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

本项目主要研究基于金/氧化物杂化体系的甲酸脱氢催化剂。该反应在h2技术和可持续能源概念的背景下具有很高的技术潜力。分散在氧化物载体上的亚纳米级和纳米级的金团簇和颗粒选择性地分解甲酸（HCOOH-> CO2 + H2），在低温下产生纯H2。甲酸作为氢源应用于质子交换膜燃料电池（PEM fc）的前提是显著提高现有催化剂的效率。由于对控制催化行为的机理原理的理解有限，要对非常先进的催化剂的成功策略进行合理化是困难的，如果不是不可能的话。在这方面，进一步阐明原子尺度上结构-催化功能的关系是至关重要的。我建议使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效应。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H2释放的先进处理策略。预期结果的好处将不仅仅局限于特定的反应，然而，它们也将补充对纳米结构金作为氧化还原-氧化反应的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）的第一性原理方法优化几何结构和电子结构，将其扩展到动力学蒙特卡罗模拟，以模拟现实条件下的反应动力学。此外，将特别注意在模型中的活性位点与实际催化剂上的活性位点之间建立联系。关于这个目标，我将讨论探针分子方法。项目的一部分将用于方法论评估。特别是，应用第一性原理方法来处理分子和催化剂之间的弱相互作用的能力将是检验的主题。将拟定可能的纠正措施。要完成这项任务，与所考虑的系统相关的高质量基准测试是先决条件。因此，我将尝试将基于波函数的高级方法实现到模型中。

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.