基于MOFs的改性生物焦复合吸附剂脱碳特性及机理研究

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摘要为进一步探究高性能的金属有机骨架材料MOFs基CO₂复合吸附剂,首先通过掺杂Ce、Cu、Mn、Co多元金属对生物焦进行改性修饰,在探究最优制备方法的基础上,基于生物焦及Mg-MOF-74共同含有不饱和金属位点和含氧官能团的基础特性进行结构设计,制备Mg-MOF-74改性生物焦复合吸附剂.在获得复合吸附剂吸附特性的基础上,探究了负载多元金属、MOFs材料以及生物焦之间的耦合及协同作用机制,并通过多种表征手段研究了样品的孔隙结构、表面官能团与晶态结构等微观特性,同时结合吸附动力学、吸附热力学以及元素价态变化揭示了复合吸附剂的脱碳机理.研究发现,溶胶凝胶法利于制备改性生物焦;负载的多元金属以金属氧化物形式存在于改性生物焦中,氧化边缘晶格缺陷,为改性生物焦引入含氧官能团,且所获得的10%Fe+4%Ce+2%Cu样品效果最优,其吸附量为1.53mmol/g;复合吸附剂对CO₂的吸附是物理吸附与化学吸附共同作用的结果,MOFs材料优化了复合吸附剂的孔隙结构,改性生物焦因其石墨微晶结构与掺杂多元金属修饰而在表面产生电子转移,发生了化学吸附,即二者的复合在脱碳过程中发挥了相互促进与协同的作用,使复合吸附剂吸附性能得到明显提升,对于前驱体共热解法制备的样品相较于改性生物焦和Mg-MOF-74分别提升了230.7%和75.7%.

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	王晨星
	贾里
	柳晴瑞
	王玉莹
	程鹏
	乔晓磊
	聂浩田
	金燕

关键词 ：生物焦, MOFs, 复合吸附剂, 改性修饰, 吸附机理

Abstract：In order to further explore high performance MOFs-based CO₂ composite adsorbents, firstly, biochar was modified by doping Ce, Cu, Mn, and Co multi-metals, and on the basis of exploring the optimal preparation method, Mg-MOF-74modified biochar composite adsorbents were prepared by structural design based on the basic properties that biochar and Mg-MOF-74 contain unsaturated metal sites and oxygen-containing functional groups together. On the basis of obtaining the composite adsorption properties of Mg-MOF-74 modified biochar, the coupling and synergistic mechanisms among the loaded multi-metals, MOFs materials and biochar were investigated, and the microscopic properties such as pore structure, surface functional groups and crystalline structure of the samples were studied by various characterization methods. The decarbonization mechanism of the composite adsorbent was also investigated by combining adsorption kinetics, adsorption thermodynamics and elemental valence changes. It was found that the sol-gel method is favorable for the preparation of modified biochar. The loaded multi-metals existed as metal oxides in the modified biochar, and the oxidized edge lattice defects introduced oxygen-containing functional groups to the modified biochar, and the best results were obtained for the 10% Fe+4% Ce+2% Cu sample with an adsorption capacity of 1.53mmol/g. The adsorption of CO₂ by the composite adsorbent was the result of the combined effect of physical and chemical adsorption, and the MOFs material optimized the pore structure of the composite adsorbent. The pore structure of the composite adsorbent was optimized by the MOFs material, and the chemisorption occurred on the surface of the modified biochar due to its graphite microcrystalline structure and doped multi-metal modification, the composite of the two played a mutually promoting and synergistic role in the decarbonization process, so that the adsorption performance of the composite adsorbent was significantly improved. The improvement was 230.7% and 75.7% compared to modified biochar and Mg-MOF-74, respectively.

Key words： biochar MOFs composite adsorbents modified modifications adsorption mechanism

收稿日期: 2023-10-04

PACS:

X773

基金资助:国家自然科学基金资助项目(U1910214);电力系统国家重点实验室资助课题(SKLD21KM16);山西省基础研究计划资助项目(20210302124449)

通讯作者: 金燕,博士,jinyan@tyut.edu.cn E-mail: jinyan@tyut.edu.cn

作者简介: 王晨星(1999-),男,陕西咸阳人,硕士研究生,主要从事煤清洁燃烧与污染物控制等方向.1070321814@qq.com.

引用本文:

王晨星, 贾里, 柳晴瑞, 王玉莹, 程鹏, 乔晓磊, 聂浩田, 金燕. 基于MOFs的改性生物焦复合吸附剂脱碳特性及机理研究[J]. 中国环境科学, 2024, 44(5): 2879-2892. WANG Chen-xing, JIA Li, LIU Qing-rui, WANG Yu-ying, CHENG Peng, QIAO Xiao-lei, NIE Hao-tian, JIN Yan. Study on decarbonization properties and mechanism of composite adsorbent with modified biochar based on MOFs. CHINA ENVIRONMENTAL SCIENCECE, 2024, 44(5): 2879-2892.

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