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基于氧化钒催化剂的预占据锚定策略促进 C-Cl 键活化用于 NO 和含氯芳烃的多污染物控制。

Promoting C-Cl Bond Activation via a Preoccupied Anchoring Strategy on Vanadia-Based Catalysts for Multi-Pollutant Control of NO and Chlorinated Aromatics.

机构信息

State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, China.

School of Environmental Science and Engineering, Yancheng Institute of Technology, Yancheng 224051, China.

出版信息

Environ Sci Technol. 2024 Sep 17;58(37):16357-16367. doi: 10.1021/acs.est.4c06220. Epub 2024 Sep 2.

DOI:10.1021/acs.est.4c06220
PMID:39219475
Abstract

Regulating vanadia-based oxides has been widely utilized for fabricating effective difunctional catalysts for the simultaneous elimination of NO and chlorobenzene (CB). However, the notorious accumulation of polychlorinated species and excessively strong NH adsorption on the catalysts lead to the deterioration of multipollutant control (MPC) activity. Herein, protonated sulfate (-HSO) supported on vanadium-titanium catalysts via a preoccupied anchoring strategy are designed to prevent polychlorinated species and alleviate NH adsorption for the multipollutant control. The obtained catalysts with -HSO modification achieve an excellent NO and CB conversion with turnover frequency values of ∼ 3.63 and 17.7 times higher than those of the pristine, respectively. The protonated sulfate promotes the formation of polymeric vanadyl with a higher chemical state and d-band center of V. The modulated catalysts not only substantially alleviate the competitive adsorption of multipollutant via the "V 3d-O 2p-S 3p" network, but also distinctly strengthen the Brønsted acid sites. Besides, the introduced proton donor of the -HSO connecting polymeric structure could markedly reduce the reaction barrier of breaking the C-Cl bond. This work paves an advanced way for low-loading vanadium SCR catalysts to achieve highly efficient NO and CB oxidation at a low temperature.

摘要

调控基于钒的氧化物已被广泛用于制备有效的双功能催化剂,以同时消除 NO 和氯苯 (CB)。然而,催化剂上多氯物种的严重积累和 NH 的过度强吸附导致多污染物控制 (MPC) 活性恶化。本文通过预占据的锚定策略,将负载在钒钛催化剂上的质子化硫酸盐 (-HSO) 设计为防止多氯物种的积累和减轻 NH 的吸附,从而用于多污染物控制。具有 -HSO 改性的获得的催化剂具有优异的 NO 和 CB 转化率,其转化频率值分别比原始催化剂高约 3.63 和 17.7 倍。质子化硫酸盐促进了聚合氧钒的形成,具有更高的化学状态和 V 的 d 带中心。调制后的催化剂不仅通过“V 3d-O 2p-S 3p”网络大大减轻了多污染物的竞争吸附,而且明显增强了 Brønsted 酸位。此外,-HSO 连接的聚合物结构中引入的质子供体可以显著降低断裂 C-Cl 键的反应势垒。这项工作为低温下实现高效的 NO 和 CB 氧化,提供了一种低负载量钒 SCR 催化剂的先进方法。

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