碳包覆纳米四氧化三铁颗粒的合成与结构研究
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摘要
碳包覆纳米金属氧化物材料(Carbon-encapsulated metal oxide nanoparticles,CEMONs)是一种新型的纳米碳/金属氧化物复合材料,其中纳米金属氧化物粒子作为核心,数层石墨片层有序地将其紧密围绕,形成核壳结构。由于碳包覆层的存在,可避免内部的纳米粒子受环境影响。针对目前碳包覆金属氧化物纳米材料制备中存在的产物纯度低、步骤复杂、形态结构不易控制和难以大量合成等缺点,本论文采用一种新型制备方法——共热解法,通过芳烃物质和有机金属化合物在中温下的共炭化热解制备CEMONs,该方法具有工艺路线简单、反应条件温和、产物组成均匀、结构易于控制及容易实现大量制备等特点。
本论文主要以间苯二酚为氧源和碳源、以二茂铁为金属源和碳源,采用共热解法制备碳包覆纳米金属氧化物。在详细考察制备工艺参数对CEMONs形成、转化及其形态结构影响的基础上,利用TEM,HREM,XRD,SEM,TG-DSC等测试分析手段研究了材料的形貌和结构,并与制备工艺相关联,实现材料的可控合成；阐明CEMONs的形成机理。
研究结果表明,以间苯二酚和二茂铁为原料,采用共热解法可以大量制备碳包覆纳米Fe3O4颗粒。在450℃的反应温度下,间苯二酚：二茂铁=10.0g：20.0g时,制备出纯度高的、具有明显核壳结构的碳包覆纳米Fe3O4颗粒。在450℃的反应温度下,提高二茂铁的量从50wt.%到75wt.%时,会使碳包覆颗粒内核中金属相从Fe3O4→α-Fe→Fe3C逐渐转变,同时内部压力升高,颗粒变小,包覆层厚度增加。保持间苯二酚和二茂铁比例恒定,随着反应温度的升高从430℃度到495℃度,内核中金属相也呈现Fe3O4→α-Fe→Fe3C转变。
通过原料组成、结构分析和合成工艺参数与产物形貌和结构的关系研究,推断出共热解法形成碳包覆纳米金属氧化物是基于Fe纳米颗粒对含氧芳烃分子的催化作用,以及Fe原子在催化芳香烃过程中与氧基团发生氧化物还原反应,而此过程是基于溶解-析出以及动力学平衡的机制。碳包覆纳米金属氧化物的形成需要两个必要因素：体系中有适当比例的铁纳米原子簇和含氧芳香烃,以及适中的反应活性。
Carbon-encapsulated metal oxide nanoparticles (CEMONs) are a new kind of carbon/metal oxide nanocomposite, in which graphite arrange around metal oxide nanoparticles located in the center to form core-shell structure. Because of the carbon layers preventing metal oxide nanoparticles from environment effection, they have good stability in environment. For the preparation of CEMONs, the present techniques, such as the arc-discharge technique, chemical vapor deposition, liquid-impregnating carbonization of non-graphitizing carbon and etc., show some disadvantages, e.g., the morphology and the structure of the resulting nanocrystals are not easy to control, and it is difficult to produce high-purity nanomaterials in large quantities. Here we proposed a novel method for the preparation of CEMONs by co-carbonization of aromatics with metal compounds, i.e., co-pyrolysis method. It featured in simplicity, low temperature, good controllability and high yield.
The research focused on the preparation of CEMONs by co-pyrolysis of 1,3-benzenediol and ferrocene in which 1,3-benzenediol is oxygen source and carbon source, ferrocene is the metal source and carbon source. The effects of synthesis parameters on the formation and transformation of CEMONs were investigated in detail. The morphology, structure and particular properties of the product were characterized by TEM, HREM, XRD, SEM, and TG-DSC measurements. The formation mechanism of CEMONs was elucidated.
The results show that large amount of carbon-encapsulated Fe3O4 nanoparticles were obtained by co-pyrolysis of 1,3-benzenediol and ferrocene. The CEMONs with higher purity were prepared in the presence of 33.3 wt.% of 1,3-benzenediol at the reaction temperature of 450℃. With the increase of ferrocene content from 50wt.% to 75wt.% or reaction temperature from 430℃to 495℃, the encapsulated metal core in the product was changed from single Fe3O4 to a-Fe to iron carbides, gradually. Meanwhile, nanoparticles become smaller, and the thickness of corbon layers increases.
The above research afforded a novel and effective method for the preparation of carbon-encapsulated metal oxide nanomaterials. By analysis of raw feedstock and the investigation on the relationship among the morphology, structure and the synthesis parameters, it is concluded that the formation of CEMONs by co-pyrolysis method is based on the catalysis and oxidation/reduction of iron nano-cluster for the oxygen-containing aromatic molecules. And this process is based on the dissolution-precipitation, and dynamic equilibrium mechanisms. It is assumed that two essential factors must be met for the formation of the nanoparticles, including proper proportion of iron nano-clusters and oxygen aromatics, and moderate reaction activity in the system.
本论文主要以间苯二酚为氧源和碳源、以二茂铁为金属源和碳源,采用共热解法制备碳包覆纳米金属氧化物。在详细考察制备工艺参数对CEMONs形成、转化及其形态结构影响的基础上,利用TEM,HREM,XRD,SEM,TG-DSC等测试分析手段研究了材料的形貌和结构,并与制备工艺相关联,实现材料的可控合成；阐明CEMONs的形成机理。
研究结果表明,以间苯二酚和二茂铁为原料,采用共热解法可以大量制备碳包覆纳米Fe3O4颗粒。在450℃的反应温度下,间苯二酚：二茂铁=10.0g：20.0g时,制备出纯度高的、具有明显核壳结构的碳包覆纳米Fe3O4颗粒。在450℃的反应温度下,提高二茂铁的量从50wt.%到75wt.%时,会使碳包覆颗粒内核中金属相从Fe3O4→α-Fe→Fe3C逐渐转变,同时内部压力升高,颗粒变小,包覆层厚度增加。保持间苯二酚和二茂铁比例恒定,随着反应温度的升高从430℃度到495℃度,内核中金属相也呈现Fe3O4→α-Fe→Fe3C转变。
通过原料组成、结构分析和合成工艺参数与产物形貌和结构的关系研究,推断出共热解法形成碳包覆纳米金属氧化物是基于Fe纳米颗粒对含氧芳烃分子的催化作用,以及Fe原子在催化芳香烃过程中与氧基团发生氧化物还原反应,而此过程是基于溶解-析出以及动力学平衡的机制。碳包覆纳米金属氧化物的形成需要两个必要因素：体系中有适当比例的铁纳米原子簇和含氧芳香烃,以及适中的反应活性。
Carbon-encapsulated metal oxide nanoparticles (CEMONs) are a new kind of carbon/metal oxide nanocomposite, in which graphite arrange around metal oxide nanoparticles located in the center to form core-shell structure. Because of the carbon layers preventing metal oxide nanoparticles from environment effection, they have good stability in environment. For the preparation of CEMONs, the present techniques, such as the arc-discharge technique, chemical vapor deposition, liquid-impregnating carbonization of non-graphitizing carbon and etc., show some disadvantages, e.g., the morphology and the structure of the resulting nanocrystals are not easy to control, and it is difficult to produce high-purity nanomaterials in large quantities. Here we proposed a novel method for the preparation of CEMONs by co-carbonization of aromatics with metal compounds, i.e., co-pyrolysis method. It featured in simplicity, low temperature, good controllability and high yield.
The research focused on the preparation of CEMONs by co-pyrolysis of 1,3-benzenediol and ferrocene in which 1,3-benzenediol is oxygen source and carbon source, ferrocene is the metal source and carbon source. The effects of synthesis parameters on the formation and transformation of CEMONs were investigated in detail. The morphology, structure and particular properties of the product were characterized by TEM, HREM, XRD, SEM, and TG-DSC measurements. The formation mechanism of CEMONs was elucidated.
The results show that large amount of carbon-encapsulated Fe3O4 nanoparticles were obtained by co-pyrolysis of 1,3-benzenediol and ferrocene. The CEMONs with higher purity were prepared in the presence of 33.3 wt.% of 1,3-benzenediol at the reaction temperature of 450℃. With the increase of ferrocene content from 50wt.% to 75wt.% or reaction temperature from 430℃to 495℃, the encapsulated metal core in the product was changed from single Fe3O4 to a-Fe to iron carbides, gradually. Meanwhile, nanoparticles become smaller, and the thickness of corbon layers increases.
The above research afforded a novel and effective method for the preparation of carbon-encapsulated metal oxide nanomaterials. By analysis of raw feedstock and the investigation on the relationship among the morphology, structure and the synthesis parameters, it is concluded that the formation of CEMONs by co-pyrolysis method is based on the catalysis and oxidation/reduction of iron nano-cluster for the oxygen-containing aromatic molecules. And this process is based on the dissolution-precipitation, and dynamic equilibrium mechanisms. It is assumed that two essential factors must be met for the formation of the nanoparticles, including proper proportion of iron nano-clusters and oxygen aromatics, and moderate reaction activity in the system.
引文
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