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荧光 N 掺杂碳点/水凝胶复合材料的合成与应用:揭示 Cr(VI)吸附中的离子物种转化和荧光猝灭机制。

Synthesis and application of fluorescent N-doped carbon dots/hydrogel composite for Cr(VI) adsorption: Uncovering the ion species transformation and fluorescent quenching mechanism.

机构信息

Synchrotron Light Research Institute, Nakhon Ratchasima, 30000, Thailand.

Department of Chemistry, Faculty of Science, Srinakharinwirot University, Bangkok, 10110, Thailand.

出版信息

Environ Geochem Health. 2023 Jul;45(7):5293-5309. doi: 10.1007/s10653-023-01576-x. Epub 2023 May 2.

Abstract

A fluorescent composite material fabricated from nitrogen-doped carbon dots with polyvinyl alcohol (PVA)/polyvinylpyrrolidone (PVP)/citric acid (CA) hydrogel was synthesized using a microwave-assisted hydrothermal method. The composite was used as a metal ion sensor and adsorbent to remove chromium (Cr(VI)) from water. The chemical structure and Cr(VI) removal performance of the fluorescent composite films were also characterized. Fluorescent quenching upon Cr(VI) adsorption showed that Cr(VI) binding was attributed to the N-doped carbon dots. The results were confirmed by several analytical techniques, including X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and X-ray absorption spectroscopy (XAS). The mechanism of Cr(VI) removal from water by the fluorescent composite film was based on the adsorption and subsequent reduction of N-doped carbon dots within the 3D porous composite film. XPS measurements showed that 53.2% Cr(III) and 46.8% Cr(VI) were present on the composite surface after Cr(VI) adsorption. Moreover, XAS revealed a change in the oxidation state of Cr(VI) to Cr(III) after adsorption and in the Cr-O bond length (1.686 Å to 2.284 Å) after reduction. The Cr(VI) adsorption capacity of the composite film was 4.90 mg g at pH 4 and fit the pseudo-second-order kinetic and Freundlich models. The results of this study could be used as a platform to further apply CDs/HD composites to remove Cr(VI) from water sources.

摘要

采用微波辅助水热法合成了一种以氮掺杂碳点(N-doped carbon dots,N-CDs)为荧光探针、以聚乙烯醇(polyvinyl alcohol,PVA)/聚乙烯吡咯烷酮(polyvinylpyrrolidone,PVP)/柠檬酸(citric acid,CA)水凝胶为基质的荧光复合材料。该复合材料被用作金属离子传感器和吸附剂,以去除水中的铬(Cr(VI))。荧光复合薄膜的化学结构和 Cr(VI)去除性能也得到了表征。Cr(VI)吸附导致荧光猝灭表明,Cr(VI)的结合归因于 N-CDs。这一结果得到了几种分析技术的证实,包括 X 射线光电子能谱(X-ray photoelectron spectroscopy,XPS)、傅里叶变换红外光谱(Fourier transform infrared spectroscopy,FTIR)和 X 射线吸收光谱(X-ray absorption spectroscopy,XAS)。荧光复合薄膜从水中去除 Cr(VI)的机制基于 3D 多孔复合薄膜内 N-CDs 的吸附和随后的还原。XPS 测量表明,Cr(VI)吸附后,复合表面有 53.2%的 Cr(III)和 46.8%的 Cr(VI)。此外,XAS 揭示了吸附后 Cr(VI)的氧化态向 Cr(III)的变化以及 Cr-O 键长(从 1.686 Å 到 2.284 Å)的变化。复合薄膜对 Cr(VI)的吸附容量在 pH 4 时为 4.90 mg g,符合准二级动力学和 Freundlich 模型。本研究结果可作为进一步将 CDs/HD 复合材料应用于从水源中去除 Cr(VI)的平台。

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