【作者】 王波；

【导师】 黄翔；

【作者基本信息】 中国海洋大学 ， 材料物理与化学， 2012， 硕士

【摘要】 石油作为当前十分重要的化石燃料，在机动车燃料、化学化工方面有着十分广泛的应用。然而当下石油原油重质化、劣质化趋势与全球日益严格的环保法规之间的矛盾越来越突出。因此，研制开发新型深度加氢脱硫（HDS）和加氢脱氮（HDN）催化剂随之成为研究热点。过渡金属碳化物和过渡金属氮化物首先被发现具有类似Pt等贵金属的催化性能。随后，过渡金属磷化物被发现是在继承碳化物和氮化物优良催化性能基础上，拥有更好的抗硫中毒性能的催化剂。本论文采用无毒的红磷作为磷源，水热合成了新型高效石油精炼催化剂Ni₂P、NiCoP。以乙醇胺作为溶剂，在溶剂热条件下合成了磷化锡（Sn₄P₃）纳米粉体。利用XRD、SEM、TEM、EDS、BET和DTA-TG等测试手段对合成的产物进行了表征研究，最终获得以下研究结论：1.微米级Ni₂P、Ni₁₂P₅的合成实验红磷与氯化镍分别作为磷源和镍源，在酸性反应环境中：（1）在论文研究范围内，P/Ni摩尔比小于20时，在200℃下反应所得的产物为Ni₁₂P₅，提高P/Ni摩尔比至25时，所得反应产物为Ni₂P，两种产物均为不规则微米级粉体。（2）合成物相均一、结晶良好产物的最佳反应温度为200℃，降低温度则所得产物结晶度降低。2.纳米级Ni₂P的合成实验红磷与氯化镍分别作为磷源和镍源，在碱性反应环境中：（1）强碱性环境是水热法合成磷化镍时获得纳米粉体的关键因素。体系由酸性环境改为强碱性环境后产物粒径由微米级别降至纳米级别。（2）起始反应溶液中磷镍比例对于产物物相有决定性影响：论文研究范围内，当P/Ni≤20时水热反应得到Ni₁₂P₅，提高比例至P/Ni≥25，水热反应所得产物为Ni₂P。反应产物为粒径在10-50nm的不规则纳米颗粒。（3）相比于酸性环境中的实验，强碱性环境下只需要10小时即可获得预期反应产物，低于该反应时间时产物结晶度下降。（4）强碱性环境中合成结晶良好的纳米级磷化镍的最佳反应温度为200℃，低于此温度不能获得预期物相的产物，高于此温度则产物结晶度开始下降。3.纳米级Ni₂P的比表面积测试及热稳定性测试（1）利用N₂吸附法对所得产物进行了比表面积测试，结果表明纳米级Ni₂P拥有约6m²/g的比表面积，微米级产物比表面积约是其一半。（2）DTA-TG测试显示纳米级Ni₂P在空气环境中煅烧至300℃时Ni₂P仍为主要物相，这表明在300℃以下的空气氛围中水热法合成的Ni₂P粉体具有较好的稳定性。4.双金属磷化物磷化镍钴（NiCoP）的水热合成探索利用水热法进行了双金属磷化物磷化镍钴的合成实验，对所得产物通过XRD、TEM和EDS等测试。结果表明所得产物为10-20nm的纳米粉体，并且随着反应物中镍含量的增加所得产物结晶度提高。5.纳米磷化锡（Sn₄P₃）粉体的合成合成以红磷和氯化亚锡分别作为磷源和锡源，在乙醇胺为溶剂的溶剂热体系中合成了磷化锡（Sn₄P₃）粉体，并探索了外加还原剂、反应物起始比例、反应时间和反应温度对于实验的影响，获得了合成物相均一、结晶良好的磷化锡粉体的理想实验条件。（1）外加还原剂KBH₄合成磷化锡粉体时，可制得Sn₄P₃粉体，但产物物相不纯，实验操作复杂。（2）可直接利用氯化亚锡和红磷分别作为锡源和磷源来制得磷化锡纳米粉体，该方法合成物相均一、结晶良好的纳米磷化锡（Sn₄P₃）粉体的条件为：P:Sn=3:4，200℃下反应10小时。更多还原

【Abstract】 Petroleum is widely used as vehicle fuel and raw materials of chemicalengineering. However, the conflicts between low-quality trend of petroleum and theworld’s increasing stringent environmental regulations are becoming more prominent.To solve this problem, developing a new type of deep hydrodesulfurization （HDS）and hydrodenitrogenation （HDN） catalysts has become a research focus of the cleanproduction. Owning to their excellent anti-sulfur poisoning property and superiorcatalytic activity, transition metal phosphide compounds have great applicationprospects in the catalytic field.In this paper, Ni₂P, Ni₁₂P₅and NiCoP were prepared by a mild hydrothermalmethod. At the same time, Sn₄P₃was synthesized by a solvothermal method withnon-toxic ethanolamine as solvents. All of these works, the red phosphor （anenvironment-friendly material） was used as the phosphor resource. Characterizationtechniques such as XRD, SEM, TEM, EDS, BET and DTA-TG were used for thecharacterization of the samples. And the major research results are as follows:1. The synthesis of Ni₂Pand Ni₁₂P₅micron meter powders by hydrothermal method.Reactions which were taken place in an acidity reaction system.（1）When the molar ratio of P and Ni was smaller than20（P/Ni≤20） thehydrothermal products were Ni₁₂P₅. The increasing of the ratio benefited to thesynthesis of Ni₂P. Both Ni₁₂P₅and Ni₂P powders were in micron meter level and theirmorphology were controlled by the red phosphor in raw materials.（2） The ideal hydrothermal temperature was200℃, lower temperature wouldlead to poor crystallinity of the products.2. The synthesis of Ni₂Pand Ni₁₂P₅nano meter powders by hydrothermal method.Reactions which were taken place in an alkaline system. （1）The alkaline environment was the key factor to prepare nano meter nickelphophide by hydrothermal method. Similar to the reaction in acidity environment,when the P/Ni≤20/1, the final product was Ni₁₂P₅, and when the P/Ni≥25/1, the mainphase of the products was Ni₂P. Both of the two kinds of nano powders were wellcrystallized and particle sizes ranged from10to50nm. And morphology of theproducts had nothing to do with the red phosphor.（2）The ideal reaction time to synthesize nano Ni₂P was10hours, which wasshorter than the time to synthesize micron Ni₂P.（3）200℃was the ideal temperature for the synthesizing of well crystallized Ni₂Pby hydrothermal method.3. Investigation on the special surface area and thermal stability of as-prepared Ni₂Ppowders.（1）The special area of as-prepared Ni₂P powders was measured by nitrogenadsorption method. The results showed nano Ni₂P had6m²/g special surface area,which was about two times of the micron Ni₂P.（2）The TG-DTA analysis indicated the as-prepared Ni₂P products were stableunder300oC even in air atmosphere.4. Hydrothermal synthesis exploration of cobalt–nickel bimetallic phosphidesUltrafine cobalt–nickel bimetallic phosphides were prepared by mildhydrothermal method and characterized by techniques, such as XRD, EDS, and TEM.The results showed that the as-prepared products were well crystallized and particlesizes ranged from10to20nm. With the increasing amount of Ni²⁺ in the suspensions,the crystallinity of obtained products was improved gradually and the crystallite sizesincreased accordingly.5. The synthesis Sn₄P₃powders by solvothermal method.Red phosphor and stannous chloride were used as phosphor and tin resourcesrespectively. Parameters such as reaction temperature, holding time and initial molarratio of P and Ni were investigated.（1）KBH₄could help to synthesize Sn₄P₃, but the products were not pure Sn₄P₃.（2）Sn₄P₃could be prepared with red phosphor and stannous chloride by solvothermal method with non-toxic ethanolamine as solvent. The ideal solvothermalconditions to prepare Sn₄P₃were: P/Sn=3/4, T=200℃, t=10h.更多还原