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Toward Hydrogen Economy: Selective Guaiacol Hydrogenolysis under Ambient Hydrogen Pressure
Applied Catalysis B: Environment and Energy ( IF 22.1 ) Pub Date : 2020-03-20 , DOI: 10.1016/j.apcatb.2020.118890
Hui Zhou , Hsin Wang , Aaron D. Sadow , Igor I. Slowing

The conversion of guaiacol into the nylon precursors, cyclohexanol and cyclohexanone, is catalyzed by palladium supported on high surface area ceria (Pd/HS CeO2) under mild conditions (100 °C, ≤1 bar H2) via sequential hydrodemethoxylation and hydrogenation. In contrast, the 2-methoxycyclohexanol side product is generated by direct guaiacol hydrogenation. Reaction selectivity is determined by competing C-O bond hydrogenolysis versus arene hydrogenation. Hydrogenolysis selectivity increases as H2 pressure decreases, and over 80% H2 is incorporated into the products at 1 bar H2. Higher reactivity of guaiacol than anisole implies that the hydroxyl group is essential in Pd/HS CeO2 catalysis. Participation of water in the conversion is evidenced by deuterium incorporation at non-exchangeable positions when the reaction is performed in D2O. The combination of near quantitative mass balance of H2, high recyclability, and use of water as a solvent offers a simple, green and efficient conversion of lignin-derived aromatics into commercial products.



中文翻译:

迈向氢经济:常压下的选择性愈创木酚氢解

在连续的加氢脱甲氧基化和氢化作用下,在温和的条件下(100°C,≤1bar H 2),负载在高表面积二氧化铈(Pd / HS CeO 2)上的钯催化了愈创木酚向尼龙前体环己醇和环己酮的转化。相反,通过直接愈创木酚氢化产生2-甲氧基环己醇副产物。反应选择性是通过竞争CO键氢解与芳烃氢化来确定的。氢解选择性随H 2压力降低而增加,并且在1 bar H 2下将超过80%的H 2掺入产物中。愈创木酚的反应性高于苯甲醚,表明羟基在Pd / HS CeO 2中必不可少催化。在转换的水参与当反应在d执行通过氘掺入在不可交换的位置证实2 O. h的接近定量质量平衡的组合2,高可回收性,和使用水作为溶剂提供了一个简单,绿色高效地将木质素衍生的芳烃转化为商品。

更新日期:2020-03-20
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