Collaborative Research: Preparation,Characterization,and Evaluation of Bimetallic Catalysts Using Electroless Deposition Methods for Selective Oxidation of Biomass-Related Alcohols

0854339 现代催化研究的一个主要目标是设计和制造对特定官能团反应具有选择性的催化剂。在试图为选择性定制催化表面时，不仅重要的是对表面组成具有高水平的控制，而且重要的是使用可以按比例放大以经济地生产大量催化剂的方法来实现这种控制。一种有前景的技术是无电沉积（艾德），其允许一种金属组分以受控的量沉积在第二金属的表面上。由于艾德是一种可规模化的方法，可用于在负载型催化剂颗粒上制备真正的表面，因此它在催化应用中显示出很大的前景，其中选择性可通过调节表面组成来调节。在所提出的努力，艾德将被用作一种工具，用于定制的生物质相关的醇的选择性氧化的催化剂。除了对未来燃料和化学品的生产非常重要之外，它们还作为评估艾德制备这类反应的高选择性催化剂的能力的优良探针分子。拟议的努力将整合一套广泛的表征技术，追求选择性催化剂：1。艾德将用于制备一系列具有目标金属组成的Au、Ag和Cu改性的Pt和Pd催化剂;这些催化剂将使用一系列光谱技术进行表征，并将对甘油氧化进行评价。2. DFT计算研究的催化剂组合物将被用来更好地理解和证实的表征结果，并提出进一步的催化剂组合物的方向。3.催化剂评估结果将在催化剂表征和计算预测的指导方针内进行解释，以制造后续的催化剂。这种迭代循环应促进催化剂的开发，从而产生改进的醇氧化催化剂。总体目标是利用这些不同的能力来评估艾德用于制备氧化催化剂的效用，并采取步骤，基于对氧化催化剂的电子和结构特征的基本理解，对催化剂设计进行合理改进。智力优势。这些工作将有助于发展艾德作为一个潜在的重要技术，用于大规模生产的催化剂。这些努力也将提供一个模板，旨在识别多功能分子反应的选择性催化剂的程序。此外，（a）负载型金属催化剂的制备和表征与（B）基础建模和表面科学研究之间的紧密结合将有助于进一步发展基础科学与应用催化的整合，最终促进催化和材料合成的合理设计方法。更广泛的影响。生物质相关醇的选择性氧化是生产一类新的生物衍生产品的重要工业目标。ED制备的催化剂具有更高的选择性，有助于降低工艺分离成本、原料的过度使用和对环境的排放。这种合作努力还将使研究生和本科生参与催化社区内的各种研究方法的整合，从表面科学实验到计算化学，再到现实催化剂的选择性探针。从事该项目的学生所获得的广泛经验，以及与不同机构的多个PI的互动，将使这些学生认识到这些不同类型的催化研究的重要贡献。

0854339 MonnierA major goal of modern catalysis research is design and fabrication of catalysts that are selective toward reaction of a particular functional group. In attempting to tailor catalytic surfaces for selectivity, not only is it important to have a high level of control over the surface composition, but also to achieve this control using methods that can be scaled up for the economical production of large amounts of catalyst. One promising technique is electroless deposition (ED), which allows one metal component to be deposited in controlled quantities on the surface of a second metal. Because ED is a scaleable method that can be used to prepare truly bimetallic surfaces on supported catalyst particles, it shows great promise for catalytic applications in which selectivity can be tuned through adjustment of the surface composition. In the proposed effort, ED will be employed as a tool for tailoring bimetallic catalysts for the selective oxidation of biomass-related alcohols. In addition to being very important for the future production of fuels and chemicals, they serve as excellent probe molecules for assessing the capability of ED to prepare highly selective catalysts this class of reactions. The proposed effort will integrate a wide-ranging set of characterization techniques in pursuit of selective catalysts: 1. ED will be used to prepare a series of Au, Ag, and Cu-modified Pt and Pd catalysts having targeted metal compositions; these catalysts will be characterized using an array of spectroscopic techniques, and will be evaluated for glycerol oxidation. 2. DFT computational studies on the bimetallic compositions will be used to better understand and corroborate the characterization results and to suggest directions for further bimetallic catalyst compositions. 3. Catalyst evaluation results will be interpreted within the guidelines predicted by catalyst characterization and computation to make subsequent generations of catalysts. This iterative cycle should facilitate catalyst development leading to improved alcohol oxidation catalysts. The overall goal is to use these diverse capabilities to assess the utility of ED for preparation of bimetallic oxidation catalysts, and to take steps toward making rational improvements in catalyst design based on a fundamental understanding of electronic and structural features of the bimetallic catalysts. Intellectual Merit. The proposed work will help to develop ED as a potentially important technique for large-scale production of bimetallic catalysts. These efforts will also provide a template for programs aimed at identification of selective catalysts for reactions of multifunctional molecules. Furthermore, the close integration between (a) preparation and characterization of supported metal catalysts and (b) fundamental modeling and surface science studies will help to further develop the integration of basic science with applied catalysis, ultimately promoting rational design approaches for catalysis and materials synthesis. Broader Impact. The selective oxidation of biomass-related alcohols represents an important industrial target for production of a new class of bio-derived products. ED-prepared catalysts that facilitate higher selectivity can help to reduce process separations costs, over-use of feedstocks, and emissions to the environments. This collaborative effort will also allow graduate and undergraduate students to be involved in the integration of diverse research approaches within the catalysis community, ranging from surface science experiments to computational chemistry to selectivity probes of realistic catalysts. The broad experience gained by the students who work on this project, as well as the interactions with multiple PIs at different institutions, will allow those students to recognize the important contributions available from these different types of catalysis studies.