Investigation of critical effects in formic acid decomposition over highly dispersed gold catalysts by means of theoretical chemistry

通过理论化学研究高度分散的金催化剂对甲酸分解的关键影响

• 批准号: 252615961
• 负责人: Dr. Jan Kucera
• 金额: --
• 依托单位: Kommunikations- und Informationszentrum (kiz)
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2014
• 资助国家: 德国
• 起止时间: 2013-12-31 至 2020-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/252615961?language=en
• 关键词: Investigation; critical; effects; formic; acid

This project focuses on dehydrogenation of formic acid on the catalysts based on hybrid Au/oxide systems. This reaction has the high technological potential with respect to H2-technology and sustainableenergy concept on the background.Au subnanometer- and nanometer-sized clusters and particles dispersed on oxide supports decompose selectively formic acid (HCOOH-> CO2 + H2) to provide pure H2 already at low temperatures. Prerequisite for an application of formic acid as a hydrogen source in proton-exchange membrane fuel cells (PEM FCs) is to significantly improve the efficiency of the current catalysts. To rationalize a successful strategy towards remarkably advanced catalysts is difficult, if not impossible, due to limited understanding of mechanistic principles controlling the catalytic behavior. With this respect, mainly to shed more light on the atomic scale level structure-catalytic function relationship is crucial.I propose to use methods of modern quantum chemistry in order to understand key effects operating in gas phase decomposition of formic acid over Au/oxide catalysts. Analysis of these effects will provide a platform on which the progressive strategy for advanced processing of the H2 release within the selective formic acid decomposition will be outlined. Benefits of prospective outcomes will not be limited to only the particular reactions, however, they will also supplement a fundamental understanding of the activity of nanostructured gold as versatile catalysts of redox-oxidation reactions.Optimizations of geometry and electronic structures by first-principles methods mainly based on periodical density functional theory (DFT) will be extended by kinetic Monte Carlo simulations in order to model reaction kinetic under realistic conditions. In addition, specific attention will be given to an establishment of a link between active sites in the models and those on real catalysts. Regarding to this aim I will address a probe molecule approach.A part of the project will be dedicated to methodology evaluation. In particular, capability of the applied first-principles methods to treat weak interactions between molecule and catalysts will be a subject of the examination. Potential corrections will be developed. To accomplish this task high-quality benchmarks relevant for the considered systems is prerequisite. Therefore I will make an attempt to implement high-level wavefunction-based methods into the models.

本项目主要研究了甲酸在Au/氧化物复合体系催化剂上的脱氢反应。该反应在氢气技术和可持续能源概念的基础上具有很高的技术潜力。分散在氧化物载体上的亚纳米和纳米级的团簇和颗粒选择性地分解甲酸(HCOOH-&GT；CO2+H2)，在低温下就可以得到纯净的氢气。将甲酸作为氢源应用于质子交换膜燃料电池(PEM FCS)的前提条件是显著提高现有催化剂的效率。由于对控制催化行为的机械原理的了解有限，要使一个成功的战略合理化是困难的，如果不是不可能的话。在这方面，主要是阐明原子尺度的结构-催化功能关系是至关重要的，我建议用现代量子化学的方法来理解在Au/氧化物催化剂上甲酸气相分解的关键影响因素。对这些影响的分析将提供一个平台，在此平台上将概述选择性甲酸分解中氢气释放的高级处理的渐进战略。然而，预期结果的好处将不仅限于特定的反应，但它们也将补充对纳米结构金作为氧化还原反应多功能催化剂的活性的基本理解。主要基于周期密度泛函理论(DFT)的第一性原理方法对几何结构和电子结构的优化将通过动力学蒙特卡罗模拟扩展，以便在现实条件下模拟反应动力学。此外，还将特别注意在模型中的活性中心和真实催化剂上的活性中心之间建立联系。关于这一目标，我将介绍一种探针分子方法。该项目的一部分将致力于方法学评估。特别是，应用第一性原理方法处理分子和催化剂之间弱相互作用的能力将是审查的主题。将制定潜在的修正措施。要完成这项任务，与所考虑的系统相关的高质量基准是先决条件。因此，我将尝试在模型中实现基于波函数的高级方法。