吸附相反应技术制备镍基催化剂的过程研究
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摘要
本论文研究吸附相反应技术制备NiO／SiO_2纳米复合粒子的过程规律，并通过肼还原法制备Ni／SiO_2催化剂，并考察了其催化性能。
论文首先综述了纳米Ni和NiO的性能和应用，简单介绍了目前纳米材料的一些传统制备方法，并对纳米镍和氧化镍的制备研究进展作出总结。在总结已有研究成果的基础上，提出了本论文的研究设想和实验思路。
作者采用吸附相反应技术在乙醇-水体系中通过NaOH与Ni(NO_3)_2反应制备NiO／SiO_2纳米粒子。研究中设计了对比实验比较吸附相反应法、反应-吸附法和直接反应法制备得到的样品，发现吸附相反应法有利于获得较小粒径粒子，且粒子分散性相对较好。通过透射电子显微镜(TEM)分析粒子形貌、X-射线衍射仪(XRD)分析粒子粒径、酸碱滴定NaOH浓度、络合滴定Ni~(2+)含量等多种表征和分析手段，研究了反应物浓度、水浓度、以及温度等各种影响因素对产物粒子NiO的粒径和形貌的影响规律。通过这些研究对过程规律有了一个较为清晰的认识：水浓度较小时，反应主要发生在化学吸附层中，而化学吸附层中的反应速率相对较慢，反应物浓度对过程有较大影响；水浓度增加，物理吸附层逐渐形成，反应过程逐渐转移到物理吸附层中，物理吸附层中反应速率极快，反应主要受Ni(NO_3)_2进入吸附层的速率控制；温度升高有助于反应速率的加快，但温度过高导致吸附层破坏，反应会在体相中发生。
作者在吸附相反应技术得到Ni(OH)_2／SiO_2的基础上，通过水合肼还原法制备了纳米Ni催化剂，利用TEM、XRD分析粒子形貌和粒径，并将其应用于肼还原硝基苯制备苯胺的催化体系中。实验首先比较了不同催化剂用量对催化性能的影响，发现催化活性和选择性随催化剂用量的增加而增大，且一定量后基本不变。为了考察硅胶载体表面Ni负载量对催化性能的影响，作者比较了两种不同负载量的催化剂的催化活性，发现负载量低有利于Ni粒子的分散和稳定，催化活性较高。实验还比较了在制备Ni(OH)_2／SiO_2过程中的不同水量对催化剂的影响，实验表明，水量为2mL时化学吸附层完全形成，还原得到的Ni粒子与硅胶表面较强的结合，分散性较好，催化活性较高；而其他水量条件下Ni粒子容易团聚，催化剂稳定性较差。Ag掺杂实验研究表明，Ag的掺杂有助于Ni粒子的生成和分散，大幅提高了Ni催化剂的催化活性；不同掺杂条件对Ni催化剂的粒子大小和结构有一定的影响，从而影响其催化性能。
最后总结了论文工作，并提出了论文中没有解决的问题，为以后进一步的研究工作明确了方向。
Synthesis of NiO/SiO_2 nanocomposite materials in a nanoreactor which formed by the water-rich adsorption layer on the surface of SiO_2 were studied in this dissertation. Ni/SiO_2 catalyst was prepared by aqueous reducing method and the catalystic properties were studied.
First the dissertation generalized the characteristic and application of nickel and nickel oxide nanoparticles, and their preparation methods were simply introduced. Based on the generalization of research that had been done, the dissertation's research orientation and experiment strategies were proposed.
Based on the adsorption phase reactor technology, NiO/SiO_2 nanocomposite materials were successfully prepared by reaction of NaOH with Ni(NO_3)_2 in alcohol-water system. The samples prepared in different methods were compared, it was found that nanoparticles were smaller and more dispersed by adsorption phase reactor technology.
Water concentration, reactant concentration and temperature influence the pattern and size of NiO nanoparticles. The author designed a series of experiments including water concentration, reactant concentration and temperature experiments. The influence of these factors to the size and pattern of products NiO were gained with the help of many kinds of analytical methods such as TEM, XRD, Acid & alkali titrate and complexometric titration, and some rules were gained:
When water concentration was low, reaction mainly happened in chemical adsorption phase, in which the velocity was relatively low, the reactant concentration mainly influenced on this situation. When water concentration increased, physical adsorption phase formed gradually, the reaction was relatively fast in this phase, and was controlled by the velocity of nickel nitrate's diffusion. Reaction quickened up as the temperature increased. However, the adsorption phase was destroyed when temperature was too high, and reaction happened in bulk phase.
Based on Ni(OH)_2/SiO_2 prepared by adsorption phase reactor technology, nickel catalyst was prepared by aqueous reducing method. The pattern and size of particles were analyzed by TEM and XRD, then catalyzed the reduction of nitrobenzene to aniline by hydrazine.
The influence of catalyst quality was firstly studied. It was found that catalytic activity increased with the increase of catalyst quality, and basically unchanged after a certain amount. In order to investigate the influence of Ni loading on catalytic properties, the author compared the two catalysts with different loading for activity and found that catalyst with low-loading of the Ni particles had higher activity. The experiments also showed that chemical adsorption phase was fully formed under 2mL water, the Ni particles was strongly combined with silica surface after reduced, while Ni particles prepared in other water conditions were easily reunited and poor in stability. Ag doping experiments showed that it was contributed to the formation and dispersion of Ni, thereby greatly increased the activity. Different conditions on doping influeneced the particle size and structure of Ni catalysts, thus affected their catalytic properties.
At last, the work in the dissertation was generalized, and the problems which still need to discuss in paper were represented.
论文首先综述了纳米Ni和NiO的性能和应用，简单介绍了目前纳米材料的一些传统制备方法，并对纳米镍和氧化镍的制备研究进展作出总结。在总结已有研究成果的基础上，提出了本论文的研究设想和实验思路。
作者采用吸附相反应技术在乙醇-水体系中通过NaOH与Ni(NO_3)_2反应制备NiO／SiO_2纳米粒子。研究中设计了对比实验比较吸附相反应法、反应-吸附法和直接反应法制备得到的样品，发现吸附相反应法有利于获得较小粒径粒子，且粒子分散性相对较好。通过透射电子显微镜(TEM)分析粒子形貌、X-射线衍射仪(XRD)分析粒子粒径、酸碱滴定NaOH浓度、络合滴定Ni~(2+)含量等多种表征和分析手段，研究了反应物浓度、水浓度、以及温度等各种影响因素对产物粒子NiO的粒径和形貌的影响规律。通过这些研究对过程规律有了一个较为清晰的认识：水浓度较小时，反应主要发生在化学吸附层中，而化学吸附层中的反应速率相对较慢，反应物浓度对过程有较大影响；水浓度增加，物理吸附层逐渐形成，反应过程逐渐转移到物理吸附层中，物理吸附层中反应速率极快，反应主要受Ni(NO_3)_2进入吸附层的速率控制；温度升高有助于反应速率的加快，但温度过高导致吸附层破坏，反应会在体相中发生。
作者在吸附相反应技术得到Ni(OH)_2／SiO_2的基础上，通过水合肼还原法制备了纳米Ni催化剂，利用TEM、XRD分析粒子形貌和粒径，并将其应用于肼还原硝基苯制备苯胺的催化体系中。实验首先比较了不同催化剂用量对催化性能的影响，发现催化活性和选择性随催化剂用量的增加而增大，且一定量后基本不变。为了考察硅胶载体表面Ni负载量对催化性能的影响，作者比较了两种不同负载量的催化剂的催化活性，发现负载量低有利于Ni粒子的分散和稳定，催化活性较高。实验还比较了在制备Ni(OH)_2／SiO_2过程中的不同水量对催化剂的影响，实验表明，水量为2mL时化学吸附层完全形成，还原得到的Ni粒子与硅胶表面较强的结合，分散性较好，催化活性较高；而其他水量条件下Ni粒子容易团聚，催化剂稳定性较差。Ag掺杂实验研究表明，Ag的掺杂有助于Ni粒子的生成和分散，大幅提高了Ni催化剂的催化活性；不同掺杂条件对Ni催化剂的粒子大小和结构有一定的影响，从而影响其催化性能。
最后总结了论文工作，并提出了论文中没有解决的问题，为以后进一步的研究工作明确了方向。
Synthesis of NiO/SiO_2 nanocomposite materials in a nanoreactor which formed by the water-rich adsorption layer on the surface of SiO_2 were studied in this dissertation. Ni/SiO_2 catalyst was prepared by aqueous reducing method and the catalystic properties were studied.
First the dissertation generalized the characteristic and application of nickel and nickel oxide nanoparticles, and their preparation methods were simply introduced. Based on the generalization of research that had been done, the dissertation's research orientation and experiment strategies were proposed.
Based on the adsorption phase reactor technology, NiO/SiO_2 nanocomposite materials were successfully prepared by reaction of NaOH with Ni(NO_3)_2 in alcohol-water system. The samples prepared in different methods were compared, it was found that nanoparticles were smaller and more dispersed by adsorption phase reactor technology.
Water concentration, reactant concentration and temperature influence the pattern and size of NiO nanoparticles. The author designed a series of experiments including water concentration, reactant concentration and temperature experiments. The influence of these factors to the size and pattern of products NiO were gained with the help of many kinds of analytical methods such as TEM, XRD, Acid & alkali titrate and complexometric titration, and some rules were gained:
When water concentration was low, reaction mainly happened in chemical adsorption phase, in which the velocity was relatively low, the reactant concentration mainly influenced on this situation. When water concentration increased, physical adsorption phase formed gradually, the reaction was relatively fast in this phase, and was controlled by the velocity of nickel nitrate's diffusion. Reaction quickened up as the temperature increased. However, the adsorption phase was destroyed when temperature was too high, and reaction happened in bulk phase.
Based on Ni(OH)_2/SiO_2 prepared by adsorption phase reactor technology, nickel catalyst was prepared by aqueous reducing method. The pattern and size of particles were analyzed by TEM and XRD, then catalyzed the reduction of nitrobenzene to aniline by hydrazine.
The influence of catalyst quality was firstly studied. It was found that catalytic activity increased with the increase of catalyst quality, and basically unchanged after a certain amount. In order to investigate the influence of Ni loading on catalytic properties, the author compared the two catalysts with different loading for activity and found that catalyst with low-loading of the Ni particles had higher activity. The experiments also showed that chemical adsorption phase was fully formed under 2mL water, the Ni particles was strongly combined with silica surface after reduced, while Ni particles prepared in other water conditions were easily reunited and poor in stability. Ag doping experiments showed that it was contributed to the formation and dispersion of Ni, thereby greatly increased the activity. Different conditions on doping influeneced the particle size and structure of Ni catalysts, thus affected their catalytic properties.
At last, the work in the dissertation was generalized, and the problems which still need to discuss in paper were represented.
引文
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