Electrocatalytic hydrogenation of the formyl group and heteroaromatic ring in furfural on activated carbon cloth-supported ruthenium†

Meheryar R. Kasad, James E. Jackson and Christopher M. Saffron
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Abstract

Electrocatalytic hydrogenation (ECH) was explored as a mild technique (≤50 °C under atmospheric pressure) to produce valuable products from furfural, a promising biomass-derived platform chemical. In situ hydrogen equivalents made by water splitting were used to reduce the formyl group and saturate the heteroaromatic ring of furfural on an activated carbon cloth-supported ruthenium electrocatalyst. A systematic study was conducted to understand the relationship between the reaction conditions and the products. The factors analyzed include catholyte solution organic co-solvent content, catholyte solution acid content, and temperature. Acidity of the catholyte solution had the most significant effect on the yield of tetrahydrofurfuryl alcohol (THFA). The highest THFA yield was obtained in mildly acidic catholyte solutions (0.02 M HCl and 0.002 M HCl–0.02 M NaCl). The low carbon mole balance closure in the experiments was attributed to the side reactions of the reactants, intermediates, and products. The effects of current density on faradaic efficiency and of the functional groups attached to the furan ring on the formation of saturated heterocyclic products were also explored.

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在活性碳布支撑的钌上对糠醛中的甲酰基和杂芳环进行电催化加氢反应
电催化加氢(ECH)作为一种温和的技术(常压下温度≤50 °C),被用来从糠醛(一种有前景的生物质衍生平台化学品)中生产有价值的产品。利用水分裂产生的原位氢当量,在活性炭布支撑的钌电催化剂上还原糠醛的甲酰基并使其杂芳环饱和。为了解反应条件与产物之间的关系,进行了系统研究。分析的因素包括阴溶液中有机助溶剂的含量、阴溶液中酸的含量和温度。电解质溶液的酸度对四氢呋喃甲醇(THFA)的产率影响最大。在弱酸性的阴溶液(0.02 M HCl 和 0.002 M HCl-0.02 M NaCl)中,四氢糠醇的产量最高。实验中出现的低碳分子平衡闭合是由于反应物、中间产物和产物的副反应造成的。此外,还探讨了电流密度对法拉第效率的影响,以及呋喃环上的官能团对饱和杂环产物形成的影响。
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