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