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负载金纳米颗粒的富土纳米管作为催化剂用于吩噻嗪染料的降解和 4-(4-硝基苯基)吗啉的还原

Gold nanoparticle-decorated earth-abundant clay nanotubes as catalyst for the degradation of phenothiazine dyes and reduction of 4-(4-nitrophenyl)morpholine.

机构信息

Advanced Ceramics and Nanotechnology Laboratory, Department of Materials Engineering, Universidad de Concepción, Concepción, Chile.

Departamento de Físico-Química, Facultad de Ciencias Químicas, Universidad de Concepción, Edmundo Larenas 129, Casilla 160-C, Concepción, Chile.

出版信息

Environ Sci Pollut Res Int. 2023 Dec;30(60):124447-124458. doi: 10.1007/s11356-022-19523-1. Epub 2022 Mar 16.

Abstract

In the present work, halloysite nanotubes modified with gold nanoparticles (AuNPs-HNT) are successfully prepared by wet chemical method for the catalytic degradation of phenothiazine dyes (azure B (AZB) and toluidine blue O (TBO)) and also cleaner reduction of 4-(4-nitrophenyl)morpholine (4NM) in the sodium borohydride (NaBH) media. The catalyst is formulated by modifying the HNT support with a 0.964% metal loading using the HNT supports modified with 3-aminopropyl-trimethoxysilane (APTMS) coupling agent to facilitate the anchoring sites to trap the AuNPs and to prevent their agglomeration/aggregation. The AuNPs-HNT catalyst is investigated for structural and morphological characterization to get insights about the formation of the catalyst for the effective catalytic reduction of dyes and 4NM. The microscopic studies demonstrate that AuNPs (2.75 nm) are decorated on the outer surface of HNT. The as-prepared AuNPs-HNT catalyst demonstrates AZB and TBO dye degradation efficiency up to 96% in 10 and 11 min, respectively, and catalytic reduction of 4NM to 4-morpholinoaniline (MAN) is achieved up to 97% in 11 min, in the presence of NaBH without the formation of any by-products. The pseudo-first-order rate constant (K) value of the AuNPs-HNT catalyst for AZB, TBO, and 4NM were calculated to be 0.0078, 0.0055, and 0.0066 s, respectively. Moreover, the synthesized catalyst shows an excellent reusability with stable catalytic reduction for 7 successive cycles for both the dyes and 4NM. A plausible mechanism for the catalytic dye degradation and reduction of 4NM by AuNPs-HNT catalyst is proposed as well. The obtained results clearly indicate the potential of AuNPs-HNT as an efficient catalyst for the removal of dye contaminants from the aquatic environments and cleaner reduction of 4NM to MAN, insinuating future pharmaceutical applications.

摘要

在本工作中,通过湿化学法成功制备了金纳米粒子(AuNPs-HNT)修饰的埃洛石纳米管,用于催化降解吩噻嗪染料(天青 B(AZB)和甲苯胺蓝 O(TBO)),并在硼氢化钠(NaBH)介质中更清洁地还原 4-(4-硝基苯基)吗啉(4NM)。该催化剂通过使用 3-氨丙基三甲氧基硅烷(APTMS)偶联剂修饰 HNT 载体,将金属负载量提高到 0.964%,从而对 HNT 载体进行了配方设计,以促进固定在其上的锚定位点来捕获 AuNPs 并防止其聚集/团聚。对 AuNPs-HNT 催化剂进行了结构和形态特征研究,以深入了解催化剂的形成,从而实现对染料和 4NM 的有效催化还原。微观研究表明,AuNPs(2.75nm)修饰在 HNT 的外表面上。所制备的 AuNPs-HNT 催化剂在存在 NaBH 的情况下,分别在 10 和 11min 内实现了高达 96%的 AZB 和 TBO 染料降解效率,以及高达 97%的 4NM 催化还原为 4-吗啉苯胺(MAN),而没有形成任何副产物。AuNPs-HNT 催化剂对 AZB、TBO 和 4NM 的表观一级速率常数(K)值分别计算为 0.0078、0.0055 和 0.0066s。此外,该合成催化剂表现出出色的可重复使用性,在 7 个连续循环中对染料和 4NM 的催化还原均稳定。还提出了 AuNPs-HNT 催化剂催化降解染料和还原 4NM 的可能机理。所得结果清楚地表明,AuNPs-HNT 作为一种从水环境中去除染料污染物和更清洁地还原 4NM 为 MAN 的有效催化剂具有很大的潜力,暗示着未来在制药方面的应用。

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