蚕沙基生物多孔炭的制备及对杀虫单/呋虫胺的协同吸附与缓释性能

doi:10.16085/j.issn.1000-6613.2023-0925

摘要/Abstract

摘要：

以桑蚕业废弃物蚕沙为原料，氯化锌为活化剂，在900℃下高温活化得到蚕沙基生物多孔炭（biochar of silkworm excrement，BCSE）。利用氮气吸脱附、扫描电子显微镜、X射线衍射及傅里叶变换红外光谱对BCSE的理化性质进行表征分析，并测试其对农药杀虫单和呋虫胺的协同吸附与脱附性能，以及吸附农药后的贮藏稳定性。结果表明：BCSE具有丰富的孔道结构，其最优材料BCSE-3的BET比表面积可达833.0m²/g，对杀虫单和呋虫胺的单独吸附分别可达0.83mmol/g和1.43mmol/g，双组分协同吸附时两种农药的吸附容量和吸附速率与单组分相比都显著提升。同时贮藏稳定性结果也证明在54℃下两种农药在BCSE-3中都拥有长达35d以上的稳定性（农药降解率<2%），远超农业农村部对农药贮藏稳定性的要求。最后通过分子模拟计算发现，呋虫胺上高电子密度的含氧五元杂环与BCSE上苯环形成π-π相互作用是呋虫胺具有更高吸附量和更快吸附速率的主要原因，而杀虫单和呋虫胺间的氢键作用是二者混合吸附量大于单组分吸附量的主要原因。

关键词: 蚕沙基生物炭, 杀虫单/呋虫胺, 协同吸附, 缓释, 热稳定性

Abstract:

The biochar of silkworm excrement(BCSE) was obtained by activation at 900℃, using silkworm excrement as raw material and zinc chloride as activator. The physicochemical property of BCSE were analyzed by nitrogen adsorption and desorption, SEM, XRD and FTIR, and its synergistic adsorption and desorption performance on pesticide monosultap and dinotefuran, as well as the storage stability after adsorption were tested. The results showed that BCSE had a rich pore structure, the BET specific surface area of BCSE-3 reached 833.0m²/g, and the individual adsorption of monosultap and dinotefuran was 0.83mmol/g and 1.43mmol/g respectively. Compared with the individual component, the adsorption capacity and adsorption rate of the two pesticides were significantly improved when the components were adsorbed synergistically. The results also proved that the two pesticides had a stability of more than 35 days in BCSE-3 at 54℃ (pesticide degradation rate<2%), far exceeding the requirements in relevant regulations of the Ministry of Agriculture. Finally, molecular simulation calculations showed that the π-π interaction between the oxygen-containing five-membered heterocyclic ring with high electron density on dinotefuran and the benzene ring on BCSE was the main reason for the higher adsorption capacity and faster adsorption rate of dinotefuran. The hydrogen bond between monosultap and dinotefuran was the main reason why the adsorption capacity of the mixture of the two was greater than that of the individual component.

Key words: silkworm excrement-based biochar, monosultap/dinotefuran, synergistic adsorption, slow-release, thermal stability

中图分类号:

黄军, 张应娟, 林茵童, 韦雪纯, 吴雨桐, 毋高博, 莫钧麟, 赵祯霞, 赵钟兴. 蚕沙基生物多孔炭的制备及对杀虫单/呋虫胺的协同吸附与缓释性能[J]. 化工进展, 2024, 43(7): 3964-3971.

HUANG Jun, ZHANG Yingjuan, LIN Yintong, WEI Xuechun, WU Yutong, WU Gaobo, MO Junlin, ZHAO Zhenxia, ZHAO Zhongxing. Preparation of silkworm excrement-based porous biocarbon and synergistic adsorption and slow-release performance for monosultap and dinotefuran[J]. Chemical Industry and Engineering Progress, 2024, 43(7): 3964-3971.

图/表 9

图1 蚕沙与BCSE-3的SEM图像

图2 四种BCSE的N2吸脱附曲线与孔径分布

表1 四组BCSE的比表面积与孔径数据

蚕沙基生物多孔炭	BET比表面积/m²·g^-1	微孔面积/m²·g^-1	微孔占比/%	总孔容/cm³·g^-1	平均孔径/nm
BCSE-1	635.0	530.6	83.6	0.322	1.27
BCSE-2	775.2	588.6	75.9	0.432	1.45
BCSE-3	833.0	531.9	63.9	0.608	2.01
BCSE-4	654.5	418.6	64.0	0.502	1.95

图3 BCSE-3的XRD与红外光谱图

图4 BCSE-3对杀虫单和呋虫胺单独吸附与混合吸附的吸附动力学及ln(Qe-Qt )对t的曲线

图5 BCSE-3对杀虫单和呋虫胺单独脱附与混合脱附的释放动力学及ln(Qe-Qt )对t的曲线

图6 杀虫单和呋虫胺在BCSE-3中的贮藏稳定性

图7 杀虫单（左）与呋虫胺（右）分子的静电势

图8 杀虫单与呋虫胺水溶液体系微观结构(1Å=0.1nm)

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