二氧化硅负载高分散纳米零价铁:硫脲诱导合成及其Ni(Ⅱ)吸附特性与机理研究

Thiourea-mediated synthesis of highly dispersed silica-supported nano zero-valent iron: adsorption performance and mechanistic understanding for Ni(Ⅱ) removal

摘要

以氨基化二氧化硅(NH₂-SiO₂)为载体,以硫脲作为结构控制剂,采用液相还原法合成了具有高分散Fe⁰负载的WD-Fe⁰@NH₂-SiO₂复合材料用于水体重金属去除.借助扫描电镜(SEM)、元素能谱分析(EDS)、X射线衍射(XRD)等表征手段对WD-Fe⁰@NH₂-SiO₂进行了结构组成表征,分析了NH₂-SiO₂负载Fe⁰过程中,硫脲的缓释作用对Fe⁰尺寸的影响.同时系统研究了投加量、初始质量浓度、反应时间等因素对Ni(Ⅱ)去除率的影响.吸附实验证实,WD-Fe⁰@NH₂-SiO₂对Ni(Ⅱ)的吸附容量和去除率分别达到362mg/g和90.5%,与未采用硫脲辅助制备的样品相比得到了较大幅提升(308mg/g和76.9%).最后,利用X射线光电子能谱(XPS)分析反应前后样品中镍元素价态演变,结合吸附动力学模拟,证实WD-Fe⁰@NH₂-SiO₂对Ni(Ⅱ)的吸附为化学吸附主导的过程.

Abstract

A well-dispersed Fe ⁰-loaded composite material, WD-Fe ⁰@NH ₂-SiO ₂, was successfully synthesized via the liquid-phase reduction method using NH ₂-SiO ₂ as a carrier and thiourea as a structure-directing agent for efficient removal of heavy metals from aqueous solutions. The structure and composition of WD-Fe ⁰@NH ₂-SiO ₂ were characterized by scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), and X-ray diffraction (XRD). The influence of thiourea's slow-release behavior on controlling the particle size of Fe ⁰ during immobilization onto NH ₂-SiO ₂ was systematically investigated. A systematic investigation was conducted to evaluate the effects of dosage, initial concentration, and reaction time on the Ni(Ⅱ) removal efficiency. The adsorption experiments demonstrated that the adsorption capacity and removal efficiency of WD-Fe ⁰@NH ₂-SiO ₂ for Ni(Ⅱ) were 362 mg/g and 90.5%, respectively, representing a significant improvement compared with those prepared without thiourea (308 mg/g and 76.9%). Finally, X-ray photoelectron spectroscopy (XPS) was employed to investigate the valence state evolution of nickel in the samples before and after adsorption. Integrated with kinetic modeling, the results confirm that Ni(Ⅱ) adsorption onto WD-Fe ⁰@NH ₂-SiO ₂ proceeds predominantly via chemisorption.

关键词

纳米零价铁 / 氨基化二氧化硅 / 硫脲 / Ni(Ⅱ)

Key words

nano zero-valent iron / amino-functionalized silica / thiourea / Ni(Ⅱ)

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基金资助

国家自然科学基金(22206046)

河南省自然科学基金(262300420243)

河南省自然科学基金(242300421645)

河南省线缆先进材料与智能制造重点实验室开放课题(CAMIM2025008)