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水氧化与镍催化的羰基化合物和不饱和碳-碳键的电催化氢化反应相耦合。

Water oxidation couples to electrocatalytic hydrogenation of carbonyl compounds and unsaturated carbon-carbon bonds by nickel.

作者信息

Behrouzi Leila, Zand Zahra, Fotuhi Mobina, Kaboudin Babak, Najafpour Mohammad Mahdi

机构信息

Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan, 45137-66731, Iran.

Center of Climate Change and Global Warming, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan, 45137-66731, Iran.

出版信息

Sci Rep. 2022 Nov 19;12(1):19968. doi: 10.1038/s41598-022-23777-7.

Abstract

Artificial photosynthesis, an umbrella term, is a chemical process that biomimetics natural photosynthesis. In natural photosynthesis, electrons from the water-oxidation reaction are used for carbon dioxide reduction. Herein, we report the reducion of aldehydes and ketones to corresponding alcohols in a simple undivided cell. This reaction utilized inexpensive nickel foam electrodes (1 cm) and LiClO (0.05 M) as a commercially accessible electrolyte in an aqueous medium. Under electrochemical conditions, a series of alcohols (21 examples) produces high selectivity in good yields (up to 100%). Usage the current method, 10 mmol (1060 mg) of benzaldehyde is also successfully reduced to benzyl alcohol (757 mg, 70% isolated yield) without any by‑products. This route to alcohols matched several green chemistry principles: (a) atom economy owing to the use of HO as the solvent and the source of hydrogen, (b) elimination of the homogeneous metal catalyst, (c) use of smooth reaction conditions, (d) waste inhibition due to low volumetric of by-products, and (e) application of safe EtOH co-solvent. Moreover, the ability of the system to operate with alkyne and alkene compounds enhanced the practical efficiency of this process.

摘要

人工光合作用是一个统称,是一种模拟自然光合作用的化学过程。在自然光合作用中,水氧化反应产生的电子用于二氧化碳的还原。在此,我们报道了在一个简单的无隔膜电解池中,醛和酮被还原为相应的醇。该反应使用廉价的泡沫镍电极(1厘米)和高氯酸锂(0.05 M)作为水介质中一种可商购的电解质。在电化学条件下,一系列醇(21个例子)以高选择性和良好产率(高达100%)生成。使用当前方法,10毫摩尔(1060毫克)苯甲醛也成功还原为苯甲醇(757毫克,分离产率70%),且无任何副产物。这条制备醇的路线符合多项绿色化学原则:(a)由于使用水作为溶剂和氢源,原子经济性高;(b)无需均相金属催化剂;(c)反应条件温和;(d)副产物量少,抑制了废物产生;(e)使用安全的乙醇共溶剂。此外,该体系与炔烃和烯烃化合物反应的能力提高了这一过程的实际效率。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a314/9675855/1ce3b01c4ccb/41598_2022_23777_Fig1_HTML.jpg

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