Abstract Heterogeneous and combined hetero-/homogeneous chemical processes have attracted increased attention in many energy conversion systems, which include large-scale power generation, microreactors for portable power generation, household burners, fuel-processing technologies and automotive exhaust gas after treatment. Progress in such systems crucially depends on the development of catalysts with enhanced activity and thermal stability and on the comprehensive understanding of the fundamental processes occurring near gas–solid reacting interfaces. Recent advances in non-intrusive lased-based measurements of gas-phase thermoscalars over the catalyst boundary layer are reviewed. Such measurements, combined with theoretical analyses and numerical simulations, have fostered fundamental investigations of the catalytic and gas-phase chemical processes and their coupling at industrially-relevant operating conditions. The methodology for assessing local catalytic reaction rates and validating gas-phase reaction mechanisms under steady conditions using 1-D Raman and planar laser induced fluorescence (PLIF) of radical species, respectively, is presented first. Progress in the measurement of minor and major stable species using PLIF is outlined and the potential of this technique as a suitable method for assessing the catalytic reactivity under dynamic operating conditions is discussed. State of the art numerical modeling necessary for the interpretation of the measurements is presented in parallel with the laser-based techniques. Turbulence modeling, direct numerical simulation (DNS) and near-wall non-intrusive measurements of species concentrations and velocity have clarified aspects of the complex interplay between interphase turbulent transport and hetero-/homogeneous kinetics. Controlling parameters are the competition between the heterogeneous and homogeneous reaction pathways, diffusional imbalance of the deficient reactant, flow laminarization induced by the hot catalytic walls, and fuel leakage through the gaseous reaction zone that leads to concurrent catalytic and gas-phase combustion. Experimental needs for assessing turbulent fluctuations of catalytic reaction rates as well as for investigating intrinsic instabilities (heterogeneously or homogeneously driven) are discussed. Future directions for combining in situ surface science diagnostics with in situ non-intrusive gas-phase thermoscalar diagnostics and for advancing current numerical tools are finally proposed.

中文翻译：

---

基于非侵入式激光的气相热标量测量和催化界面附近支持建模的进展

摘要 多相和多相结合的多相/均相化学过程在许多能量转换系统中引起了越来越多的关注，包括大规模发电、便携式发电微反应器、家用燃烧器、燃料处理技术和汽车尾气后处理。这种系统的进展关键取决于具有增强活性和热稳定性的催化剂的开发，以及对气固反应界面附近发生的基本过程的全面理解。综述了催化剂边界层上气相热标量的非侵入式激光测量的最新进展。这种测量，结合理论分析和数值模拟，促进了催化和气相化学过程及其在工业相关操作条件下的耦合的基础研究。首先介绍了分别使用自由基物种的一维拉曼和平面激光诱导荧光 (PLIF) 评估局部催化反应速率和验证气相反应机制的方法。概述了使用 PLIF 测量次要和主要稳定物种的进展，并讨论了该技术作为评估动态操作条件下催化反应性的合适方法的潜力。解释测量值所需的最先进的数值建模与基于激光的技术并行呈现。湍流建模，直接数值模拟 (DNS) 和物质浓度和速度的近壁非侵入式测量阐明了相间湍流输运与异质/均质动力学之间复杂相互作用的各个方面。控制参数是多相和均相反应途径之间的竞争、缺陷反应物的扩散不平衡、由热催化壁引起的流动层化以及通过气态反应区的燃料泄漏导致催化和气相同时燃烧。讨论了评估催化反应速率的湍流波动以及研究内在不稳定性（非均相或均相驱动）的实验需求。