First-principles kinetic modeling for solar hydrogen production

太阳能制氢的第一原理动力学模型

基本信息

批准号：
232329072
负责人：
Professor Dr. Karsten Reuter
金额：
--
依托单位：
Department of Chemistry
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2013
资助国家：
德国
起止时间：
2012-12-31 至 2016-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/232329072?language=en
关键词：
First principles kinetic modeling solar

项目摘要

The development of sustainable and efficient energy conversion processes at interfaces is at the center of the rapidly growing field of basic energy science. How successful this challenge can be addressed will ultimately depend on the acquired degree of molecular-level understanding. In this respect, the severe knowledge gap in electro- or photocatalytic conversions compared to corresponding thermal processes in heterogeneous catalysis is staggering. This discrepancy is most blatant in the present status of predictive-quality, viz. first-principles based modelling in the two fields, which largely owes to multifactorial methodological issues connected with the treatment of the electrochemical environment and the description of the surface redox chemistry driven by the photo-excited charges or external potentials.Successfully tackling these complexities will advance modelling methodology in (photo)electrocatalysis to a similar level as already established in heterogeneous catalysis, with an impact that likely even supersedes the one seen there in the last decade. A corresponding method development is the core objective of the present proposal, with particular emphasis on numerically efficient approaches that will ultimately allow to reach comprehensive microkinetic formulations. Synergistically combining the methodological expertise of the two participating groups we specifically aim to implement and advance implicit and mixed implicit/explicit solvation models, as well as QM/MM approaches to describe energy-related processes at solid-liquid interfaces. With the clear objective to develop general-purpose methodology we will illustrate their use with applications to hydrogen generation through water splitting. Disentangling the electro- resp. photocatalytic effect with respect to the corresponding dark reaction, this concerns both the hydrogen evolution reaction at metal electrodes like Pt and direct water splitting at oxide photocatalysts like TiO2. Through this we expect to arrive at a detailed mechanistic understanding that will culminate in the formulation of comprehensive microkinetic models of the light- or potential-driven redox process. Evaluating these models with kinetic Monte Carlo simulations will unambiguously identify the rate-determining and overpotential-creating steps and therewith provide the basis for a rational optimization of the overall process. As such our study will provide a key example of how systematic method development in computational approaches to basic energy sciences leads to breakthrough progress and serves both fundamental understanding and cutting-edge application.

界面上可持续和有效的能源转化过程的发展是基本能源科学快速增长的领域的中心。如何成功解决这一挑战将最终取决于分子层面的理解程度。在这方面，与异质催化的相应热过程相比，电催化转化的严重知识差距令人震惊。这种差异在预测质量的当前状态中最为公然，即。这两个领域的基于第一原则的建模，这在很大程度上归功于与电化学环境处理相关的多因素方法论问题，以及由光启用电荷或外部电位驱动的表面氧化还原化学的描述。成功解决这些复杂性的努力也将在（照片中）在（照片中）与类似的级别的建模级别，即使在（照片中）的电气化级别，即使在（照片）中，该级别的电位构成了类似的态度。取代了过去十年中看到的那个。相应的方法开发是本提案的核心目标，特别着重于数值有效的方法，最终将允许达到全面的微动力表述。协同结合了我们特别旨在实施和推进隐式和混合隐式/显式溶剂化模型的两个参与群体的方法论专业知识，以及QM/MM的方法来描述固体液体接口处的能源相关过程。有了明确的目标，我们将说明它们通过水分割来应用于氢生成的应用。解开电源。相对于相应的黑暗反应，光催化作用涉及金属电极在PT（例如PT）和氧化物光催化剂（如TiO2）上的直接水分的氢进化反应。通过这种情况，我们期望获得详细的机械理解，该理解将在制定光或潜在驱动的氧化还原过程的综合微动力模型中达到顶峰。用动力学的蒙特卡洛模拟评估这些模型将明确确定速率确定的和过度的创建步骤，从而为整个过程的合理优化提供了基础。因此，我们的研究将提供一个关键的例子，说明如何在基本能源科学的计算方法中开发系统的方法开发如何导致突破性的进步，并为基本的理解和尖端应用提供。