GOALI: Novel Impregnated Layer Combustion Synthesis for Catalysts Preparation: Hydrogen Production from Methanol

目标：新型浸渍层燃烧合成催化剂制备：甲醇制氢

• 批准号: 0730190
• 负责人: Eduardo Wolf
• 金额: --
• 依托单位: University of Notre Dame
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2007
• 资助国家: 美国
• 起止时间: 2007-09-01 至 2011-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0730190&HistoricalAwards=false
• 关键词: GOALI; Novel; Impregnated; Layer; Combustion

Eduardo E. Wolf0730190This work is motivated by the need to find a controllable preparation method of high surface area metal/oxide catalysts for the production of hydrogen from the oxidative reforming of methanol (ORM) for small fuel cell applications. The objective of the research is twofold: 1) to study a novel method for catalyst preparation based on solution combustion synthesis, referred to as Impregnated Layer Combustion Synthesis, or ILCS, and, 2) develop structure-activity correlations of catalysts prepared by the ILCS method for the ORM reaction along with spectroscopic studies to identify active sites and links those with surface and material properties. Preliminary studies conducted in the PIs groups' show that Pd/Cu/ZnO/ZrO2 catalysts prepared by co-precipitation are active and selective for the ORM reaction. The PIs have also identified the Cu metal surface area and oxidation state as determining factors of activity and selectivity. The ILCS method has shown to yield high surface area oxides as well as metals supported onto high area oxides. The ILCS method involves the controlled propagation of a reaction front in a narrow area for a short time, which along with the evolution of gases, inhibits particle size growth leading to the formation of oxides of high surface area (50-200 m2/g), high purity and crystallinity, which do not require additional calcination. A proof of concept is provided that by using ILCS they were able to synthesize a catalyst that has high area and activity and selectivity similar to co-precipitated catalyst. Further studies of the ILCS method are expected to yield even higher active areas and increase activity and selectivity. On the basis of the above results they hypothesize that i) Fundamental understanding of how preparative variables of ILCS affect material properties will lead to the design of active and selective catalysts for the ORM reaction, ii) Establishing structure-activity correlations for ORM reactions could lead to the rational design of more active and selective oxidation catalysts. A detailed program is planned to study how the preparative variables used in ILCS (solution concentration, fuel composition, substrate impregnation, ignition temperature) affect the bulk material and surface properties such as total and active surface area, degree of crystallinity, phase composition, dispersion of promoters, and oxidation state under different environments. Activity and selectivity results for various catalysts prepared by ILCS will be evaluated by various advanced techniques. The kinetics of selected catalysts will be measured in detail for correlation with the material properties and preparative variables. EXAFS and IR spectroscopy of selected catalysts will be used to determine the catalysts' oxidation state and type of adsorbates under reaction conditions (operando) and to determine the key surface variable(s) responsible for activity and selectivity. The rate constants from the kinetics studies will be then correlated with the key surface properties and these in turn with the ILCS preparative variables. The results obtained will provide new knowledge of the novel ILCS as a method for the rational design of oxidation catalysts as well as the factors determining hydrogen production from the ORM. The intellectual merit is that through the combined expertise of the PIs, new knowledge will be gained in the field of catalysts synthesis applied to the problem that is currently of considerable societal importance and could have a broad technical impact. The comprehensive program proposed will integrate research at both the graduate level, and at undergraduate level via REU grants. A broader educational impact is planned by setting aside funds for supporting the effort of the minority engineering program at Notre Dame to help increase recruiting of underrepresented groups in engineering. The funds will support an outreach program to bring prospective students to Notre Dame and have them participate on experiments related to this proposal.

Eduardo E. Wolf0730190这项工作是出于需要找到高表面积金属/氧化物催化剂的可控制备方法，用于用于用于小型燃料电池应用的甲醇（ORM）的氧化重构。 The objective of the research is twofold: 1) to study a novel method for catalyst preparation based on solution combustion synthesis, referred to as Impregnated Layer Combustion Synthesis, or ILCS, and, 2) develop structure-activity correlations of catalysts prepared by the ILCS method for the ORM reaction along with spectroscopic studies to identify active sites and links those with surface and material properties.在PIS组中进行的初步研究表明，通过共同沉淀制备的PD/Cu/ZnO/ZRO2催化剂对ORM反应具有活性和选择性。 PI还确定了Cu金属表面积和氧化状态是活性和选择性的决定因素。 ILCS方法已证明可以在高面积氧化物上产生高表面积氧化物以及支持的金属。 ILCS方法涉及狭窄区域中反应前沿的控制繁殖，这与气体的演变一起抑制粒径的生长，导致形成高表面积（50-200 m2/g）的氧化物，高纯度和结晶度，这不需要额外的钙化。提供了概念证明，通过使用ILC，它们能够合成具有高面积，活性和选择性类似于共沉淀催化剂的催化剂。预计ILCS方法的进一步研究将产生更高的活性区域，并提高活动和选择性。在上述结果的基础上，他们假设i）i）对ILC的制备变量如何影响材料特性的基本了解将导致ORM反应的主动和选择性催化剂的设计，ii）建立ORM反应的结构活性相关性可以导致更多活跃和选择性的氧化催化催化剂。计划一项详细的程序研究ILC中使用的制备变量如何（溶液浓度，燃料组成，底物浸渍，点火温度）影响散装物质和表面特性，例如总表面积，结晶度，相位分别，相位组成，启动子的分散体以及不同环境下的氧化状态。由ILC制备的各种催化剂的活性和选择性结果将通过各种高级技术评估。选定催化剂的动力学将详细测量与材料特性和制备变量相关。选定催化剂的EXAF和红外光谱法将用于确定催化剂在反应条件下（Operando）在催化剂的氧化状态和吸附物的类型，并确定负责活性和选择性的关键表面变量。然后，动力学研究的速率常数将与关键表面特性相关，而这些特性又与ILCS制备变量相关。获得的结果将为新的ILC提供新的知识，以作为氧化催化剂的合理设计的一种方法以及决定了ORM氢生产的因素。智力优点是，通过PI的综合专业知识，将在催化剂综合领域获得新知识，该领域适用于目前具有相当大的社会重要性的问题，并且可能具有广泛的技术影响。拟议的综合计划将通过REU赠款在研究生层面和本科层面整合研究。通过拨出资金来支持巴黎圣母院的少数族裔工程计划的努力来帮助增加工程中代表性不足的群体的招聘，从而计划了更广泛的教育影响。这些资金将支持一项外展计划，将准学生带到巴黎圣母院，并让他们参加与该提案相关的实验。