Light-driven ultrafast dual C–C cleavage and coupling of dihydroxyacetone into high-purity carbon monoxide and ethylene glycol†

IF 11.3 1区 化学 Q1 CHEMISTRY, PHYSICAL
ACS Catalysis Pub Date : 2024-09-19 DOI:10.1039/D4GC04180A
Fanhao Kong, Hongru Zhou, Zhiwei Chen, Zhaolin Dou and Min Wang
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Abstract

Bulk chemicals, such as carbon monoxide (CO) and ethylene glycol (EG), derived from biomass feedstocks instead of traditional fossil fuels present a renewable and sustainable energy alternative. However, their direct production under ambient conditions with high purity is challenging. Herein, we report a distinctive photochemical process to produce CO together with EG through the ultrafast C–C cleavage of dihydroxyacetone induced by ultraviolet illumination at ambient temperature and pressure in water. The obtained CO yield was nearly 98% with a high purity above 99.9%, and the EG yield was nearly 80%. The two hydroxyls at the alpha carbons of dihydroxyacetone reduced the energy barriers of photoexcitation and the radical reaction, accounting for fast C–C cleavage to produce CO and EG. A home-built flow reactor achieved the continuous production of CO and EG over 1000 h and maintained efficient operation for 100 h in the sunlight-electricity-ultraviolet light mode. Benefitting from the fast reaction rate and high-purity gas generation, a safe, laboratory-scale, portable, ready-to-use CO generator was designed and assembled. The maximum CO production rate of the CO generator reached 30 mL min−1, and CO purity reached over 99% for 25 L.

Abstract Image

光驱动的超快双 C-C 裂解以及将二羟基丙酮偶联为高纯度一氧化碳和乙二醇†的过程
一氧化碳(CO)和乙二醇(EG)等大宗化学品来自生物质原料而非传统化石燃料,是一种可再生和可持续的能源替代品。然而,要在环境条件下直接生产出高纯度的这两种物质却极具挑战性。在此,我们报告了一种独特的光化学工艺,即在环境温度和压力下,通过紫外线照射诱导二羟基丙酮在水中发生超快的 C-C 裂解,从而产生一氧化碳和乙二醇。获得的 CO 收率接近 98%,纯度高于 99.9%,EG 收率接近 80%。二羟基丙酮α碳上的两个羟基降低了光激发和自由基反应的能量障碍,从而使 C-C 快速裂解,生成 CO 和 EG。自制的流动反应器可在 1000 小时内连续生产 CO 和 EG,并在日光-电-紫外光模式下保持高效运行 100 小时。得益于快速的反应速率和高纯度气体的生成,我们设计并组装了一个安全的、实验室规模的、便携式的、可直接使用的 CO 发生器。一氧化碳发生器的最大一氧化碳生成速率达到 30 mL min-1,25 L 的一氧化碳纯度达到 99% 以上。
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来源期刊
ACS Catalysis
ACS Catalysis CHEMISTRY, PHYSICAL-
CiteScore
20.80
自引率
6.20%
发文量
1253
审稿时长
1.5 months
期刊介绍: ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.
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