最简单的单糖的电化学还原：二羟基丙酮和甘油醛,ACS Catalysis

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最简单的单糖的电化学还原：二羟基丙酮和甘油醛
ACS Catalysis ( IF 11.3 ) Pub Date : 2020-11-16 , DOI: 10.1021/acscatal.0c04131
Zhiqin Liang ₁ , Matias A. Villalba ₁ , Giulia Marcandalli ₁ , Kasinath Ojha ₁ , Arthur J. Shih ₁ , Marc T. M. Koper ₁

Affiliation

自然界中最简单的单糖二羟基丙酮（DHA）和甘油醛（GA）都是有机合成中必不可少的组成部分。对于通过铂催化的甘油的电化学氧化选择性生产DHA和GA进行了详细的研究，甘油是生物柴油的多余副产物。但是，对DHA和GA本身的电化学行为的关注较少。在这里，我们报告了在铂和钯电极上不同pH下DHA和GA的电化学还原。钯对DHA和GA的脱羟基和氢化均表现出优异的活性。使用在线高效液相色谱，我们显示DHA和GA均显示出两步还原。特别是先将DHA还原为丙酮醇，然后再还原为丙酮，首先将GA还原为3-羟基丙醛（3-HPA），然后将其氢化为1,3-丙二醇。两种分子的还原都伴随着催化剂表面的中毒。原位傅里叶变换红外光谱测量表明，吸附的一氧化碳是中毒物质，这是由于DHA和GA的解离吸附所致。提出并讨论了减少DHA和GA的机理反应途径。

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Electrochemical Reduction of the Simplest Monosaccharides: Dihydroxyacetone and Glyceraldehyde

Dihydroxyacetone (DHA) and glyceraldehyde (GA)—the simplest monosaccharides in nature—are both essential building blocks in organic synthesis. There have been detailed investigations on the selective production of DHA and GA through the platinum-catalyzed electrochemical oxidation of glycerol, which is a surplus byproduct from biodiesel. However, less attention has been paid to the electrochemical behavior of DHA and GA themselves. Here, we report the electrochemical reduction of DHA and GA at different pH on platinum and palladium electrodes. Palladium exhibits a superior activity toward both the dehydroxylation and hydrogenation of DHA and GA. Using online high-performance liquid chromatography, we show that both DHA and GA display a two-step reduction. In particular, DHA is reduced first to acetol and then sequentially to acetone, while GA is first reduced to 3-hydroxypropionaldehyde (3-HPA), followed by hydrogenation to 1,3-propanediol. The reduction of both molecules is accompanied by a poisoning of the catalyst surface. In situ Fourier-transform infrared spectroscopy measurements suggest adsorbed carbon monoxide as the poisoning species, resulting from the dissociative adsorption of DHA and GA. Mechanistic reaction pathways for both DHA and GA reduction are proposed and discussed.

更新日期：2020-12-04

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