College of Resources and Environmental Engineering, Guizhou University, Guiyang 550025, China.
Research Center for Carbon-Neutral Environmental & Energy Technology, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 611731, China.
Environ Sci Technol. 2023 Aug 29;57(34):12890-12900. doi: 10.1021/acs.est.3c03396. Epub 2023 Aug 17.
An appealing strategy for ensuring environmental benefits of the photocatalytic NO oxidation reaction is to convert NO into NO instead of NO, yet the selectivity of products remains challenging. Here, such a scenario could be realized by tailoring the exposure of Lewis acid sites on the surface of ZrO, aiming to precisely regulate the ROS evolution process for the selective oxidation of NO into NO. As evidenced by highly combined experimental characterizations and density functional theory (DFT) simulations, Lewis acid sites serving as electron acceptors could induce itinerant electron redistribution, charge-carrier transfer, and further oxidation of •O, which promotes the oriented formation of O. As a result, monoclinic ZrO with more Lewis acid sites exhibited an outstanding NO conversion efficiency (56.33%) and extremely low NO selectivity (5.04%). The ROS-based reaction process and promotion mechanism of photocatalytic performance have been revealed on the basis of ESR analysis, ROS-quenching experiments, and ROS-quenching DRIFTS. This work could provide a critical view toward oriented ROS formation and advance a unique mechanism of selective NO oxidation into NO.
确保光催化 NO 氧化反应环境效益的一种有吸引力的策略是将 NO 转化为 NO，而不是 NO，但产物的选择性仍然具有挑战性。在这里，可以通过调整 ZrO 表面路易斯酸位的暴露来实现这种情况，旨在精确调节 ROS 演化过程，从而选择性地将 NO 氧化为 NO。实验和密度泛函理论（DFT）模拟的综合结果表明，作为电子受体的路易斯酸位可以诱导巡游电子重新分布、电荷载流子转移和进一步氧化•O，从而促进 O 的定向形成。结果表明，具有更多路易斯酸位的单斜 ZrO 表现出优异的 NO 转化率（56.33%）和极低的 NO 选择性（5.04%）。基于 ESR 分析、ROS 猝灭实验和 ROS 猝灭 DRIFTS，揭示了基于 ROS 的反应过程和光催化性能的促进机制。这项工作为定向 ROS 形成提供了一个重要的视角，并推进了一种独特的选择性将 NO 氧化为 NO 的机制。
