CN118321542A - A size-controllable, highly dispersed ultra-small nanocluster and its preparation method and application - Google Patents

A size-controllable, highly dispersed ultra-small nanocluster and its preparation method and application Download PDF

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CN118321542A
CN118321542A CN202410433817.1A CN202410433817A CN118321542A CN 118321542 A CN118321542 A CN 118321542A CN 202410433817 A CN202410433817 A CN 202410433817A CN 118321542 A CN118321542 A CN 118321542A
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束远
张鹏飞
刘谦
毕淑娴
张泽群
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Ningxia University
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Abstract

本发明属于纳米材料和多相催化领域,具体涉及一种尺寸可控高分散的超小纳米团簇及其制备方法与应用。所述制备方法包括:以环己烷和乙醇为溶剂,加入过量表面改性剂和氧化物载体超声分散,然后通过旋转蒸发仪去除溶剂,在高温下吸附一段时间后,使用适量环己烷通过洗涤控制表面改性剂含量,干燥后与金属前驱体盐混合后进行球磨、锻烧,即得。该制备方法采用液相前处理+固相结合的方式,使制得的尺寸可控高分散的超小纳米团簇具有尺寸可控、分散度高的优点,解决了现有液相沉淀法、热分解法和溶胶‑凝胶法、溶液浸渍法等合成过程中负载金属氧化物尺寸不均、分散度低易团聚等问题。

The present invention belongs to the field of nanomaterials and heterogeneous catalysis, and is particularly related to a kind of ultra-small nano clusters with controlled size and high dispersion, and its preparation method and application. The preparation method includes: using cyclohexane and ethanol as solvent, adding excessive surface modifier and oxide carrier ultrasonic dispersion, then removing the solvent by rotary evaporator, adsorbing at high temperature for a period of time, using appropriate amount of cyclohexane to control the content of surface modifier by washing, and mixing with metal precursor salt after drying, ball milling and calcining are performed to obtain. The preparation method adopts the mode of liquid phase pretreatment + solid phase combination, so that the obtained ultra-small nano clusters with controlled size and high dispersion have the advantages of controlled size and high dispersion, and solve the problems of uneven size of loaded metal oxides, low dispersion and easy agglomeration in the synthesis process such as existing liquid phase precipitation method, thermal decomposition method and sol-gel method, solution impregnation method.

Description

一种尺寸可控高分散的超小纳米团簇及其制备方法与应用A size-controllable, highly dispersed ultra-small nanocluster and its preparation method and application

技术领域Technical Field

本发明属于纳米材料和多相催化领域,具体涉及一种尺寸可控高分散的超小纳米团簇及其制备方法与应用。The invention belongs to the field of nano materials and heterogeneous catalysis, and specifically relates to a size-controllable and highly dispersed ultra-small nano cluster and a preparation method and application thereof.

背景技术Background technique

纳米尺寸小于100nm的金属纳米团簇具有独特的电子、磁性、光学和化学性质,而小于3nm的团簇便具有量子尺寸效应、高比表面积,在多相催化领域中具有非常意义。Metal nanoclusters with a nanosize of less than 100 nm have unique electronic, magnetic, optical and chemical properties, while clusters smaller than 3 nm have quantum size effects and high specific surface areas, which are of great significance in the field of heterogeneous catalysis.

对于目前合成纳米团簇的方法主要基于是化学方法和重新暴露纳米团簇表面的方法,但都存在这严重问题,如湿化学方法一般使用的包覆剂会严重阻塞催化剂外表面;重新暴露纳米团簇表面的热处理、氧化处理等通常会导致纳米团簇的大小和形态发生不可逆变化。也有一些较为精细的方法可以合成纳米团簇但均仅适用于实验室级产品的合成,无法大规模的制备。The current methods for synthesizing nanoclusters are mainly based on chemical methods and methods for re-exposing the surface of nanoclusters, but both have serious problems. For example, the coating agents generally used in wet chemical methods will seriously block the outer surface of the catalyst; heat treatment and oxidation treatment of re-exposing the surface of nanoclusters usually cause irreversible changes in the size and morphology of nanoclusters. There are also some more sophisticated methods for synthesizing nanoclusters, but they are only suitable for the synthesis of laboratory-level products and cannot be prepared on a large scale.

故基于此,提出本发明技术方案。Therefore, based on this, the technical solution of the present invention is proposed.

发明内容Summary of the invention

为了解决现有技术存在的问题,本发明提出了一种固态“锚定”策略的概念来合成尺寸可控高分散的超小纳米团簇。具体来说,通过基于路易斯酸的相互作用,加强表面改性剂和氧化物载体之间的相互作用。锚定的表面改性剂分子在后续的合成过程中作为络合剂,在固态球磨过程中进一步捕获和分散乙酰丙酮金属盐配合物。机械球磨过程除了提供剪切力分散金属前驱体盐外,还加强了金属阳离子和氧化物载体之间的相互作用。因此,即使在500℃的空气中煅烧后,仍然可以高度分散的Ni,甚至在750℃的高温煅烧条件下仍可以保持6.5nm的超小尺寸In order to solve the problems existing in the prior art, the present invention proposes the concept of a solid-state "anchoring" strategy to synthesize ultra-small nanoclusters with controllable size and high dispersion. Specifically, the interaction between the surface modifier and the oxide support is strengthened through Lewis acid-based interactions. The anchored surface modifier molecules act as complexing agents in the subsequent synthesis process to further capture and disperse the acetylacetone metal salt complex during the solid-state ball milling process. In addition to providing shear force to disperse the metal precursor salt, the mechanical ball milling process also strengthens the interaction between the metal cations and the oxide support. Therefore, even after calcination in air at 500°C, Ni can still be highly dispersed, and even under high-temperature calcination conditions at 750°C, it can still maintain an ultra-small size of 6.5nm.

本发明的方案是提供一种尺寸可控高分散的超小纳米团簇的制备方法,所述制备方法包括如下步骤:The solution of the present invention is to provide a method for preparing size-controllable and highly dispersed ultra-small nanoclusters, the preparation method comprising the following steps:

(1)将表面改性剂和氧化物加入溶剂中进行超声分散,得到分散液;(1) adding a surface modifier and an oxide into a solvent and performing ultrasonic dispersion to obtain a dispersion;

(2)对所述分散液进行旋蒸以除去溶剂,并在加热条件下使表面改性剂与氧化物吸附完全,得到旋蒸物;(2) performing rotary evaporation on the dispersion to remove the solvent, and allowing the surface modifier and the oxide to be completely adsorbed under heating conditions to obtain a rotary evaporator;

(3)对所述旋蒸物进行洗涤,并依次离心、干燥,得到前处理氧化物;(3) washing the rotary evaporation product, centrifuging and drying the product in sequence to obtain a pre-treated oxide;

(4)将所述前处理氧化物与金属前驱体盐进行混合,然后依次球磨、煅烧,即得到尺寸可控高分散的超小纳米团簇。(4) The pretreated oxide is mixed with a metal precursor salt, and then ball-milled and calcined in sequence to obtain ultra-small nanoclusters with controllable size and high dispersion.

优选地,步骤(1)中,所述表面改性剂为油胺、油酸、油酸钠、甘油、聚乙二醇、十八硫醇、十八烯、十六烷基三甲基溴化铵中的一种;Preferably, in step (1), the surface modifier is one of oleylamine, oleic acid, sodium oleate, glycerol, polyethylene glycol, octadecyl mercaptan, octadecene, and hexadecyltrimethylammonium bromide;

和/或,所述氧化物为氧化铝、二氧化钛、二氧化铈、二氧化硅、氧化锆、氧化镁、氧化铁、氧化锌中的一种;And/or, the oxide is one of aluminum oxide, titanium dioxide, cerium dioxide, silicon dioxide, zirconium oxide, magnesium oxide, iron oxide, and zinc oxide;

和/或,所述溶剂为环己烷和乙醇。And/or, the solvent is cyclohexane and ethanol.

优选地,所述环己烷和乙醇的体积比为0.3~0.5:1;Preferably, the volume ratio of cyclohexane to ethanol is 0.3-0.5:1;

和/或,所述油胺和氧化铝的摩尔比为0.5~0.9:1。And/or, the molar ratio of oleylamine to aluminum oxide is 0.5-0.9:1.

优选地,步骤(2)中,在70~100℃条件下使表面改性剂与氧化物吸附完全。Preferably, in step (2), the surface modifier and the oxide are completely adsorbed at 70-100°C.

优选地,步骤(3)中,采用环己烷对所述旋蒸物进行洗涤。Preferably, in step (3), cyclohexane is used to wash the rotary evaporation product.

优选地,步骤(4)中,所述金属前驱体盐为乙酰丙酮盐或醋酸盐中的一种或两种的组合;Preferably, in step (4), the metal precursor salt is one or a combination of acetylacetonate or acetate;

和/或,所述金属前驱体盐和氧化物的摩尔比为0.005~0.1:1;and/or, the molar ratio of the metal precursor salt to the oxide is 0.005 to 0.1:1;

和/或,所述球磨的时间为0.25~1h;And/or, the ball milling time is 0.25 to 1 h;

和/或,所述煅烧的温度为350~800℃,煅烧的时间为1~4h。And/or, the calcination temperature is 350-800° C., and the calcination time is 1-4 hours.

优选地,所述乙酰丙酮盐包括乙酰丙酮铂,乙酰丙酮铜、乙酰丙酮镍、乙酰丙酮钯、乙酰丙酮铷、乙酰丙酮铑、乙酰丙酮铈和乙酰丙酮镧;Preferably, the acetylacetonate includes platinum acetylacetonate, copper acetylacetonate, nickel acetylacetonate, palladium acetylacetonate, rubidium acetylacetonate, rhodium acetylacetonate, cerium acetylacetonate and lanthanum acetylacetonate;

和/或,球磨过程中采用的球磨机为行星式球磨机、高能球磨机、三维高速振动球磨机(MSK-SFM-3)或手动研磨。And/or, the ball mill used in the ball milling process is a planetary ball mill, a high-energy ball mill, a three-dimensional high-speed vibration ball mill (MSK-SFM-3) or manual grinding.

基于相同的技术构思,本发明的再一方案是提供一种上述制备方法得到的尺寸可控高分散的超小纳米团簇。Based on the same technical concept, another solution of the present invention is to provide a size-controllable and highly dispersed ultra-small nanoclusters obtained by the above preparation method.

基于相同的技术构思,本发明的另一方案是提供一种尺寸可控高分散的超小纳米团簇在制备多相热催化剂、电催化剂、光催化剂和吸附剂中的应用。Based on the same technical concept, another solution of the present invention is to provide an application of size-controllable and highly dispersed ultra-small nanoclusters in the preparation of heterogeneous thermal catalysts, electrocatalysts, photocatalysts and adsorbents.

本发明的有益效果为:The beneficial effects of the present invention are:

(1)本发明采用液相+固相结合的制备方式进行尺寸可控高分散的超小纳米团簇的制备,本发明利用长链有机物作为载体表面改性剂,在Lewis酸(Al-OH和NH2-R)的相互作用下,使表面改性剂与氧化物载体锚定在一起。在固相球磨的作用下,将金属前驱体盐溶解到氧化物载体的晶格中,实现氧化物载体和金属前驱体盐的均匀混合,然后在煅烧过程中存在的表面改性剂发挥作用,增加了纳米团簇的分散性并限制其过度增长,即得尺寸可控高分散的超小纳米团簇。该制备方法解决了现有液相沉淀法、浸渍法、热分解法和溶胶-凝胶法等合成过程中尺寸可控高分散的纳米团簇尺寸不均、颗粒较大、分散度低等问题,所制备的纳米团簇还具有一定的疏水能力,在一些有水产生的反应中有着意想不到的用处。此外,该制备方法简单,制备效率高,能耗小,具备工业放大合成的可能,适用于工业化大规模生产。(1) The present invention adopts a liquid phase + solid phase combined preparation method to prepare ultra-small nano clusters with controllable size and high dispersion. The present invention uses long-chain organic matter as a carrier surface modifier. Under the interaction of Lewis acid (Al-OH and NH2 -R), the surface modifier is anchored with the oxide carrier. Under the action of solid phase ball milling, the metal precursor salt is dissolved into the lattice of the oxide carrier to achieve uniform mixing of the oxide carrier and the metal precursor salt. Then, the surface modifier present in the calcination process plays a role, increasing the dispersibility of the nano clusters and limiting their excessive growth, thus obtaining ultra-small nano clusters with controllable size and high dispersion. The preparation method solves the problems of uneven size, large particles, and low dispersion of nano clusters with controllable size and high dispersion in the existing liquid phase precipitation method, impregnation method, thermal decomposition method, and sol-gel method. The prepared nano clusters also have a certain hydrophobicity and have unexpected uses in some reactions where water is produced. In addition, the preparation method is simple, has high preparation efficiency, low energy consumption, and the possibility of industrial scale-up synthesis, and is suitable for industrial large-scale production.

(2)本发明制得的尺寸可控高分散的超小纳米团簇具有尺寸均一、大小可控、分散度高、疏水、颗粒最小可至1nm、形态可控和环境友好的优点;可应用于多相热催化剂、电催化剂、光催化剂和吸附剂等领域。(2) The size-controllable and highly dispersed ultrasmall nanoclusters prepared by the present invention have the advantages of uniform size, controllable size, high dispersion, hydrophobicity, particles as small as 1 nm, controllable morphology and environmental friendliness; they can be applied to the fields of multiphase thermal catalysts, electrocatalysts, photocatalysts and adsorbents.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

图1是实施例1制得1%-Ni-Al2O3-OAm-500的透射电子显微镜照片和mapping照片。FIG. 1 is a transmission electron microscope photo and a mapping photo of 1%-Ni-Al 2 O 3 -OAm-500 prepared in Example 1. FIG.

图2是实施例1制得1%-Ni-Al2O3-OAm-500的制备过程中各个阶段的疏水角测试图。FIG. 2 is a test diagram of the hydrophobic angle at each stage in the preparation process of 1%-Ni-Al 2 O 3 -OAm-500 prepared in Example 1. FIG.

图3是实施例1制得5%-Ni-Al2O3-OAm-750的透射电子显微镜照片和mapping照片。FIG. 3 is a transmission electron microscope photo and a mapping photo of 5%-Ni-Al 2 O 3 -OAm-750 prepared in Example 1. FIG.

图4是实施例2制得1%-Pt-Al2O3-OAm-500的透射电子显微镜照片和mapping照片。FIG. 4 is a transmission electron microscope photo and a mapping photo of 1%-Pt-Al 2 O 3 -OAm-500 prepared in Example 2. FIG.

图5是实施例3制得1%-Cu-SiO2-OAm-500的透射电子显微镜照片和mapping照片。FIG. 5 is a transmission electron microscope photo and a mapping photo of 1%-Cu-SiO 2 -OAm-500 prepared in Example 3.

具体实施方式Detailed ways

为使本发明的目的、技术方案和优点更加清楚,下面将对本发明的技术方案进行详细的描述。显然,所描述的实施例仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动的前提下所得到的所有其它实施方式,都属于本发明所保护的范围。To make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described in detail below. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other implementation methods obtained by ordinary technicians in this field without creative work belong to the scope of protection of the present invention.

实施例1Example 1

本实施例提供一种尺寸可控高分散的超小纳米团簇的制备方法,所述制备方法包括如下步骤:This embodiment provides a method for preparing size-controllable and highly dispersed ultra-small nanoclusters, the preparation method comprising the following steps:

将2g的Al2O3(19.62mmol)和5mL(15.48mmol)油胺加入到含有20mL环己烷和50mL乙醇的烧瓶中,超声分散30min,使用旋转蒸发仪去除溶剂环己烷和乙醇,封口后放入100℃烘箱中使氧化铝充分吸收油胺12h。使用50mL环己烷洗涤去除多余油胺,离心、干燥,将21.8mg乙酰丙酮镍和预处理的氧化铝放入一个50mL的不锈钢球磨机罐中,罐中装有4个直径为20mm的不锈钢大球和12个直径为10mm的不锈钢小球。将球磨罐密封,转移到三维高速振动球磨机(MSK-SFM-3)上,球磨运行0.5h。2g of Al2O3 (19.62mmol) and 5mL (15.48mmol) of oleylamine were added to a flask containing 20mL of cyclohexane and 50mL of ethanol, and ultrasonically dispersed for 30min. The solvents cyclohexane and ethanol were removed by rotary evaporator, and the flask was sealed and placed in a 100℃ oven to allow the alumina to fully absorb the oleylamine for 12h. 50mL of cyclohexane was used to wash and remove the excess oleylamine, and the flask was centrifuged and dried. 21.8mg of nickel acetylacetonate and pretreated alumina were placed in a 50mL stainless steel ball mill jar, which contained 4 stainless steel large balls with a diameter of 20mm and 12 stainless steel small balls with a diameter of 10mm. The ball mill jar was sealed and transferred to a three-dimensional high-speed vibration ball mill (MSK-SFM-3), and the ball milling was run for 0.5h.

随后,在500℃下煅烧2h,升温速率5℃/min,根据含量、吸附剂、煅烧温度将制备出的样品命名为“1%-Ni-Al2O3-OAm-500”。Subsequently, the sample was calcined at 500°C for 2 h with a heating rate of 5°C/min. The prepared sample was named "1%-Ni-Al 2 O 3 -OAm-500" according to the content, adsorbent and calcination temperature.

对制得的“1%-Ni-Al2O3-OAm-500”在5%的H2/Ar气氛下500℃(5℃/min)还原2h,进行透射电子显微镜测试和EDS(Energy Dispersive Spectrometer)的测试,如图1所示。The prepared “1%-Ni—Al 2 O 3 -OAm-500” was reduced at 500° C. (5° C./min) for 2 h in a 5% H 2 /Ar atmosphere, and then tested by transmission electron microscopy and EDS (Energy Dispersive Spectrometer), as shown in FIG1 .

从图1看出,采用OAm锚定法在500℃下煅烧2小时后,氢气还原后的Al2O3衬底上没有镍颗粒。随后在同一位置进行高角度环形暗场扫描透射电子显微镜(HADDF)成像。然而,没有观察到明显的镍颗粒。通过EDS发现Ni在Al2O3上分散的非常均匀,并没有出现团聚现象。As shown in Figure 1, after calcination at 500°C for 2 hours using the OAm anchoring method, there are no nickel particles on the Al 2 O 3 substrate after hydrogen reduction. High-angle annular dark field scanning transmission electron microscopy (HADDF) imaging was then performed at the same location. However, no obvious nickel particles were observed. EDS found that Ni was very evenly dispersed on Al 2 O 3 and no agglomeration occurred.

从图2的疏水角实验发现,OAm的应用使催化剂从亲水变为疏水,这对催化剂在抗水方面的应用提供了应用前景。From the hydrophobic angle experiment in Figure 2, it was found that the application of OAm changed the catalyst from hydrophilic to hydrophobic, which provides application prospects for the application of catalysts in water resistance.

随后对Ni-Al2O3-OAm进行了高温抗团聚实验测试,为了更加明显的观察颗粒变化,采用5%的Ni负载量。如图3所示,在750℃(5℃/min)煅烧了2h,然后在5%的H2/Ar气氛下500℃(5℃/min)还原2h,命名为“5%-Ni-Al2O3-OAm-750”,通过统计得到Ni颗粒也仅仅只有6.8nm,EDS也证明Ni分散良好,并未有明显团聚现象出现。这说明本方法所制备的催化剂具有更好的耐高温团聚性能,可应用在一些高温导致颗粒团聚从而反应失活的应用中。Subsequently, a high-temperature anti-agglomeration test was conducted on Ni-Al 2 O 3 -OAm. In order to observe the particle changes more clearly, a 5% Ni loading was used. As shown in Figure 3, it was calcined at 750°C (5°C/min) for 2h, and then reduced at 500°C (5°C/min) for 2h in a 5% H 2 /Ar atmosphere. It was named "5%-Ni-Al 2 O 3 -OAm-750". According to statistics, the Ni particles were only 6.8nm. EDS also proved that Ni was well dispersed and no obvious agglomeration occurred. This shows that the catalyst prepared by this method has better high-temperature agglomeration resistance and can be used in some applications where high temperature causes particle agglomeration and reaction deactivation.

实施例2Example 2

本实施例提供一种尺寸可控高分散的超小纳米团簇的制备方法,所述制备方法包括如下步骤:This embodiment provides a method for preparing size-controllable and highly dispersed ultra-small nanoclusters, the preparation method comprising the following steps:

将2g的Al2O3(19.62mmol)和5mL(15.48mmol)油胺加入到含有20mL环己烷和50mL乙醇的烧瓶中,超声分散30min,使用旋转蒸发仪去除溶剂环己烷和乙醇,封口后放入100℃烘箱中使氧化铝充分吸收油胺12h。使用50mL环己烷洗涤去除多余油胺,离心、干燥,将10.8mg乙酰丙酮铂和预处理的氧化铝放入一个50mL的不锈钢球磨机罐中,罐中装有4个直径为20mm的不锈钢大球和12个直径为10mm的不锈钢小球。将球磨罐密封,转移到三维高速振动球磨机(MSK-SFM-3)上,球磨运行0.5h。2g of Al2O3 (19.62mmol) and 5mL (15.48mmol) of oleylamine were added to a flask containing 20mL of cyclohexane and 50mL of ethanol, and ultrasonically dispersed for 30min. The solvents cyclohexane and ethanol were removed by rotary evaporator, and the flask was sealed and placed in a 100℃ oven to allow the alumina to fully absorb the oleylamine for 12h. 50mL of cyclohexane was used to wash and remove excess oleylamine, and the flask was centrifuged and dried. 10.8mg of acetylacetonate platinum and pretreated alumina were placed in a 50mL stainless steel ball mill jar, which contained 4 stainless steel large balls with a diameter of 20mm and 12 stainless steel small balls with a diameter of 10mm. The ball mill jar was sealed and transferred to a three-dimensional high-speed vibration ball mill (MSK-SFM-3), and the ball milling was run for 0.5h.

随后,在500℃下煅烧2h,升温速率5℃/min,根据含量、吸附剂、煅烧温度将制备出的样品命名为“1%-Pt-Al2O3-OAm-500”。Subsequently, the sample was calcined at 500°C for 2 h with a heating rate of 5°C/min. The prepared sample was named "1%-Pt-Al 2 O 3 -OAm-500" according to the content, adsorbent and calcination temperature.

“1%-Pt-Al2O3-OAm-500”的TEM和EDS如图4所示,从图4中可知,Pt的颗粒只要惊人的1.41nm,EDS证实了Pt在Al2O3上的均匀分散。The TEM and EDS of "1%-Pt-Al 2 O 3 -OAm-500" are shown in FIG4 . As can be seen from FIG4 , the Pt particles are surprisingly only 1.41 nm. EDS confirms the uniform dispersion of Pt on Al 2 O 3 .

实施例3Example 3

本实施例提供一种尺寸可控高分散的超小纳米团簇的制备方法,所述制备方法包括如下步骤:This embodiment provides a method for preparing size-controllable and highly dispersed ultra-small nanoclusters, the preparation method comprising the following steps:

将2g的Al2O3(19.62mmol)和5mL(15.48mmol)油胺加入到含有20mL环己烷和50mL乙醇的烧瓶中,超声分散30min,使用旋转蒸发仪去除溶剂环己烷和乙醇,封口后放入100℃烘箱中使氧化铝充分吸收油胺12h。使用50mL环己烷洗涤去除多余油胺,离心、干燥,将20.6mg乙酰丙酮铜和预处理的氧化铝放入一个50mL的不锈钢球磨机罐中,罐中装有4个直径为20mm的不锈钢大球和12个直径为10mm的不锈钢小球。将球磨罐密封,转移到三维高速振动球磨机(MSK-SFM-3)上,球磨运行0.5h。2g of Al2O3 (19.62mmol) and 5mL (15.48mmol) of oleylamine were added to a flask containing 20mL of cyclohexane and 50mL of ethanol, and ultrasonically dispersed for 30min. The solvents cyclohexane and ethanol were removed by rotary evaporator, and the flask was sealed and placed in a 100℃ oven to allow the alumina to fully absorb the oleylamine for 12h. 50mL of cyclohexane was used to wash and remove excess oleylamine, and the flask was centrifuged and dried. 20.6mg of copper acetylacetonate and pretreated alumina were placed in a 50mL stainless steel ball mill jar, which contained 4 stainless steel large balls with a diameter of 20mm and 12 stainless steel small balls with a diameter of 10mm. The ball mill jar was sealed and transferred to a three-dimensional high-speed vibration ball mill (MSK-SFM-3), and the ball milling was run for 0.5h.

随后,在500℃下煅烧2h,升温速率5℃/min,根据含量、吸附剂、煅烧温度将制备出的样品命名为“1%-Cu-SiO2-OAm-500”。Subsequently, the sample was calcined at 500°C for 2 h with a heating rate of 5°C/min. The prepared sample was named "1%-Cu-SiO 2 -OAm-500" according to the content, adsorbent and calcination temperature.

图5是是1%-Cu-SiO2-OAm-500的TEM和EDS图像。根据图5所示的大量统计数据,是1%-Cu-SiO2-OAm-500的平均粒径为2.3nm。这是因为SiO2与OAm之间的相互作用有限,只有少量OAm分子被吸附,导致CuNCs的尺寸不如Ni和PtNCs均匀。但仍没有观察到金属聚集现象,如图5所示的Cu元素能谱图证实了这一点。Figure 5 is the TEM and EDS images of 1%-Cu-SiO 2 -OAm-500. According to the large amount of statistical data shown in Figure 5, the average particle size of 1%-Cu-SiO 2 -OAm-500 is 2.3nm. This is because the interaction between SiO 2 and OAm is limited, and only a small number of OAm molecules are adsorbed, resulting in the size of CuNCs being less uniform than that of Ni and PtNCs. However, no metal aggregation phenomenon was observed, which was confirmed by the Cu element energy spectrum shown in Figure 5.

以上所述,仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应以所述权利要求的保护范围为准。The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art who is familiar with the technical field can easily think of changes or substitutions within the technical scope disclosed by the present invention, which should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims (9)

1. The preparation method of the size-controllable high-dispersion ultra-small nanoclusters is characterized by comprising the following steps of:
(1) Adding a surface modifier and an oxide into a solvent for ultrasonic dispersion to obtain a dispersion liquid;
(2) Spin-evaporating the dispersion liquid to remove the solvent, and completely adsorbing the surface modifier and the oxide under the heating condition to obtain a spin-evaporated product;
(3) Washing the rotary steaming material, and sequentially centrifuging and drying to obtain a pretreatment oxide;
(4) And mixing the pretreated oxide with metal precursor salt, and then sequentially ball-milling and calcining to obtain the size-controllable high-dispersion ultra-small nanocluster.
2. The method for preparing the size-controllable high-dispersion ultra-small nanoclusters according to claim 1, wherein in the step (1), the surface modifier is one of oleylamine, oleic acid, sodium oleate, glycerin, polyethylene glycol, stearyl mercaptan, octadecene, and cetyltrimethylammonium bromide;
And/or the oxide is one of alumina, titanium dioxide, cerium dioxide, silicon dioxide, zirconium oxide, magnesium oxide, ferric oxide and zinc oxide;
And/or the solvent is cyclohexane and ethanol.
3. The method for preparing the size-controllable high-dispersion ultra-small nanoclusters according to claim 2, wherein the volume ratio of cyclohexane to ethanol is 0.3 to 0.5:1;
and/or the mol ratio of the oleylamine to the alumina is 0.5-0.9:1.
4. The method for preparing ultra-small nanoclusters of controllable size and high dispersion according to claim 1, wherein the surface modifier and the oxide are fully adsorbed at 70 to 100 ℃ in the step (2).
5. The method for preparing the size-controllable high-dispersion ultra-small nanoclusters according to claim 1, wherein in the step (3), cyclohexane is used for washing the spin-steamed material.
6. The method for preparing size-controllable highly-dispersed ultra-small nanoclusters according to claim 1, wherein in the step (4), the metal precursor salt is one or a combination of two of acetylacetonate and acetate;
and/or the molar ratio of the metal precursor salt to the oxide is 0.005-0.1:1;
And/or the ball milling time is 0.25-1 h;
and/or the calcining temperature is 350-800 ℃ and the calcining time is 1-4 h.
7. The method for preparing the size-controllable high-dispersion ultra-small nanoclusters according to claim 6, wherein the acetylacetonate includes platinum acetylacetonate, copper acetylacetonate, nickel acetylacetonate, palladium acetylacetonate, rubidium acetylacetonate, rhodium acetylacetonate, cerium acetylacetonate and lanthanum acetylacetonate;
and/or the ball mill adopted in the ball milling process is a planetary ball mill, a high-energy ball mill, a three-dimensional high-speed vibration ball mill or manual grinding.
8. The ultra-small nanocluster of controllable size and high dispersion obtained by the preparation method of any one of claims 1 to 7.
9. Use of size-controllable highly dispersed ultra-small nanoclusters according to claim 8 for the preparation of heterogeneous thermal, electrocatalyst, photocatalyst and adsorbent.
CN202410433817.1A 2024-04-11 2024-04-11 A size-controllable, highly dispersed ultra-small nanocluster and its preparation method and application Pending CN118321542A (en)

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