MXene Aerogel Derived Ultra-Active Vanadia Catalyst for Selective Conversion of Sustainable Alcohols to Base Chemicals
MXene Aerogel Derived Ultra-Active Vanadia Catalyst for Selective Conversion of Sustainable Alcohols to Base Chemicals
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DOI：
10.1021/acsami.2c22720
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发表时间：
2023-03-24
影响因子：
9.5
通讯作者：
Etzold, Bastian J. M.
中科院分区：
文献类型：
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作者：
Oefner, Niklas;Shuck, Christopher E.;Etzold, Bastian J. M.
选择性氧化反应是当前化学工业的一个重要类别，对于未来的可持续化学生产将非常重要。特别是，伯醇的选择性氧化预计将是未来的高度兴趣，因为醇可以从生物质发酵获得的技术规模。伯醇的氧化产生醛，这是重要的中间体。虽然选择性甲醇氧化在工业上已经建立，但商业催化剂存在失活的问题。乙醇选择性氧化尚未商业化，但当使用可再生乙醇时，将获得可持续的乙醛生产。在这项工作中，它表明，采用2D MXene作为构建块，允许人们设计一种由混合价钒氧化物组成的纳米结构氧化物催化剂，其在活性上优于两种已知材料的反应近一个数量级，同时显示出高选择性和稳定性。研究表明，采用二维材料的合成路线是获得这些有吸引力的催化剂的关键。需要采用作为气凝胶前体结构化的V4C3Tx MXene，并在醇和氧气气氛中温和氧化，以产生由混合价态VO2、V6O13和V3O7组成的期望纳米结构催化剂。很可能，材料的本体稳定的还原价态与纳米棒排列一起允许前所未有的氧迁移率以及活性位点，并导致超活性催化剂。
Selective oxidation reactions are an important class of the current chemical industry and will be highly important for future sustainable chemical production. Especially, the selective oxidation of primary alcohols is expected to be of high future interest, as alcohols can be obtained on technical scales from biomass fermentation. The oxidation of primary alcohols produces aldehydes, which are important intermediates. While selective methanol oxidation is industrially established, the commercial catalyst suffers from deactivation. Ethanol selective oxidation is not commercialized but would give access to sustainable acetaldehyde production when using renewable ethanol. In this work, it is shown that employing 2D MXenes as building blocks allows one to design a nanostructured oxide catalyst composed of mixed valence vanadium oxides, which outperforms on both reactions known materials by nearly an order of magnitude in activity, while showing high selectivity and stability. The study shows that the synthesis route employing 2D materials is key to obtain these attractive catalysts. V4C3Tx MXene structured as an aerogel precursor needs to be employed and mildly oxidized in an alcohol and oxygen atmosphere to result in the aspired nanostructured catalyst composed of mixed valence VO2, V6O13, and V3O7. Very likely, the bulk stable reduced valence state of the material together coupled with the nanorod arrangement allows for unprecedented oxygen mobility as well as active sites and results in an ultra-active catalyst.