Selective Vapor-Phase C1-Elongation of Methanol and Ethanol with H2 and CO2 by Tailoring Active Sites Immobilized in UiO-66-Type Metal Organic Frameworks

通过定制固定在 UiO-66 型金属有机框架中的活性位点，用 H2 和 CO2 选择性气相 C1 延伸甲醇和乙醇

• 批准号: 512819724
• 负责人: Dr. Ken Luca Abel
• 金额: --
• 依托单位: Institut für Technische Chemie
• 依托单位国家: 德国
• 项目类别: WBP Fellowship
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/512819724?language=en
• 关键词: Selective; Vapor; Phase; C1; Elongation

C1-compounds such as methane, methanol, formic acid or carbon monoxide can already be formed selectively via heterogenous catalysis by CO2 hydrogenation with H2. Molecules containing more than one C atom, however, can with the exception of ethanol so far only obtained as one component in a distribution of products from CO2 hydrogenation with H2 in the gas phase. This due to the difficulty to simultaneously control C-C-formation and CO2 hydrogenation. Given this challenge, this project intends to form specifically one C-C bond in a gas stream of CO2, H2 and an aliphatic alcohol (methanol, ethanol). In this way, the C1-elongated carboxylic acid or the respective alcohol is synthesized selectively. To this end, solid catalysts based on UiO-66-type metal-organic frameworks, on which metal atoms or clusters are immobilized, will be used. The project follows three definite objectives: 1) demonstration of the formation of the C1-elongated carboxylic acid or alcohol by gas-phase halide-free CO2 hydrogenation with H2 and methanol or ethanol; 2) understanding of the reaction mechanism from the individual roles of both the MOF framework and the immobilized metal atoms or clusters within the solid catalyst; 3) tailoring of the solid catalysts, e.g., by changing the active sites or the coordination environment around it, to drive the selectivity towards either a specific C1-elongated carboxylic acid or its corresponding alcohol. Meeting these three objectives may ultimately allow for a removal of the alcohol from the gas feed, thus opening a new path for the selective formation of higher (C2+) carboxylic acids and alcohols from direct CO2 hydrogenation with H2 in the gas phase

C1-化合物如甲烷、甲醇、甲酸或一氧化碳已经可以通过CO2与H2氢化的非均相催化选择性地形成。然而，除了乙醇之外，含有多于一个C原子的分子到目前为止只能作为气相中用H2氢化CO2的产物分布中的一种组分获得。这是由于难以同时控制C-C-形成和CO2氢化。鉴于这一挑战，该项目旨在在CO2，H2和脂肪醇（甲醇，乙醇）的气流中形成一个C-C键。以这种方式，选择性地合成C1-延长的羧酸或相应的醇。为此，将使用基于UiO-66型金属有机骨架的固体催化剂，在其上固定有金属原子或簇。该项目遵循三个明确的目标：1）通过气相无卤素CO2氢化与H2和甲醇或乙醇形成C1-延长的羧酸或醇的示范; 2）从MOF框架和固体催化剂内固定的金属原子或簇的单独作用理解反应机理; 3）定制固体催化剂，例如，通过改变活性位点或其周围的配位环境，以驱动对特定C1-延长羧酸或其相应醇的选择性。满足这三个目标可以最终允许从气体进料中除去醇，从而为从气相中用H2直接CO2氢化选择性形成高级（C2+）羧酸和醇开辟了新的途径