Sustainable transformation of biomass platform molecules to valuable C1 building blocks by selective heterogeneous catalytic oxidation

目前，大多数生物质转化过程导致几种Cn（n = 1）产物的分布，这需要昂贵的分离。因此，驱动生物质增值过程朝向选择的目标产物的优先形成是高度期望的，然而这仅在需要关于结构-反应性关系的深入知识的定制催化剂的情况下是可能的。该提案的主要目的是通过氧化C-C裂解将生物质衍生的平台分子选择性地转化为具有作为化学合成和/或能量储存的结构单元的高潜力的简单C1分子（HCHO或HCOOH）。为此，将制备具有不同表面酸碱性质和不同尺寸的活性Cu位的双功能负载Cu基催化剂。将使用不同孔径和结构的载体（沸石Y、介孔MCM和/或SBA材料），因为催化剂的孔系统内的限制可以影响活性位点的结构和尺寸以及从离析物到产物的反应途径。此外，为了提高对所需HCHO和/或HCOOH的选择性，已知支持C-C裂解但不支持完全氧化成CO2的第二金属（例如，G. Pd、Ag和Ni）将使用不同的方法引入。因此，将建立具有有目的地变化的性质的催化剂基质。催化剂将通过标准分析方法进行全面表征。此外，它们在反应条件下的动态行为将通过原位或操作光谱分析。从所有催化和表征结果的综合评价中，将得出优化催化剂以形成所需目标产物的规则。

Currently, most biomass transformation processes lead to a distribution of several Cn (n1) products which requires costly separation. Therefore, driving biomass valorization processes towards preferential formation of selected target products is highly desirable, yet this is only possible with tailor-made catalysts for which in-depth knowledge on structure-reactivity relationships is needed. The major aim of this proposal is to convert biomass-derived platform molecules by oxidative C-C cleavage selectively to simple C1 molecules (HCHO or HCOOH) with a high potential as building blocks for chemical synthesis and/or energy storage. To this end, bifunctional supported Cu-based catalysts with different surface acid-base properties and different size of the active Cu sites will be prepared. Supports of different pore size and structure (zeolite Y, mesoporous MCM and/or SBA materials) will be used since confinement within the pore system of catalysts can influence both structure and size of the active sites as well as reaction pathways from educts to products. Furthermore, to improve selectivity to desired HCHO and/or HCOOH a second metal known to support C-C cleavage but not total oxidation to CO2 (e. g. Pd, Ag and Ni) will be introduced using different methods. Thus, a matrix of catalysts with purposefully varied properties will be established. Catalysts will be characterized comprehensively by standard analytical methods. Moreover, their dynamic behavior under reaction conditions will be analyzed by in situ or operando spectroscopy. From the combined evaluation of all catalytic and characterization results, rules for optimizing catalysts towards the formation of desired target products will be derived.