Influence of vanadate structure and support identity on catalytic activity in the oxidative cleavage of methyl ketones
Influence of vanadate structure and support identity on catalytic activity in the oxidative cleavage of methyl ketones
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DOI：
10.1016/j.jcat.2017.12.034
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发表时间：
2018-03
影响因子：
7.3
通讯作者：
Ran Zhu;Anargyros Chatzidimitriou;Jesse Q. Bond
中科院分区：
文献类型：
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作者：
Ran Zhu;Anargyros Chatzidimitriou;Jesse Q. Bond
氧化性酮分裂是一类有趣的反应;它们产生醛和羧酸作为产物，并且它们在分子氧存在下通过可还原的氧化物进行。这种化学过程可以在负载型钒氧化物上从乙酰丙酸（LA）生产生物基马来酸酐（MA）中发挥作用。在这里，我们探讨的作用，活性中心的结构和支持身份在支配酮氧化的速度。具体地说，我们制备了SiO2、γ-Al 2 O3、TiO 2和CeO 2负载量范围内的钒氧化物，并量化了它们在2-戊酮氧化裂解中的内在活性。采用傅里叶变换拉曼光谱和程序升温表面氧化（TPSO）的吸附甲醇探测钒的形态和氧化位密度。我们的分析表明，负载钒酸盐的固有活性是敏感的钒氧化物结构和支持身份。
Oxidative ketone scissions are an interesting class of reactions; they yield aldehyde and carboxylic acids as products, and they proceed over reducible oxides in the presence of molecular oxygen. This chemistry can be leveraged in the production of bio-based maleic anhydride (MA) from levulinic acid (LA) over supported vanadium oxides. Here, we probe the role of active site structure and support identity in dictating the rate of ketone oxidation. Specifically, we have prepared supported vanadium oxides in a range of loadings on SiO2, γ-Al2O3, TiO2and CeO2, and we have quantified their intrinsic activity in the oxidative cleavage of 2-pentanone. FT-Raman spectroscopy and temperature programmed surface oxidation (TPSO) of adsorbed methanol were employed to probe vanadium speciation and oxidation site densities. Our analysis suggests that the intrinsic activity of supported vanadates is sensitive to both vanadium oxide structure and support identity.