以氧化反应底物的键型特征为标的，从原子水平对活性位进行调制以增强对特定键型的活化效率，是此类催化剂进行从头设计的主要挑战。项目以对贵金属基PM-TM与PM-MOx型纳米合金实现原子级别调控为目标，将通过对纳米合金粒子进行组分调整与优化，并采用热化学处理以及载体模板等后期调控技术，构筑与反应底物键型相匹配的表面结构。在研究中除借助电子显微镜与原位红外、拉曼等常规表征工具外，将利用非探针分子依赖的同步辐射HEXRD-PDF技术对活性位的构筑、调控与临氧反应过程进行原位实时检测，以期对该活性中心在热化学处理作用下的构筑动态，及其促进分子氧及探针型底物活化的催化动力学机制进行直接解读。在建立活性中心与底物指向的完全氧化特性之间的构效关系后，针对具有C-C、C-H复合键型特征的链烃与低碳醇分子的完全氧化反应，通过对各类键型匹配的活性中心进行组装，实现"面向对象"的催化剂设计。

The ability to tune the active sites on a catalyst at atomic scale is a major challenge for the ultimate design of active and stable catalysts for the catalytic complete oxidations of molecules such as hydrocarbons and alcohols. The basic hypothesis of this project is to harness the noble metal - transition metal and noble metal - metal oxide interactions in nanoalloy based catalysts towards achieving the atomic-scale tunability. To this end, proposed approach is to construct the nanoscale structure specific to an oxidation substrate. The strategies include the synthetic tuning and optimization of the nanoalloy composition in terms of noble metals vs. transition metals, thermochemical treatment under reactive gases, and manipulation of the support-nanoalloy interaction (SNI). In addition to conventional characterization tools such as in-situ FTIR, Raman and electron microscopy, synchrotron based High Energy X-ray Diffraction coupled with Pairs Distribution Function (HEXRD-PDF) will be utilized for in-situ real time monitoring the atomic-scale nanostructural evolution under thermochemical reactive conditions and the catalytic activation mechanism of molecular oxygen and the probe substrate. By investigating the correlation between the structure of active sites and the oxidative kinetics of the activation of specific chemical bonds in terms of the active sites oriented to C-C and C-H bonds in hydrocarbon and lower-carbon alcohol molecules, we will establish the ability in the reaction-specific manipulation of the nanoscale catalytic active sites, which is fundamental for the design of highly-active complete oxidation catalysts.