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

doi:10.11949/j.issn.0438-1157.20171357

Abstract

Abstract:

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

摘要：

选用桑蚕废弃物蚕沙为炭源，通过炭化活化的方式获得了一种高比表面的中微双孔道生物炭材料SCSE，并采用不同氧化剂对其表面氧化处理以调控材料孔径和表面积对农药噻虫嗪分子的吸附作用力，以实现SCSE材料对农药噻虫嗪的缓控释，并系统研究了氧化改性后材料的比表面积、孔径和表面基团性质的变化对材料吸附噻虫嗪的热力学和动力学平衡以及噻虫嗪的释放动力学等性能的影响。结果表明：SCSE孔隙结构发达，其BET比表面和孔容分别为1290.95 m²/g和0.690 cm³/g；在室温下，该材料对噻虫嗪分子的吸附容量达到560 mg/g。噻虫嗪在四种SCSE上的释放动力学可分为快速持续释放过程和慢速释放过程两个过程，其中快速持续释放过程的释放动力学常数约是慢速释放过程的29～34倍；其中硝酸改性后的SCSE-HN对噻虫嗪的释放比例最大，释放速度最快。本实验所获得的四种SCSE材料对噻虫嗪的释放均表现出长效释放效力。按照一般农作物的需药量，该吸附剂只要按照0.5 g/（d·m²）的投入量便能很好地对农作物进行长效的虫害防治（>40 d）。

关键词: 蚕沙基多孔生物炭, 氧化改性, 噻虫嗪, 吸附平衡和动力学, 缓控释

CLC Number:

WU Yuxiang, WANG Xinhui, CHAI Kungang, LIN Guoyou, ZHAO Zhenxia, ZHAO Zhongxing. Oxidized modification of novel silkworm excrement-based porous biocarbon with various acids for sustained release of pesticide thiamethoxam[J]. CIESC Journal, 2018, 69(6): 2797-2804.

武煜翔, 王欣辉, 柴坤刚, 林国友, 赵祯霞, 赵钟兴. 蚕沙基多孔炭表面氧化改性对农药噻虫嗪吸附及缓控释影响[J]. 化工学报, 2018, 69(6): 2797-2804.

References 30

[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.