将反应液离心并洗涤至中性，于70℃烘箱中干燥，研磨得到负载的高分散Pt纳米粒子。其中Pt颗粒的平均粒径为0.5nm，催化剂中Pt元素的质量百分含量为0.1％。Add 6.41g of Mg(NO3 )2 6H2 O, 1.66g of FeCl2 6H2 O, and 2 mL of 19.3 mmol/L H2 PtCl6 solution into 50 mL of deionized water to remove carbon dioxide, Denoted as solution A. Add 6.0 g of NaOH and 7.4 g of Na2 CO3 into 100 ml of deionized water from which carbon dioxide has been removed, and record it as solution B. In an oxygen atmosphere, add solution B to solution A drop by drop until the pH value in the system reaches 11, then crystallize at 40°C for 15 hours in an oxygen atmosphere, centrifuge and wash the reaction solution to neutrality, and store at 70°C Dried in an oven and ground to obtain loaded highly dispersed Pt nanoparticles. Wherein the average particle diameter of the Pt particles is 0.5nm, and the mass percent content of the Pt element in the catalyst is 0.1%.
对得到的负载型纳米Pt催化剂进行结构表征测试。图1为实施例1合成的LDH负载Pt后催化剂的X射线衍射(XRD)谱图，由图中可以看出LDH的(003)、(006)、(009)、(015)、(018)、(110)、(113)晶面的特征衍射峰，说明通过该方法能够成功合成晶型完整且较纯的LDH。同时没有出现明显的Pt纳米粒子的特征衍射峰，说明催化剂中Pt纳米颗粒的粒径较小且高度分散。图2为实施例1中所述催化剂的透射电子显微镜(TEM)照片。可以看出Pt纳米粒子均匀地高分散在载体表面上，且尺寸均一，平均粒径为0.5nm。图3为扫描电镜图(SEM)，从图中可以看出LDH片生长的较为均匀，有利于Pt的还原且高度分散在其表面。图4为实施例1中所述催化剂的X射线光电子能谱分析(XPS)，从结果看，电子结合能在71.8eV和74.1eV附近的峰归属于Pt0，结合能在73.5eV和75.9eV附近的峰归属于Pt2+，这表明在当前的催化剂中，Pt2+物种和Pt0物种是同时存在的，说明Pt成功被还原。Structural characterization tests were carried out on the obtained supported nano-Pt catalysts. Fig. 1 is the X-ray diffraction (XRD) spectrogram of the catalyst behind the LDH loaded Pt synthesized in Example 1, as can be seen from the figure (003), (006), (009), (015), (018) of LDH , (110), (113) characteristic diffraction peaks of crystal planes, indicating that this method can successfully synthesize LDH with complete crystal form and relatively pure. At the same time, there is no obvious characteristic diffraction peak of Pt nanoparticles, indicating that the particle size of Pt nanoparticles in the catalyst is small and highly dispersed. FIG. 2 is a transmission electron microscope (TEM) photograph of the catalyst described in Example 1. FIG. It can be seen that the Pt nanoparticles are uniformly and highly dispersed on the surface of the carrier with a uniform size and an average particle diameter of 0.5 nm. Figure 3 is a scanning electron microscope image (SEM). It can be seen from the figure that the LDH flakes grow relatively uniformly, which is conducive to the reduction of Pt and is highly dispersed on its surface. Fig. 4 is the X-ray photoelectron spectrum analysis (XPS) of the catalyst described in embodiment 1, from the result, the peak of electron binding energy at 71.8eV and 74.1eV vicinity belongs to Pt0 , binding energy at 73.5eV and 75.9eV The nearby peak is assigned to Pt2+ , which indicates that in the current catalyst, Pt2+ species and Pt0 species exist simultaneously, indicating that Pt was successfully reduced.
实施例2Example 2
将6.41g的Mg(NO3)2·6H2O、1.66g的FeCl2·6H2O、量取2mL的25mmol/L的HAuCl4溶液加入到50mL的除去二氧化碳的去离子水中，记为溶液甲。将6.0g的NaOH和7.4g的Na2CO3加入到100ml的除去二氧化碳的去离子水中，记为溶液乙。在氧气气氛下，将溶液乙逐滴加入到溶液甲中，直到体系中的PH值达到11，然后在氧气气氛中，40℃晶化15h后将反应液离心并洗涤至中性，于70℃烘箱中干燥，研磨得到负载的高分散Au纳米粒子。其中Au颗粒的平均粒径为1.5nm，催化剂中Au元素的质量百分含量为0.4％。Add 6.41g of Mg(NO3 )2 6H2 O, 1.66g of FeCl2 6H2 O, and 2 mL of 25 mmol/L HAuCl4 solution into 50 mL of deionized water from which carbon dioxide has been removed, and record it as solution First. Add 6.0 g of NaOH and 7.4 g of Na2 CO3 into 100 ml of deionized water from which carbon dioxide has been removed, and record it as solution B. In an oxygen atmosphere, add solution B to solution A drop by drop until the pH value in the system reaches 11, then in an oxygen atmosphere, crystallize at 40°C for 15 hours, centrifuge and wash the reaction solution to neutrality, and store at 70°C Dried in an oven and ground to obtain loaded highly dispersed Au nanoparticles. The average particle diameter of the Au particles is 1.5nm, and the mass percent content of the Au element in the catalyst is 0.4%.
图5为实施例2中所述催化剂的透射电子显微镜(TEM)照片。可以看出Au纳米粒子均匀地高分散在载体表面上，且尺寸均一，颗粒的平均粒径为1.5nm。图6为实施例2中所述催化剂的X射线光电子能谱分析(XPS)，从结果看，由于Mg的2s轨道与Au的4f轨道有重合，对其进行分峰，电子结合能在83.4eV和87.7eV附近的峰归属于Au0，说明Au成功被还原。FIG. 5 is a transmission electron microscope (TEM) photograph of the catalyst described in Example 2. FIG. It can be seen that the Au nanoparticles are uniformly and highly dispersed on the surface of the carrier, and the size is uniform, and the average particle diameter of the particles is 1.5nm. Fig. 6 is the X-ray photoelectron spectrum analysis (XPS) of the catalyst described in embodiment 2, from the result, because the 2s orbit of Mg overlaps with the 4f orbit of Au, it is carried out to divide the peak, electron binding energy is at 83.4eV and the peaks around 87.7eV are assigned to Au0 , indicating that Au has been successfully reduced.
实施例3Example 3
将6.55g的Co(NO3)2·6H2O、1.49g的FeCl2·6H2O和量取3ml，25mmol/L的RuCl3溶液加入到50mL的除去二氧化碳的去离子水中，记为溶液甲。将6.0g的NaOH和7.4g的Na2CO3加入到100ml的除去二氧化碳的去离子水中，记为溶液乙。在氧气气氛下，将溶液乙逐滴加入到溶液甲中，直到体系中的PH值达到11，然后在氧气气氛中，40℃晶化15h后将反应液离心并洗涤至中性，于70℃烘箱中干燥，研磨得到负载的高分散Ru纳米粒子。其中Ru颗粒的平均粒径为2nm，催化剂中Ru元素的质量百分含量为0.5％。Add 6.55g of Co(NO3 )2 6H2 O, 1.49g of FeCl2 6H2 O and 3ml of 25mmol/L RuCl3 solution into 50mL of deionized water from which carbon dioxide has been removed, and record it as solution First. Add 6.0 g of NaOH and 7.4 g of Na2 CO3 into 100 ml of deionized water from which carbon dioxide has been removed, and record it as solution B. In an oxygen atmosphere, add solution B to solution A drop by drop until the pH value in the system reaches 11, then crystallize at 40°C for 15 hours in an oxygen atmosphere, centrifuge and wash the reaction solution to neutrality, and store at 70°C Dry in an oven and grind to obtain loaded highly dispersed Ru nanoparticles. The average particle size of the Ru particles is 2nm, and the mass percentage of Ru element in the catalyst is 0.5%.
实施例4Example 4
将6.54g的Ni(NO3)2·6H2O、1.49g的FeCl2·6H2O和量取4ml，25mmol/L的H2PdCl4溶液加入到50mL的除去二氧化碳的去离子水中，记为溶液甲。将4.8g的NaOH和5.3g的Na2CO3加入到100ml的除去二氧化碳的去离子水中，记为溶液乙。在氧气气氛下，将溶液乙逐滴加入到溶液甲中，直到体系中的PH值达到11，然后在氧气气氛中，40℃晶化15h后将反应液离心并洗涤至中性，于70℃烘箱中干燥，研磨得到负载的高分散Pd纳米粒子。其中Pd颗粒的平均粒径为1nm，催化剂中Pd元素的质量百分含量为0.4％。Add 6.54g of Ni(NO3 )2 6H2 O, 1.49g of FeCl2 6H2 O and 4ml of 25mmol/L H2 PdCl4 solution into 50mL of deionized water to remove carbon dioxide, record For solution A. Add 4.8 g of NaOH and 5.3 g of Na2 CO3 into 100 ml of deionized water from which carbon dioxide has been removed, and record it as solution B. In an oxygen atmosphere, add solution B to solution A drop by drop until the pH value in the system reaches 11, then in an oxygen atmosphere, crystallize at 40°C for 15 hours, centrifuge and wash the reaction solution to neutrality, and store at 70°C Dried in an oven and ground to obtain loaded highly dispersed Pd nanoparticles. The average particle diameter of the Pd particles is 1 nm, and the mass percent content of the Pd element in the catalyst is 0.4%.
可以理解的是，以上是为了阐述本发明的原理和可实施性的示例，本发明并不局限于此。对于本领域内的普通技术人员而言，在不脱离本发明的精神和实质的情况下，可以做出各种变型和改进，这些变型和改进也视为本发明的保护范围。It can be understood that the above is an example for explaining the principles and practicability of the present invention, and the present invention is not limited thereto. For those skilled in the art, various modifications and improvements can be made without departing from the spirit and essence of the present invention, and these modifications and improvements are also regarded as the protection scope of the present invention.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108777309A (en)* | 2018-05-15 | 2018-11-09 | 北京化工大学 | A kind of monatomic Pd catalyst of support type and preparation method thereof and catalytic applications |
| CN109482236A (en)* | 2018-12-09 | 2019-03-19 | 华东交通大学 | A method of noble metal nano particles are carried in metallo-organic framework |
| CN112974842A (en)* | 2021-02-05 | 2021-06-18 | 南京航空航天大学 | Nano multiphase reinforced aluminum matrix composite material and preparation method thereof |
| CN113101910A (en)* | 2021-03-31 | 2021-07-13 | 江苏晶晶新材料有限公司 | Large-pore-volume aluminum oxide material with reducibility and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6387033B1 (en)* | 2000-11-22 | 2002-05-14 | Council Of Scientific And Industrial Research | Preparation of new layered double hydroxides exchanged with osmate for asymmetric dihydroxylation of olefins to vicinal diols |
| CN102658132A (en)* | 2012-04-27 | 2012-09-12 | 北京化工大学 | Preparation method for gold-containing hydrotalcite composite material |
| CN102974365A (en)* | 2012-12-12 | 2013-03-20 | 天津工业大学 | Method for preparing load type high-dispersion multi-component precious metal nanoparticle catalyst |
| CN105148908A (en)* | 2015-08-17 | 2015-12-16 | 四川中自尾气净化有限公司 | Preparation method and application of supported noble metal catalyst |
| CN105289587A (en)* | 2014-07-01 | 2016-02-03 | 赵晓宇 | Supported-type precious metal photocatalyser and preparation method thereof |
| CN105457629A (en)* | 2015-12-11 | 2016-04-06 | 上海源由纳米科技有限公司 | Load type nano precious metal catalyst and preparation method and application thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6387033B1 (en)* | 2000-11-22 | 2002-05-14 | Council Of Scientific And Industrial Research | Preparation of new layered double hydroxides exchanged with osmate for asymmetric dihydroxylation of olefins to vicinal diols |
| CN102658132A (en)* | 2012-04-27 | 2012-09-12 | 北京化工大学 | Preparation method for gold-containing hydrotalcite composite material |
| CN102974365A (en)* | 2012-12-12 | 2013-03-20 | 天津工业大学 | Method for preparing load type high-dispersion multi-component precious metal nanoparticle catalyst |
| CN105289587A (en)* | 2014-07-01 | 2016-02-03 | 赵晓宇 | Supported-type precious metal photocatalyser and preparation method thereof |
| CN105148908A (en)* | 2015-08-17 | 2015-12-16 | 四川中自尾气净化有限公司 | Preparation method and application of supported noble metal catalyst |
| CN105457629A (en)* | 2015-12-11 | 2016-04-06 | 上海源由纳米科技有限公司 | Load type nano precious metal catalyst and preparation method and application thereof |
| Title |
|---|
| PING LI ET AL.: "Monodispersed Pd clusters generated in situ by their own reductive support for high activity andstability in cross-coupling reactions", 《JOURNAL OF MATERIALS CHEMISTRY A》* |
| 中国人民武装警察部队黄金指挥部: "《金矿地质与勘探论文集》", 31 December 1992, 冶金工业出版社* |
| 徐亮等: "水滑石定位生长高分散贵金属纳米颗粒及其电化学性能研究", 《中国化学会第30届学术年会摘要集-第三分会：纳米传感新原理新方法》* |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108777309A (en)* | 2018-05-15 | 2018-11-09 | 北京化工大学 | A kind of monatomic Pd catalyst of support type and preparation method thereof and catalytic applications |
| CN109482236A (en)* | 2018-12-09 | 2019-03-19 | 华东交通大学 | A method of noble metal nano particles are carried in metallo-organic framework |
| CN112974842A (en)* | 2021-02-05 | 2021-06-18 | 南京航空航天大学 | Nano multiphase reinforced aluminum matrix composite material and preparation method thereof |
| CN113101910A (en)* | 2021-03-31 | 2021-07-13 | 江苏晶晶新材料有限公司 | Large-pore-volume aluminum oxide material with reducibility and preparation method thereof |
| CN113101910B (en)* | 2021-03-31 | 2021-12-14 | 江苏晶晶新材料有限公司 | Large-pore-volume aluminum oxide material with reducibility and preparation method thereof |
| Publication | Publication Date | Title |
|---|---|---|
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