CIESC Journal ›› 2018, Vol. 69 ›› Issue (6): 2797-2804.doi: 10.11949/j.issn.0438-1157.20171357

Previous Articles    

Oxidized modification of novel silkworm excrement-based porous biocarbon with various acids for sustained release of pesticide thiamethoxam

WU Yuxiang, WANG Xinhui, CHAI Kungang, LIN Guoyou, ZHAO Zhenxia, ZHAO Zhongxing   

  1. School of Chemistry & Chemical Engineering, Guangxi University, Guangxi Colleges and Universities Key Laboratory of New Chemical Application Technology in Resources, Nanning 530004, Guangxi, China
  • Received:2017-10-11 Revised:2018-01-02 Online:2018-06-05 Published:2018-06-05
  • Supported by:

    supported by the National Natural Science Foundation of China (21666004, 21676059, 21606054), the Natural Science Foundation of Guangxi Zhuang Autonomous Region, China (2017GXNSFFA198009, 2016GXNSFAA380229) and the Scientific Research Foundation of Guangxi University (XGZ130963).


Oxidation modification of a novel silkworm excrement-based porous carbon (SCSE) with various acidic oxidants were prepared and applied for sustained release of pesticide thiamethoxam (TM). The effects of pore size and surface properties on TM adsorption performance of SCSE and modified SCSE were investigated. The TM adsorption equilibrium/kinetics and release kinetics on four SCSE samples were systematically measured, and the corresponding kinetic parameters were estimated by using pseudo-first-order equation in two sections. The results show that:the prepared SCSE shows a micro/mesopores structure (1290.95 m2/g and 0.690 cm3/g) and its adsorption capacity of TM reached 560 mg/g at 298 K. The total controlled-release process for TM on the SCSE samples could be divided into two stages:fast-sustained release stage and slow release stage. The release rate for the fast-sustained release stage was about 29-34 times faster than that for the slow release stage. Among which, the SCSE-HN modified by HNO3 showed the highest release ratio and fastest release rate due to its largest pore size distribution and the weakest interaction towards TM. According to actual TM using conditions for some crops (1.0-2.0 mg/m2), only 0.5 g of TM loaded PCSE can efficiently control main pest of crops per square meter last for over 40 days.

Key words: silkworm excrement-based porous biocarbon, oxidized modification, pesticide thiamethoxam, adsorption equilibrium/kinetics, controlled release

CLC Number: 

  • O69
[1] 陈伟. 关于南通地区化学农药减控使用的探索[J]. 上海农业科技, 2016, 46(1):135-137. CHEN W. About the exploration of Nantong area in chemical pesticide control to use[J]. Shanghai Agricultural Science and Technology, 2016, 46(1):135-137.
[2] 周喜应. 科学使用生物农药促进农药减量控害[J]. 农药市场信息, 2016, 31(17):25-27. ZHOU X Y. Scientific use of biological pesticide promote reducing pesticide pollution[J]. Pesticide Market News, 2016, 31(17):25-27.
[3] 孙明海, 顾士莲, 孔德生, 等. 当前农药使用存在的问题及解决对策[J]. 内蒙古农业科技, 2004, 32(S2):141-143. SUN M H, GU S L, KONG D S, et al. The problems of using pesticide and the methods to solve[J]. Inner Mongolia Agricultural Scienceand Technology, 2004, 32(S2):141-143.
[4] 束放, 熊延坤. 我国农药生产应用现状及减量使用重要意义[J]. 中国农药, 2016, 12(1):42-45. SHU F, XIONG Y K. The present situation of the application of pesticide production in China and the significance of reducing[J]. Journal of China Agrochemicals, 2016, 12(1):42-45.
[5] 宋宛桐. 我国农业土壤污染现状及其成因[J]. 农业与技术, 2016, 36(8):245-246. SONG W T. The soil pollution present situation and the reasons of Chinese agricultural[J]. Agriculture and Technology, 2016,36(8):245-246.
[6] 汤洁, 刘修树, 范高福, 等. 缓控释技术的研究进展[J]. 科技视界, 2015, 5(18):23-116. TANG J, LIU X S, FAN G F, et al. The research progress of slow controlled release technology[J]. Science and Technology Vision, 2015, 5(18):23-116.
[7] 冯建国,吴学民.国内农药剂型加工行业的现状及展望[J]. 农药科学与管理, 2016, 35(1):26-31. FENG J G, WU X M. The status and prospects of domestic pesticide processing industry[J]. Pesticide Science and Administration, 2016, 35(1):26-31.
[8] 江熠辉. 多孔材料负载农药缓释剂的制备及缓释性能的研究[D]. 北京:北京化工大学, 2011. JIANG Y H. The preparation of porous material load pesticide relievers and the performance research of slow-release[D]. Beijing:Beijing University of Chemical Technology, 2011.
[9] VIVEK D, SACHDEV Y, SARVESH P, et al. Design and evaluation of aceclofenac ocular inserts with special reference to cataracts and conjunctivitis[J]. Journal of Chinese Pharmaceutical Sciences, 2013, 22(5):449-455.
[10] 杨军星, 王琦, 王媛媛, 等. 双重载药多层海藻酸盐-壳聚糖缓释微球的制备及体外释放[J]. 高等学校化学学报, 2015,36(5):1025-1032. YANG J X, WANG Q, WANG Y Y,et al. Double for multilayer alginate-chitosan hydrogel microspheres preparation and in vitro release[J]. Chemical Journal of Chinese Universities, 2015, 36(5):1025-1032.
[11] 赵倩, 薛荣, 张毅, 等. pH敏感性两性壳聚糖/聚乙烯亚胺复合纳米粒的制备及其性能研究[J]. 今日药学, 2015, 25(12):814-818. ZHAO Q, XUE R, ZHANG Y, et al. pH sensitivity between chitosan/polyethylene imine compound preparation of nanoparticles and its performance[J]. Pharmacy Today, 2015, 25(12):814-818.
[12] 马兰可, 钱超群, 闫宪飞. 农药微囊悬浮剂研究进展[J]. 广州化工, 2016, 43(13):31-33. MA L K, QIAN C Q, YAN X F. The research progress of pesticide microcapsule suspending[J]. Guangzhou Chemical Industry, 2016, 43(13):31-33.
[13] 吕政洪, 张建新, 闫亚红. 高分子材料在农药缓释剂中的应用[J]. 南方农机, 2016, 47(10):77-78. LÜ Z H, ZHANG J X, YAN Y H. The application of pesticide relievers on polymer materials[J]. China Southern Agricultural Machinery, 2016, 47(10):77-78.
[14] 杨海霞, 朱祥瑞, 房泽民. 蚕沙的开发利用研究进展[J]. 蚕桑通报, 2002, 49(3):9-12. YANG H X, ZHU X R, FANG Z M. The development and utilization of the silkworm excrement[J]. Bulletin of Sericulture, 2002, 49(3):9-12.
[15] 王国栋, 邓先伦, 朱光真, 等. KOH活化高比表面积椰壳活性炭的制备及其性质研究[J]. 林产化学与工业, 2013, 33(2):108-112. WANG G D, DENG X L, ZHU G Z, et al. The research of KOH activation ratio of surface area of the preparation and properties of coconut shell activated carbon[J]. Chemistry and Industry of Forest Products, 2013, 33(2):108-112.
[16] KURWADKAR S T, DEWINNE D, WHEAT R, et al. Time dependent sorption behavior of dinotefuran, imidacloprid and thiamethoxam[J]. Journal of Environmental Science and Health Part B-Pesticides Food Contaminants and Agricultural Wastes, 2013, 48(4):237-242.
[17] CHEN H, LIN Y, ZHOU H, et al. Synthesis and characterization of chlorpyrifos/copper(Ⅱ) Schiff base mesoporous silica with pH sensitivity for pesticide sustained release[J]. Journal of Agricultural and Food Chemistry, 2016, 64(43):8095-8102.
[18] 胡梅, 刘永刚, 张海英, 等. HPLC检测分析噻虫嗪种衣剂在马铃薯中的残留动态变化[J]. 中国农学通报, 2012, 29(15):189-193. HU M, LIU Y G, ZHANG H Y, et al. HPLC analysis thiamethoxam in potato residue dynamically[J]. Chinese Agricultural Science Bulletin, 2012,29(15):189-193.
[19] 朱亚红, 杜巍, 苏印泉, 等. KOH活化法制备沙柳枝木活性炭的研究[J]. 中国农学通报, 2015, 29(22):26-31. ZHU Y H, DU W, SU Y Q, et al. The research of carbon prepared about KOH activation of willow[J]. Chinese Agricultural Science Bulletin, 2015, 29(22):26-31.
[20] 黄桥, 孙红娟, 杨勇辉. 氧化石墨的谱学表征及分析[J]. 无机化学, 2011, 27(9):1721-1726. HUANG Q, SUN H J, YANG Y H. Spectroscopy characterization and analysis of graphite oxide[J]. Chinese Journal of Inorganic Chemistry, 2011, 27(9):1721-1726.
[21] 李勇, 张琦. 巴旦杏核壳活性炭表征分析[J]. 塔里木大学学报, 2014, 37(2):16-19. LI Y, ZHANG Q. Paddan apricot core-shell characterization analysis of the preparation of activated carbon[J]. Journal of Tarim University, 2014, 37(2):16-19.
[22] 龚俊波, 陈明洋, 黄翠, 等. 面向清洁生产的制药结晶[J]. 化工学报, 2015, 66(9):3271-3278. GONG J B, CHEN M Y, HUANG C, et al. Clean production of pharmaceutical crystallization[J]. CIESC Journal, 2015, 66(9):3271-3278.
[23] 张鹏, 慕卫,刘峰, 等. 噻虫嗪在土壤中的吸附和淋溶特性[J]. 环境化学, 2015,34(4):705-711. ZHANG P, MU W, LIU F, et al. Thiamethoxam lamictal in the soil adsorption and leaching properties[J]. Environmental Chemistry, 2015, 34(4):705-711.
[24] 宋建刚, 岳东北, 聂永丰. 硝酸改性活性炭对渗滤液中小分子有机物的吸附性能[J]. 环境化学, 2009, 34(6):788-792. SONG J G, YUE D B, NIE Y F. Nitric acid modified activated carbon adsorption performance of leachate small molecule organic compounds[J]. Environmental Chemistry, 2009, 34(6):788-792.
[25] 高雪杉. 污泥吸附剂对铬去除效果研究[D]. 哈尔滨:哈尔滨工业大学, 2012. GAO X S. Chrome sludge adsorbent for removing effect research[D]. Harbin:Harbin Institute of Technology, 2012.
[26] 王家宏, 尹小龙. 双酚A在不同碳材料上的吸附热力学与动力学研究[J]. 陕西科技大学学报(自然科学版), 2015, 33(2):27-33. WANG J H, YIN X L. Bisphenol A in different carbon materials on the adsorption thermodynamics and dynamics research[J]. Journal of Shaanxi University of Science & Technology (Natural Science Edition), 2015, 33(2):27-33.
[27] 何明, 尹国强,王品, 等. 羽毛蛋白基高吸水性树脂吸附Cd2+的动力学和热力学研究[J]. 化工新型材料, 2013, 41(6):72-74. HE M, YIN G Q, WANG P,et al. Feather protein-based superabsorbent Cd2+ adsorption kinetics and thermodynamics[J]. New Chemical Material, 2013, 41(6):72-74.
[28] 冀有俊, 杨钊, 贺彬艳, 等. 甲烷吸附量与活性炭孔隙结构关系的研究[J]. 天然气化工(C1化学与化工), 2014, 38(4):10-12. JI Y J, YANG Z, HE B Y, et al. The findings of a study of methane adsorption capacity and activated carbon pore structure[J]. Natural Gas Chemical Industry, 2014, 38(4):10-12.
[29] WEI Y N, WU Y X, CHANG Q, et al. Ultrasonic-assisted modification of a novel silkworm-excrement-based porous carbon with various Lewis acid metal ions for the sustained release of the pesticide thiamethoxam[J]. RSC Advances, 2017, 7(48):30020-30031.
[30] 鲁秀国, 黄燕梅. 磷酸改性和普通核桃壳对水中Cr(VI)的吸附[J]. 江西农业大学学报, 2015, 37(2):353-358. LU X G, HUANG Y M. Phosphoric acid modification and ordinary walnut shell adsorption of Cr (VI) in water[J]. Acta Agriculturae Universitis Jiangxiensis, 2015, 37(2):353-358.
[1] SHI Pan, YAN Xiaoxiao, WANG Xingzheng, FENG Leyun, CHEN Dong. One-step fabrication of biocompatible oil-core microcapsules with controlled release [J]. CIESC Journal, 2021, 72(1): 619-627.
[2] Li HAO, Dandan HUANG, Mei GUAN, Hongjun ZHOU, Xinhua ZHOU. Preparation of supramolecular-assemble hydrogels as pesticide carriers based on amphiphilic amino-amide compounds [J]. CIESC Journal, 2020, 71(8): 3819-3829.
[3] ZHOU Weiqing, LI Juan, NA Xiangming, MA Guanghui. Preparation and structure control of macroporous polymer microspheres [J]. CIESC Journal, 2015, 66(8): 2846-2853.
[4] WU Wenguo1,2,LIU Wei1,WANG Shibin1,2,LIU Yuangang1,2,CHEN Aizheng1,2. Drug loading and release of poly-L-arginine/calcium alginate microcapsules [J]. Chemical Industry and Engineering Progree, 2014, 33(05): 1271-1275.
[5] LIU Guijin, WANG Hongdi, JIANG Yanbin. Research progress of Zein as carrier for drug delivery systems [J]. CIESC Journal, 2013, 64(10): 3493-3504.
[6] KAN Wentao1,LI Xin2,LUO Shunzhong1,HU Rui1. Molecularly imprinted polymer hydrogel as 5-FU controlled release carrier [J]. Chemical Industry and Engineering Progree, 2013, 32(03): 627-633.
[7] WANG Jun, LI Mingchun, XIN Meihua, ZHANG Xiaolin, MAO Yangfan. Synthesis of N-mPEG-O-quaternized chitosan microsphere and its controlled drug release [J]. Chemical Industry and Engineering Progree, 2013, 32(01): 140-144.
[8] CHU Liangyin, XIE Rui, JU Xiaojie. Stimuli-responsive Membranes: Smart Tools for Controllable Mass-transfer and Separation Processes [J]. , 2011, 19(6): 891-903.
[9] MAO Yangfan,LI Mingchun,XIN Meihua,XIE Qinqin. Synthesis of O-quarternary ammonium chitosan bearing cyclodextrin [J]. , 2010, 29(9): 1705-.
[10] LI He,CHI Defu,YU Jia,GUAN Hua’nan. Preparation and properties of hydroxyecdysone microcapsules [J]. , 2010, 29(9): 1730-.
[11] XIE Zhiyi, CHEN Nengchang, LIU Chengshuai, ZHOU Jianmin, XU Shengguang, ZHENG Yuji, LI Fangbai, XU Yanling. Synthesis and Characterization of Ethylenediamine Tetraacetic Acid Tetrasodium Salt Loaded in Microcapsules with Slow Release Properties [J]. , 2010, 18(1): 149-155.
[12] LIU Yonghui,WANG Tingjie,KAN Chengyou,WANG Minghao,JIN Yong. Development in polymer latex coated fertilizer for controlled release [J]. , 2009, 28(9): 1589-.
[13] CAO Hui,SUN Shaohua,SU Haijia,WANG Fang,TAN Tianwei. Advances in the preparation and controlled drug release of hydrogels based on polyaspartic acid and its derivatives [J]. , 2009, 28(11): 1991-.
[14] LIU Yong,CUI Yingde,YIN Guoqiang,LI Xinming,CHEN Xunjun,ZHANG Buning. Intelligent hydrogels for controlled release of drug [J]. , 2008, 27(10): 1593-.
[15] QIAO Jichao,HU Xiaoling,ZHANG Tuanhong,GUAN Ping. Application of solvent evaporation method in preparation
of drug microcapsule
[J]. , 2006, 25(8): 885-.
Full text



[1] PatrickPERRE. Evidence of Dual Scale Porous Mechanisms During Fluid Migration in Hardwood Species (Ⅱ) A Dual Scale Computational Model to Describe the Experimental Results[J]. , 2004, 12(6): 783 -791 .
[2] LIU Zhichang, MENG Xianghai, XU Chunming, GAO Jinsen. Secondary Cracking of Gasoline and Diesel from Heavy Oil Catalytic Pyrolysis[J]. , 2007, 15(3): 309 -314 .
[3] LIU Yongjian, YUAN Xigang, LUO Yiqing. Synthesis of water utilization system using concentration interval analysis method (Ⅱ)
Discontinuous process
[J]. , 2007, 15(3): 369 -375 .
[4] QIN Wei, LI Zhenyu, WANG Min, DAI Youyuan. Extraction Behavior and Wastewater Treatment of Amino Sulfonic Acid with Alamine 336[J]. , 2004, 12(1): 137 -142 .
[5] LUO Yantuo, ZHU Jianhua, CHEN Guangjin. Numerical simulation of separating gas mixtures via hydrate formation in bubble column[J]. , 2007, 15(3): 345 -352 .
[6] WANG Fei, WANG Wenchuan, HUANG Shiping, TENG Jiawei, XIE Zaiku. Experiment and modeling of pure and binary adsorption of n-butane and butene-1 on ZSM-5
zeolites with different Si/Al ratios
[J]. , 2007, 15(3): 376 -386 .
[7] DU Hongbin, TENG Hu, YAO Pingjing. Matrix Expression of the Orthogonal Wavelet (Packets) Transform[J]. , 2002, 10(6): 701 -705 .
[8] ZHAN Xinmin, ZHAO Xuan, AKANE Miyazaki, YOSHIO Nakano. Lead Removal from Aqueous Solutions Using Novel Gel Adsorbent Synthesized from Natural
Condensed Tannin
[J]. , 2003, 11(4): 426 -430 .
[9] CAI Zhenyun, LU Zuguo, LI Xiaobo. Preparation of Ethylene Glycol Monoethyl Ether Acetate Using a Tubular Reactor[J]. , 2003, 11(3): 338 -340 .
[10] JIANG Yongheng, WANG Jun, JIN Yihui. Bottleneck Analysis of the Minimum Cost Problem for the Generalized Network Based on
Augmented Forest Structure
[J]. , 2003, 11(1): 62 -67 .