First-principles kinetic modeling for solar hydrogen production

界面处可持续和高效能量转换过程的开发是基础能源科学快速发展领域的中心。如何成功地应对这一挑战将最终取决于对分子水平的理解程度。在这方面，与多相催化中相应的热过程相比，电或光催化转化中的严重知识差距是惊人的。这种差异在预测质量的现状中最为明显，即两个领域中基于第一原理的建模，这在很大程度上归因于与电化学环境的处理和由光激发电荷或外部电势驱动的表面氧化还原化学的描述相关的多因素方法问题。成功解决这些复杂性将推进建模方法（照片）电催化达到与多相催化中已经建立的类似水平，其影响甚至可能取代过去十年中所看到的影响。相应的方法开发是本提案的核心目标，特别强调数值有效的方法，最终将允许达到全面的微动力学配方。协同结合两个参与小组的方法学专业知识，我们的目标是实施和推进隐式和混合隐式/显式溶剂化模型，以及QM/MM方法来描述固液界面的能量相关过程。有了明确的目标，开发通用的方法，我们将说明他们的使用与应用，通过水分解制氢。把电感应器解开。相对于相应的暗反应，这涉及在金属电极如Pt处的析氢反应和在氧化物光催化剂如TiO 2处的直接水裂解。通过这一点，我们期望达到一个详细的机械的理解，最终将在制定全面的微观动力学模型的光或电位驱动的氧化还原过程。用动力学Monte Carlo模拟评估这些模型将明确识别速率确定和超电势产生步骤，从而为整个过程的合理优化提供基础。因此，我们的研究将提供一个关键例子，说明基础能源科学计算方法的系统方法开发如何带来突破性进展，并服务于基础理解和前沿应用。

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.