可见光驱动的温和高效的光催化耦合醇氧化脱氢和CO2还原,Green Chemistry

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可见光驱动的温和高效的光催化耦合醇氧化脱氢和CO2还原
Green Chemistry ( IF 9.3 ) Pub Date : 2022-03-18 , DOI: 10.1039/d1gc04459a
Jiekun Zhu ₁ , Zheng Yi ₁ , Mingyu Luo ₁ , Youer Deng ₁ , Jialuo She ₁ , Yachun Liu ₁ , Chao Zhang ₁ , Bo Yang ₁ , Senpei Tang ₂ , Zaihui Fu ₁

Affiliation

基于醇氧化脱氢（ODH）和CO ₂还原的先进耦合转化技术是解决当前能源和环境危机的潜在策略，对CO ₂向燃料的升级转化具有重要意义。该工作揭示了Al ³⁺物种掺杂的十钨酸盐（Al-DTs）可以在可见光和非常温和的条件下有效地催化各种脂肪族和芳香族伯/仲醇与MeCN中CO ₂的耦合转化，以及还原效率CO ₂的含量取决于 Al ^{3+的掺杂水平}Al-DTs中的物种和醇的ODH反应性。连续光照12 h后，最好的4% Al-DT在光催化耦合转化中可提供437 μmol苯乙酮作为ODH产物和218 μmol CO ₂还原产物（甲酸和甲醇），转换频率为1.82 h ^-1 α-苯乙醇与 CO ₂。此外，从光催化耦合反应中检测到痕量的 CO。_{使用重氧水 (H 2}¹⁸ O) 的紫外可见光谱和同位素示踪测试支持由醇的光催化 ODH 产生的双还原蓝色 H ₂ DT 物质变成其缺氧形式 ([DT ²⁻ ] _v )通过分子内脱水或晶格氧转移，后者在掺杂的Al ³⁺物质的帮助下，可以通过多步质子耦合电子转移（PET）途径有效地将CO ₂还原为燃料。

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Mild and efficient photocatalytic coupled alcohol oxidative dehydrogenation and CO2 reduction driven by visible light

The advanced coupled conversion technique based on the oxidative dehydrogenation (ODH) of alcohols and the reduction of CO₂ is a potential strategy to solve the current energy and environmental crisis, and is of great significance for the upgrading conversion of CO₂ to fuels. This work discloses that the Al³⁺ species-doped decatungstates (Al-DTs) can efficiently catalyze the coupled conversion of various aliphatic and aromatic primary/secondary alcohols with CO₂ in MeCN under visible light illumination and very mild conditions, and the reductive efficiency of CO₂ depends on the doping levels of Al³⁺ species in Al-DTs and the ODH reactivity of alcohols. After continuously illuminating for 12 h, the best, 4% Al-DT can provide 437 μmol acetophenone as the ODH product and 218 μmol CO₂ reduction products (formic acid and methanol) with 1.82 h⁻¹ turnover frequency in the photocatalytic coupled conversion of α-phenylethanol with CO₂. Also, a trace amount of CO is detected from the photocatalytic coupled reactions. UV-vis spectra and isotope tracing tests using heavy oxygen water (H₂¹⁸O) support that the doubly-reduced blue H₂DT species generated from the photocatalytic ODH of alcohols turns into its oxygen-deficient form ([DT²⁻]_v) via an intra-molecular dehydration or lattice oxygen transfer and the latter, with the help of doped Al³⁺ species, may efficiently reduce CO₂ to fuels via the multi-step proton-coupled electron transfer (PET) pathway.

更新日期：2022-03-18

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