Supported Bifunctional Molybdenum Oxide-Palladium Catalysts for Selective Hydrodeoxygenation of Biomass-Derived Polyols and 1,4-Anhydroerythritol
Supported Bifunctional Molybdenum Oxide-Palladium Catalysts for Selective Hydrodeoxygenation of Biomass-Derived Polyols and 1,4-Anhydroerythritol
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用于生物质衍生多元醇和 1,4-脱水赤藓糖醇选择性加氢脱氧的负载型双功能氧化钼-钯催化剂
DOI：
10.1021/acssuschemeng.1c06877
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发表时间：
2022
影响因子：
8.4
通讯作者：
Pagán-Torres, Yomaira J.
中科院分区：
文献类型：
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作者：
Albarracin-Suazo, Sandra;Freitas de Lima e Freitas, Lucas;MacQueen, Blake;Heyden, Andreas;Lauterbach, Jochen A.;Nikolla, Eranda;Pagán-Torres, Yomaira J.
从生物质衍生多元醇中选择性去除氧对于弥合生物质原料和商品化学品生产之间的差距至关重要。在这项工作中，我们证明了地球上丰富的钼氧化物基非均相催化剂对生物质衍生多元醇中邻近的C-O键的裂解具有活性，选择性和稳定性。催化剂表征（拉曼光谱，x射线光电子能谱（XPS），漫反射红外傅立叶变换光谱（DRIFTS））表明，部分还原的mooxcenter负责C-O键的裂解，并在氢解离原子在钯（Pd）纳米颗粒上生成。我们发现载体TiO2通过氢溢出促进氢解离金属和分散的mooxites之间的通信。使用生物质衍生模型底物（1,4-无水赤藓糖醇）进行的反应性研究表明，在MoOx-Pd/ tio2上有效去除邻羟基，产生四氢呋喃，转化率为29%，选择性为bb0 98%。催化剂的稳定性在循环中得到证明。这些研究对于开发低成本的非均相催化剂，以实现生物基多元醇可持续的加氢脱氧为平台化学品至关重要。
Selective removal of oxygen from biomass-derived polyols is critical toward bridging the gap between biomass feedstocks and the production of commodity chemicals. In this work, we show that earth-abundant molybdenum oxide based heterogeneous catalysts are active, selective, and stable for the cleavage of vicinal C–O bonds in biomass-derived polyols. Catalyst characterization (Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS)) shows that partially reduced MoOxcenters are responsible for C–O bond cleavage and are generatedin situby hydrogen dissociated atoms over palladium (Pd) nanoparticles. We find that the support, TiO2, facilitates communication between the hydrogen dissociating metal and dispersed MoOxsites through hydrogen spillover. Reactivity studies using a biomass-derived model substrate (1,4-anhydroerythritol) show the effective removal of vicinal hydroxyls over MoOx-Pd/TiO2producing tetrahydrofuran with >98% selectivity at 29% conversion. Catalyst stability is demonstrated upon cycling. These studies are critical toward the development of low-cost heterogeneous catalysts for sustainable hydrodeoxygenation of biobased polyols to platform chemicals.