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Preparation of Earth Abundant Metal Mesoporous Silica Materials with Implications for the Production of Liquid Fuels

机译:土质丰富的金属介孔二氧化硅材料的制备及其对生产液体燃料的意义

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摘要

The global maritime fleet is an integral part of the United States economy, albeit at the cost of substantial contributions to atmospheric particulate matter, SOx, and NOx. This is further confounded by the inadequacies of electrification to provide clean alternative to conventional diesel engines. Fortunately, methanol fuels are poised to reduce emissions in commercial shipping, while Fischer-Tropsch synthesis of diesel can reduce dependence on foreign petroleum. Efforts can be improved by new facile routes towards SiO2 supported earth abundant metals such as Cu and Fe. Through HRTEM, RAMAN, FTIR, ICP-AES, N2 physisorption, HRTEM, EDAX, 57Fe Mossbauer spectroscopy, SAXS, and XRD we investigate the structure and composition of these mesoporous silica embedded earth abundant metal materials. In addition, where applicable we demonstrate the accessibility of metal sites.;Cu functionalized zeolites show high activity for partial oxidation of methane to methanol. We developed a facile and reagent-free process for 3--5 nm Cu rich nanoparticles on commercial ZSM-5 carried out through electrolysis of Cu. The method was applied over various times, voltages, and supports. Beyond methanol, Fischer-Tropsch diesel depends on low cost Fe catalysts. Unfortunately, high temperature carburization routes used to convert Fe to Fe-carbides as well as operating conditions induce sintering of the metal particles, hindering catalysis. We have proposed a method to stabilize metals against sintering by substitution of Fe within the SiO2 framework. Strategies to incorporate Fe within mesoporous silica SBA-15 involve lowering the acidity of the synthesis gel which detrimentally effects the morphology of the final catalyst. Multi-step chemical routes may be used at the cost of complexity. Addition of the diammonium phosphate to the synthesis gel of SBA-15 improves Fe content from 0.04 to 10.14 wt. % with surface area of 613 m2 g--1. We also explored the feasibility of minimizing aqueous solvent in favor of imidazole ionic liquids. With the ability to self-assemble and dissolve metal salts 1-butyl-3-methylimidiazole tetrafluoroborate has been shown to be a suitable alternative to water as a solvent system to produce mesoporous silica embedded iron materials with surface areas near 600 m2 g--1, 10 nm pores, 1.8 wt. % Fe content.
机译:尽管付出了对大气颗粒物,SOx和NOx做出重大贡献的代价,但全球海上船队是美国经济不可或缺的一部分。由于电气化不足以提供常规柴油发动机的清洁替代品,这进一步使人感到困惑。幸运的是,甲醇燃料已准备好减少商业运输中的排放,而费托合成的柴油可以减少对外国石油的依赖。可以通过新的简便路线来改进工作,这些路线是由SiO2负载的富含铜的金属(例如Cu和Fe)制成的。通过HRTEM,RAMAN,FTIR,ICP-AES,N2物理吸附,HRTEM,EDAX,57Fe Mossbauer光谱,SAXS和XRD,我们研究了这些介孔二氧化硅包埋的地球丰富的金属材料的结构和组成。此外,在适用的情况下,我们证明了金属位置的可及性。铜官能化沸石对甲烷部分氧化为甲醇具有很高的活性。我们通过电解铜在商业ZSM-5上开发了3-3-5 nm富含铜的纳米颗粒的简便,无试剂的工艺。该方法应用于各种时间,电压和支撑。除甲醇外,费托柴油还依赖于低成本的铁催化剂。不幸的是,用于将Fe转化为Fe碳化物的高温渗碳途径以及操作条件引起金属颗粒的烧结,从而阻碍了催化作用。我们提出了一种通过在SiO2框架内置换Fe来稳定金属以防止烧结的方法。将Fe掺入中孔二氧化硅SBA-15中的策略包括降低合成凝胶的酸度,这不利地影响了最终催化剂的形态。可以以复杂性为代价使用多步化学路线。将磷酸氢二铵添加到SBA-15的合成凝胶中可将铁含量从0.04重量%提高至10.14重量%。 %,表面积为613 m2 g--1。我们还探讨了尽量减少水性溶剂对咪唑离子液体有利的可能性。具有自组装和溶解金属盐的能力,已证明1-丁基-3-甲基咪唑四氟硼酸盐是水的合适替代品,可作为溶剂体系生产介孔二氧化硅包埋的铁材料,表面积接近600 m2 g--1 ,10 nm的孔,1.8 wt。铁含量%。

著录项

  • 作者

    Davidson, Malcolm.;

  • 作者单位

    Colorado School of Mines.;

  • 授予单位 Colorado School of Mines.;
  • 学科 Materials science.;Chemistry.;Energy.
  • 学位 Ph.D.
  • 年度 2018
  • 页码 111 p.
  • 总页数 111
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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