Partial Oxidation of Methane to Synthesis Gas over Co/Mg/HZSM-5 Catalysts

本论文以Co金属为催化剂活性组分，考察了载体以及助剂对Co基催化剂甲烷部分氧化制合成气反应性能的影响，并通过优化制备方法和制备条件研制出具有高活性和稳定性的Co/Mg/HZSM-5催化剂。在此基础上，采用BET、XRD、H2-TPR、XPS以及原位XRD等实验手段，考察了催化剂的比表面积、分散度、氧化还原性能以及催化剂的体相结构和表面结构等性质，探讨了催化剂结构与性能之间的关系。主要研究结果如下： 1)在考察的Al2O3、SiO2、CaO、SBA-15和HZSM-5五种载体中，以HZSM-5为载体制得的Co/HZSM-5催化剂具有较好的催化性能。但是，在温度为750oC，空速为100000m...This dissertation focuses on the partial oxidation of methane into synthesis gas over Cobalt-based catalysts. A series of supports and promoters have been widely screened. Moreover, the effects of prepareation method and calcination temperature on the catalyst performance have also been investigated. In order to reveal the relationship between the catalytic performance and the chemical and physica...学位：理学硕士院系专业：化学化工学院化学系_物理化学(含化学物理)学号：1912005130188

Ru和Cu协同催化湿式氧化处理氨氮废水

采用化学还原法制备了RuCu/TiO2双金属催化剂,并探究了Ru和Cu的协同作用对催化湿式氧化（CWAO）无害化处理氨氮废水催化性能的影响。研究结果表明,Cu的添加可有效改善Ru/TiO2催化剂的N2选择性,而Ru的存在可有效提高Cu/TiO2催化剂的催化活性。反应条件为0.5 MPa、150℃、[NH3]0=1000 mg·L-1、pH=12、模拟废水处理量为33 L·（kg cat）-1·h-1时,1Ru2Cu/TiO2能使废水的氨氮转化率和N2选择性分别高达87.7%和85.9%。表征结果表明:Ru和Cu的协同在催化氧化氨氮废水过程中起了关键作用,主要体现在:Ru和Cu的强相互作用导致1Ru2Cu/TiO2催化剂具有良好的抗流失性能,进而使得催化剂具有良好的稳定性;Ru和Cu的电子转移使得1Ru2Cu/TiO2具有适中的亲氧性能,有效提高了催化剂的催化活性。新疆维吾尔自治区高校科研计划项目(XJEDU2016S083);;福建省自然科学基金项目(2015J05031)~

Effect of Ag loading on soot oxidation for Ag/Ce_(0.75)Zr_(0.25)O_2 catalysts

开发低温下高催化活性的柴油机碳烟颗粒燃烧催化剂是当前环境催化领域的热点问题。利用共沉淀的方法制备了用于碳烟催化燃烧反应的Ag/Ce_(0.75); Zr_(0.25)O_2催化剂。活性评价结果表明,相对于Ce_(0.75)Zr_(0.25)O_2催化剂,Ag的引入可显著降低碳烟催化燃烧温度。; 而且,Ag的负载量存在一个最佳值。以XRD、in-situ; XRD、BET、TPR等表征手段探究了该系列催化剂结构性质及其变化产生的影响。结果表明,Ag与Ce物种间的相互作用可显著降低催化剂(特别是CeO; _2表面氧)的还原温度。该相互作用使Ag/Ce_(0.75)Zr_(0.25)O_2催化剂在一定温度下(>200℃)就表现出Ag+的性质。这些性; 质与该催化剂具有较高的碳烟氧化活性相关。而且,该催化剂也表现出良好的稳定性。It is still important to develop soot oxidation catalysts with excellent; activity under low temperature. Ag/Ce_(0.75)Zr_(0.25)O_2 was synthesized; via coprecipitation method for soot oxidation. Compared with the; catalytic performance of Ce_(0.75)Zr_(0.25)O_2, the introduction of Ag; can lead to the decrease of soot-ignition temperature. Moreover, there; is an optimal Ag loading. Subsequently, several methods such as XRD,; in-situ XRD, BET, TPR were used to characterize the physicochemical; properties of Ag-based catalysts. The results showed that the; introduction of Ag resulted in decreasing the reduction temperature of; surface oxygen species, being due to the interaction of Ag and Ce. The; interaction also brings about the occurrence of Ag~+ nature. And the; feature is linked with the outstanding activity of soot oxidation for; Ag-based catalyst. Furthermore, the Ag-based catalyst possessed fairly; good stability in soot oxidation.国家自然科学基金项目; 中央高校基本科研业务费专项资金项

Mg助剂对Co/Mg/HZSM-5催化剂结构及其催化甲烷部分氧化制合成气性能的影响

采用XRD、TEM、H2-TPR、Raman、XPS和活性评价等方法,研究了Mg助剂对Co/Mg/HZSM-5催化剂物理化学性质和甲烷部分氧化(POM)制合成气反应性能的影响.研究发现,在Co/HZSM-5催化剂中添加Mg助剂,可有效地提高催化剂的催化活性和稳定性.在750℃和空速1.0×105mL·h-1·g-1反应条件下,Co/Mg/HZSM-5在连续反应30h的实验时间内催化活性稳定不变,而Co/HZSM-5因其活性中心Co0转化生成CoAl2O4非活性相,反应10h后即迅速失活.催化剂表征结果表明,在Co/Mg/HZSM-5催化剂中钴物种除以Co3O4存在外,一部分钴物种还与Mg助剂发生强相互作用生成较难还原的MgCo2O4,由此导致还原后钴金属的分散度较高.关联催化剂表征和活性评价结果,讨论了催化剂结构与性能之间的关系

Design and synthesis of hydrogenation nanocatalyst with synergetic multiple catalytic sites

基于催化剂多活性中心分工协同作用可活化两种或多种反应物,本研究工作以一种新的制备策略对贵金属-过渡金属-过渡金属氧化物催化剂进行合理设计,构筑金属与金属氧化物双活性中心。结果发现,贵金属负载于过渡金属/过渡金属氧化物(nM-TM/TMO)结构的催化剂在加氢反应中具有优异的催化活性。同时,热处理方法可有效调控催化剂微观结构,并对此构效关系进行了较为深入的研究。As synergic multiple active sites catalysts can theoretically activate two or more reactant or substrates simultaneously resulting in significantly increase of activity and stability of catalysts, we herein develop a novel catalysts preparation strategy to design and construct noble metal-transition metal-transition metal oxide(NM-TM/TMO) to form bi-active catalytic sites.The experimental results show that such a catalyst has excellent performance in catalytic hydrogenation, e.g.aromatic compounds hydrogenation as the case studies.It was also found that the nanostructure of catalyst can be tuned via thermal treatments, which are investigated and the relationship between structure and activity is explored to some extent.国家自然科学基金项目(20973140;201106118;21303140)~

水蒸气改性H-FER分子筛在催化丁烯异构化反应中的应用

为了进一步提高FER分子筛的催化性能及稳定性,以水蒸气对H-FER分子筛进行改性处理。结果表明,水蒸气处理可以有效调变对H-FER分子筛孔结构和酸性,且保持其晶型相对完整。在水蒸气流量和处理温度分别为1.0 mL/min和370℃下,处理30 min后的H-FER具有最佳的催化性能。X射线衍射和氮气吸脱附等表征结果表明,较高的水蒸气处理温度（370～420℃）和较大的水蒸气流量（1～3 mL/min）可同时调控微孔和介孔的结构。另一方面,介孔与微孔的合理匹配对H-FER催化剂的稳定性影响处于主要地位,酸性变化的影响则处于次要地位。而且,对于丁烯、异丁烯等反应物/产物,H-FER分子筛的微孔孔径不宜过大（<1.45 nm）,dmicro/dmeso也不应大于0.19,即微介孔的连通性相当重要。中央高校基本科研业务费专项(20720170029

Effect of a Mg Promoter on the Structure and Catalytic Performance of a Co/Mg/HZSM-5 Catalyst for the Partial Oxidation of Methane to Syngas

The effect of a Mg Promoter on the physical and chemical properties, as well as catalytic performance of the Co/Mg/HZSM-5 catalyst for the partial oxidation of methane(POM) to syngas was studied by XRD, H-2-TPR, TEM, Raman, XPS and activity measurements. The activity and stability of the Co/HZSM-5 catalyst was effectively improved by Mg modification. At T=750 degrees C and SV (space velocity)= 1.0x10(5) mL.h(-1).g(-1) the Mg-modified catalyst exhibited high activity and good stability during a long run. The unmodified catalyst rapidly deactivated after 10 h on stream. Catalyst deactivation was mainly due to the transformation of Co-0 into CoAl2O4 as indicated by TPR and XPS, For the Co/Mg/HZSM-5 catalyst the Co species, in addition to ones existing as Co3O4, reacted with the Mg Promoter to produce MgCo2O4. This structure, after reduction, led to a higher dispersion of Co metal, compared with the Mg-free catalyst. From the results of the characterization and activity measurements, the relationship between catalyst structure and performance was discussed

水蒸气改性H-FER分子筛在催化正丁烯骨架异构化反应中的应用

为了进一步提高H-FER分子筛的催化性能及稳定性,以水蒸气对其进行改性处理,并考察其对正丁烯骨架异构化的催化反应性能.结果表明:水蒸气处理可以有效调变H-FER分子筛的孔结构和酸性,且保持其晶型相对完整;当水蒸气流量和处理温度分别为1.0mL/min和370℃时,处理30min后的H-FER分子筛具有最佳的催化性能.X射线衍射和氮气吸脱附等表征结果表明:较高的水蒸气处理温度（370～420℃）和较大的水蒸气流量（1.0～3.0mL/min）可同时调控微孔和介孔的结构;介孔与微孔的合理匹配对H-FER催化剂的稳定性影响处于主要地位,酸性变化的影响则处于次要地位;此外,H-FER分子筛的微孔孔径不宜过大（<1.45nm）,微孔和介孔的粒径比(dmicro/dmeso)也不应大于0.19,即微介孔的连通性相当重要.中央高校基本科研业务费专项(20720170029

利用磁控溅射在石墨衬底上生长多晶硅薄膜的方法

一种利用磁控溅射在石墨衬底上生长多晶硅薄膜的方法，包括如下步骤：步骤1：选择一石墨衬底，将石墨衬底抛光；步骤2：在磁控溅射室里，将抛光的石墨衬底磁控溅射多晶硅薄膜；步骤3：溅射结束后自然降温，形成样品；步骤4：将样品置于快速热退火炉里，快速退火，完成多晶硅薄膜的制作

Design and optimization of a monolithic GaInP/GaInAs tandem solar cell

We have theoretically calculated the photovoltaic conversion efficiency of a monolithic dual-junction GaInP/GaInAs device,which can be experimentally fabricated on a binary GaAs substrate.By optimizing the bandgap combination of the considered structure,an improvement of conversion efficiency has been observed in comparison to the conventional GaInP2/GaAs system.For the suggested bandgap combination 1.83 eV/1.335 eV,our calculation indicates that the attainable efficiency can be enhanced up to 40.45%（300 suns,AM1.5d） for the optimal structure parameter（1550 nm GaInP top and 5500 nm GaInAs bottom）,showing promising application prospects due to its acceptable lattice-mismatch（0.43%） to the GaAs substrate.</span