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硫修饰壳聚糖衍生的 N,S 共掺杂碳作为一种双功能材料,用于过硫酸盐吸附和催化降解磺胺甲恶唑。

Sulfur-modified chitosan derived N,S-co-doped carbon as a bifunctional material for adsorption and catalytic degradation sulfamethoxazole by persulfate.

机构信息

Research Center for Eco-environmental Engineering, Dongguan University of Technology, Dongguan 523830, PR China.

Research Center for Eco-environmental Engineering, Dongguan University of Technology, Dongguan 523830, PR China.

出版信息

J Hazard Mater. 2022 Feb 15;424(Pt A):127270. doi: 10.1016/j.jhazmat.2021.127270. Epub 2021 Sep 20.

DOI:10.1016/j.jhazmat.2021.127270
PMID:34879545
Abstract

N,S-co-doped carbons were synthesized through the calcination of sulfur-modified chitosan for the first time, and utilized as persulfate activators for sulfamethoxazole (SMX) remediation in water. The chitosan and sulfonyl chloride underwent one-step sulfonylation reaction to generate S-modified chitosan. The catalyst NSC-3 showed both excellent adsorption and catalytic oxidation efficiency, corresponding 98.62% removal and 81.34% mineralization rate within 90 min. The rate constant (k) was up to 0.0578 min, with 75.60-folders higher than that of sulfur-free catalyst NC (7.6580 ×10 min). The synergy of N and S contributed to the improvement of removal efficiency. The adsorption and oxidation performance were highly depended on the S/N atomic ratio. At the S/N ratio of 0.18, the maximum adsorption and oxidation capability were obtained. The NSC-3/PS system exhibited outstanding adaptability at the wide pH range from 3.07 to 9.28, while the inhibitory effect occurred at strong basic conditions (pH = 11.01). The thiophene sulfur and structural defects were identified as the catalytic sites in activating PS. Both radical and non-radical pathways were responsible for degradation process, where O played a major role, SOexerted a minor contribution, and O acts as the precursor for the production of O. Another source of O was assigned to the activation of PS by structure defects. This work indicates that N,S-co-doped carbon at an optimal S/N atomic ratio effectively catalyzes persulfate, and provides an innovative method to construct bifunctional carbon materials of adsorption and oxidization.

摘要

首次通过热解硫改性壳聚糖合成了 N,S 共掺杂碳,并将其用作过硫酸盐活化剂以去除水中的磺胺甲恶唑(SMX)。壳聚糖和磺酰氯进行了一步磺化反应,生成了 S 改性壳聚糖。催化剂 NSC-3 具有出色的吸附和催化氧化效率,在 90 分钟内去除率达到 98.62%,矿化率达到 81.34%。速率常数(k)高达 0.0578 min,比无硫催化剂 NC(7.6580×10 min)高 75.60 倍。N 和 S 的协同作用提高了去除效率。吸附和氧化性能高度依赖于 S/N 原子比。在 S/N 原子比为 0.18 时,获得了最大的吸附和氧化能力。NSC-3/PS 体系在 3.07 至 9.28 的宽 pH 范围内表现出出色的适应性,而在强碱性条件(pH = 11.01)下会产生抑制作用。噻吩硫和结构缺陷被确定为激活 PS 的催化位点。自由基和非自由基途径都参与了降解过程,其中 O 起主要作用,SO 贡献较小,O 作为 O 的前体生成。O 的另一个来源归因于结构缺陷对过硫酸盐的活化。这项工作表明,在最佳 S/N 原子比下,N,S 共掺杂碳可有效催化过硫酸盐,并为构建吸附和氧化的双功能碳材料提供了一种创新方法。

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