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光氧化还原促进的缺陷 ZnInS 上二氢异喹啉和 H2O 的共产生。

Photoredox-Promoted Co-Production of Dihydroisoquinoline and H O over Defective Zn In S.

机构信息

Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062, China.

Suzhou NATA Opto-Electronic Materials Ltd, Suzhou, 215127, China.

出版信息

Adv Mater. 2023 Mar;35(10):e2210110. doi: 10.1002/adma.202210110. Epub 2023 Jan 13.

Abstract

One of the most sustainable and promising approaches for hydrogen peroxide (H O ) production in a low-cost and environment-friendly way is photosynthesis, which, however, suffers from poor carrier utilization and low H O productivity. The addition of proton donors such as isopropanol or ethanol can increase H O production, which, unfortunately, will inevitably elevate the entire cost while wasting the oxidizing power of holes (h ). Herein, the tetrahydroisoquinolines (THIQs) is employed as a distinctive proton donor for the thermodynamically feasible and selective semi-dehydrogenation reaction to highly valuable dihydroisoquinolines (DHIQs), and meanwhile, to couple with and promote H O generation in one photoredox reaction under the photocatalysis by dual-functional Zn In S photocatalyst. Surprisingly, the suitably defective Zn In S offers an excellent and near-stoichiometric co-production performance of H O and DHIQs at unprecedentedly high rates of 66.4 and 62.1 mmol h g under visible light (λ ≥ 400 nm), respectively, which outperforms all the previously available reports even though sacrificial agents were employed in those reports. Additionally, photocatalytic redox reaction mechanism demonstrates that H O can be generated through multiple pathways, highlighting the synergistic effect among ROS (·O and O ), h and proton donor, which has been ignored in previous studies.

摘要

一种低成本、环保的制备过氧化氢(H2O2)的最可持续和最有前途的方法之一是光合作用,但它存在载体利用率低和 H2O2 产率低的问题。添加异丙醇或乙醇等质子供体可以提高 H2O2 的产量,但不幸的是,这将不可避免地提高整个成本,同时浪费空穴(h+)的氧化能力。在此,四氢异喹啉(THIQs)被用作独特的质子供体,用于热力学上可行且选择性的半脱氢反应,生成高价值的二氢异喹啉(DHIQs),同时,在双功能 ZnInS 光催化剂的光催化下,在一个光氧化还原反应中与 H2O2 生成相耦合并促进其生成。令人惊讶的是,适当缺陷的 ZnInS 在前所未有的高速率下,以 66.4 和 62.1 mmol h g 的速率分别提供了 H2O2 和 DHIQs 的极好的近乎化学计量的共生产性能,尽管在那些报道中使用了牺牲剂,但仍优于所有以前的报道。此外,光催化氧化还原反应机制表明,H2O2 可以通过多种途径产生,突出了 ROS(·O2- 和 1O2)、h+和质子供体之间的协同效应,这在以前的研究中被忽视了。

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