催化学报

催化学报 ›› 2018, Vol. 39 ›› Issue (11): 1842-1853.DOI: 10.1016/S1872-2067(18)63114-6

• 论文 • 上一篇    下一篇

一步法制备铁氧化物/氮改性氧化石墨/碳纳米管异质结及其用于催化活化过一硫酸氢钾降解亚甲基蓝模型染料

赵鑫a, 安庆大a, 肖作毅a, 翟尚儒a, 施展b   

  1. a 大连工业大学轻工与化学工程学院, 辽宁大连 116034;
    b 吉林大学化学学院无机合成和制备化学国家重点实验室, 吉林长春 130012
  • 收稿日期:2018-04-13 修回日期:2018-05-28 出版日期:2018-11-18 发布日期:2018-09-01
  • 通讯作者: 安庆大, 翟尚儒
  • 基金资助:

    国家自然科学基金（21676039）；辽宁省高校创新人才基金（LR2017045）；吉林大学无机合成和制备化学国家重点实验室（2016–04）.

One-step preparation of FexOy/N-GN/CNTs heterojunctions as a peroxymonosulfate activator for relatively highly-efficient methylene blue degradation

Xin Zhaoa, Qing-Da Ana, Zuo-Yi Xiaoa, Shang-Ru Zhaia, Zhan Shib   

  1. a Faculty of Light Industry and Chemical Engineering, Dalian Polytechnic University, Dalian 116034, Liaoning, China;
    b State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, Jilin, China
  • Received:2018-04-13 Revised:2018-05-28 Online:2018-11-18 Published:2018-09-01
  • Contact: 10.1016/S1872-2067(18)63114-6
  • Supported by:

    This work was supported by the National Natural Science Foun-dation of China (21676039), Innovative talents in Liaoning universities and colleges (LR2017045), and the Opening Foundation of State Key Laboratory of Inorganic Synthesis and Preparative Chemistry of Jilin University (2016-04).

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摘要：

随着较差的生物相容性和更高毒性有机染料的应用，如酚类化合物和抗生素，水污染和食品污染变得极其严重.这不仅危害人类健康，而且严重污染自然环境.过硫酸盐去污技术利用自由基活化降解过程，成为处理一系列污染物非常有效的方法；然而设计具有多功能性的高性能催化剂仍然面临着巨大的挑战.因此，本文借鉴铁基材料、氮改性石墨和碳纳米管独特的物化性质，以尿素、铁盐、氧化石墨、碳纳米管为原材料，通过一步水热法成功制备了三维多功能铁氧化物/氮改性氧化石墨/碳纳米管异质结，用作活化过一硫酸氢钾复合盐以降解有机模型污染物亚甲基甲蓝（MB），研究了高级氧化法（AOPs）作用机理和优化反应条件.XRD、红外光谱、SEM和XPS结果表明，铁氧化物通过物理静电作用力和化学键结合力已经被牢牢固定在了氮修饰的氧化石墨结构框架内.当加入了碳纳米管之后，它会与石墨形成类似于互穿聚合物网络的结构，从而具有三维材料的优点，且提升电子转移电导率，使得催化剂的结构和性能有了很大的改善.此外，优化了降解系统、PMS负载量、初始有机污染物浓度和催化剂用量等因素.结果表明，处于催化剂/PMS系统时，亚甲基蓝可以在12min之内有效地完全降解，可归结于碳、氮以及主要活性物质铁氧化物之间的协同作用.基于数据拟合分析，污染物氧化降解系统与拟一阶动力学相符合，其速率常数约为0.33min-1.淬灭实验证明，硫酸根自由基和羟基自由基是主要的反应活性物种.这种同时富含铁/氮分级的多孔碳骨架异质结物质不仅可用作过渡金属催化剂，而且为制备其他异质结提供参考，以用于超级电容器、储能材料、电催化剂等领域.

关键词: 异质结, 有机污染物降解, 氮掺杂石墨烯, 协同作用

Abstract:

Persulfate decontamination technologies utilizing radical-driven processes are powerful tools for the treatment of a broad range of impurities. However, the design of high-performance catalytic activators with multi-functionality remains a great challenge. Therefore, in this study, three-dimensional multifunctional FexOy/N-GN/CNTs (N-GN:nitrogen-doped graphene, CNTs:carbon nanotubes) heterojunctions, which can be employed as microwave absorbers and catalysts, were synthesized via a solvothermal method and applied to activate peroxymonosulfate for the degradation of methylene blue (MB). X-ray diffraction (XRD), Fourier transform infrared spectrometer (FTIR), scanning electron microscope (SEM), and X-ray photoelectron microscopy (XPS) analyses revealed that the FexOy were anchored in-situ onto the N-GN network. Using MB as the model organic dye, various factors, such as degradation systems, PMS loading, initial organic pollutant concentration, and catalyst dosage were optimized. The results revealed that the remarkable efficiency was attributable to the synergistic effects of carbon, nitrogen, and iron-based species. The oxidation system corresponded to the pseudo-first-order kinetic with a k value of~0.33 min-1. It was demonstrated that both SO4·- and OH· were the predominant reactive species through quenching experiments. Because these heterojunctions were employed as microwave absorbers and have a semiconductor-like texture, the Fe/N co-rich hierarchical porous carbon skeleton favored electron transport and storage. These heterojunctions increase the options for transitional metal catalysts and highlights the importance of designing other heterojunctions for specific applications, such as supercapacitors, energy storage, CO2 capture, and oxygen reduction electrocatalysts.

Key words: Heterojunctions, Organic pollutant degradation, Nitrogen-doped graphene, Synergistic collaboration