CAS OpenIR
杀菌剂用纳米氢氧化铜的制备及应用性能研究
徐爽
Subtype硕士
Thesis Advisor曲景奎
2018-07
Degree Grantor中国科学院研究生院
Degree Name硕士
Degree Discipline化学工程
Keyword氢氧化铜,配位沉淀法,前驱体法,纳米线,水分散粒剂
Abstract

氢氧化铜是一种重要的工业材料,可用于医药、媒染剂、颜料、饲料添加剂、农药、纸张染色剂和催化剂等方面,近些年又发现其在能量储存和传感器上也有潜在用途。其中,氢氧化铜是广泛用于果蔬、农田作物病害防治的广谱杀菌剂,它是无机铜制剂中的一支新秀,被农业部列入无公害农产品推荐使用品种之一。对杀菌材料而言,粒度越小、分散性越好、比表面积越大,杀菌效果越好,当杀菌材料达到纳米级别时,拥有更强的抗菌活性,因此氢氧化铜的纳米化将是影响杀菌效果的关键。本文主要以直接沉淀法、前驱体法和配位沉淀法来制备氢氧化铜,在研究不同条件下制备氢氧化铜规律后,选取性能较好的氢氧化铜制成水分散粒剂,并将其与外购氢氧化铜制成的铜制剂对比。本论文主要得到以下结果:(1)直接沉淀法制备氢氧化铜的研究。氢氧化钠溶液的快速加入比滴加方式得到的氢氧化铜结晶性能好,氢氧化钠用量较低(n(Cu2+):n(OH-)=1:2相对于n(Cu2+):n(OH-)=1:2.5)时,结晶性能差一些。当n(Cu2+):n(OH-)=1:2.5时,得到由直径约20 nm、长为1 μm-2 μm的纳米线或其组装成的束状(或带状)结构堆积而成1 μm-20 μm团聚严重的大小不一的颗粒;n(Cu2+):n(OH-)=1:2时,得到是纳米球颗粒堆积而成1-15 μm的团聚严重的颗粒。直接沉淀法得到的氢氧化铜颗粒大小不均一,分散性不佳,团聚严重。(2)前驱体法制备氢氧化铜的研究。氢氧化钠法中,向硫酸铜溶液中滴加或快速倒入氢氧化钠溶液分别可以得到直径为200-300 nm的(Cu4SO4(OH)6)与Cu4SO4(OH)6·H2O纳米片前驱体,不论哪种前驱体,氢氧化钠溶液滴加方式处理前驱体得到的氢氧化铜纳米线(或纳米棒)总是比快速加入方式的长,最终均得到由纳米线(或棒)交错编织成大小不均一的颗粒。尿素法得到厚约0.5 μm、宽1-2 μm、长为1-10 μm的微米级块状前驱体。氢氧化钠溶液滴加方式处理该前驱体得到由直径约30 nm、长为1-2 μm整齐排列氢氧化铜纳米线编织成的梳形颗粒,基本保留了原前驱体的形貌特征;氢氧化钠溶液快速方式得到由直径约30 nm、长为1-3 μm氢氧化铜纳米线编织的梳形颗粒,其也和前驱体形貌相似,但易堆积而成数微米大小的颗粒。前驱体法得到的氢氧化铜颗粒大小不均一,分散性不好。 (3)配位沉淀法制备氢氧化铜的研究。不同初始浓度硫酸铜随不同氨水浓度所得氢氧化铜颗粒在形貌上有类似的规律,随着氨水浓度的增加,均是从团聚较严重的大小不均一的颗粒向有序的结构转变,低氨水浓度(对应2-5 mol/L、1.5-2.5 mol/L、1-2 mol/L)得到氢氧化铜基本是由纳米线或纳米棒堆积而成的团聚较严重的大小不均一的颗粒;而高氨水浓度(对应6-9 mol/L、3-3.5 mol/L、2.5-3 mol/L) 得到的氢氧化铜是由直径20-30 nm、长0.5 μm-2 μm的纳米线有序组装成的大小均一的花簇状(或束状)颗粒。这种花簇状颗粒粒度均一,分散性较好,纯度高,具备较高比表面积,可达83.3 m2/g。(4)表面活性剂-配位沉淀法制备氢氧化铜的研究。SDS、PEG 6000、PVP 40000对氢氧化铜形貌有较大影响,其中,SDS在减小纳米线长度的同时,还能降低束状颗粒的直径,但易引入杂质;不同浓度的PEG 6000得到的均是接近球形的花簇状颗粒,直径约1 μm,其可以减小纳米线长度,增加花簇状颗粒直径;PVP 40000主要通过降低花簇状(或束状)颗粒的直径,来影响氢氧化铜的形貌。(5)氢氧化铜水分散粒剂研究。配位沉淀法所得氢氧化铜的比表面积远高于长湖氢氧化铜,这是由于前者纳米线排列不如后者致密,而且束状(或簇状)颗粒分散性也较好。配位沉淀法所得氢氧化铜制成的水分散粒剂悬浮率要优于购于苏州的纳米氢氧化铜制成的水分散粒剂,其基本满足粒度、悬浮率和pH的要求。;AbstractCopper hydroxide is an important industrial material that can be used in medicine, mordants, pigments, feed additives, pesticides, paper dyes, and catalysts. In recent years, researchers also have found it has the potential usage in energy storage and sensors. Among them, copper hydroxide, a rookie in inorganic copper preparations, is a broad-spectrum fungicide widely used in the prevention and cure of diseases in fruits, vegetables and crops. It has been included as one of the recommended varieties of pollution-free agricultural products by the Ministry of Agriculture. For bactericidal materials, the smaller the particle size, the better the dispersibility, and the larger the specific surface area, the better the germicidal efficacy. When the bactericidal material reaches the nanoscale, it has a stronger antibacterial activity, so the nanocrystallization of copper hydroxide will be the key to the bactericidal effect. In this paper, copper hydroxide was prepared by direct precipitation method, precursor method and coordination precipitation method. After studying the rules of preparing copper hydroxide under different conditions, copper hydroxide with good performance was selected to make water dispersible granules compared with a copper preparation made of purchased copper hydroxide. The main results of this paper are as follows:(1) Preparation of copper hydroxide by direct precipitation method was studied. The rapid addition of sodium hydroxide solution had better crystal performance of copper hydroxide than that obtained by dropwise addition, and the lower(n(Cu2+):n(OH-) =1:2 relative to n(Cu2+):n(OH-)=1:2.5) amount of sodium hydroxide was, the worse crystallization performance was. When n(Cu2+):n(OH-)=1:2.5, nanowires with a diameter of about 20 nm, a length of 1-2 μm, and bundle-like (or ribbon) structure assembled by them was piled up to be severely agglomerated and ununiformed particles of 1-20 μm. When n(Cu2+):n(OH-)=1:2, nanospheres piled up and formed agglomerated particles of 1-15 μm. Copper hydroxide particles obtained by the direct precipitation method were uneven in size with poor dispersibility and serious agglomeration.(2) Preparation of copper hydroxide by precursor method was studied. By sodium hydroxide method, Cu4SO4(OH)6 and Cu4SO4(OH)6·H2O nanosheet precursors with diameters of 200-300 nm could be obtained by dropping or rapidly pouring sodium hydroxide solution into copper sulfate solution. Regardless of which precursor, the copper hydroxide nanowires (or nanorods) obtained by treating the precursors with sodium hydroxide solution dropping method were always longer than those of the fast addition method, and finally the nanowires (or rods) staggered and woven into non-uniformly sized particles. Precursor of micron-sized structure with a thickness of about 0.5 μm, a width of 1-2 μm, and a length of 1-10 μm was obtained by treating the precursor with urea method. comb-shaped particles consisting of aligned copper hydroxide nanowires with a diameter of about 30 nm and a length of 1-2 μm were obtained by dropwise addition of sodium hydroxide solution, which basically retained the original precursor's morphology characteristics. The comb-shaped particles similar to the precursor morphology were woven by copper hydroxide nanowires with a diameter of about 30 nm and a length of 1-3 μm, but comb-shaped particles were easy to accumulate as to several micrometers. Copper hydroxide particles obtained by precursor method were uneven in size with poor dispersibility. (3) Preparation of copper hydroxide by coordination precipitation method was studied. The copper hydroxide particles obtained with different initial copper sulfate concentrations and different ammonia concentrations had similar morphological characteristics. With increaseing ammonia concentration, they were all transformed from agglomerated and ununiformed particles to ordered paiticles. Low ammonia concentrations (corresponding to 2-5 mol/L, 1.5-2.5 mol/L and below, 1-2 mol/L and below) yielded that copper hydroxide was basically agglomerated with nanowires or nanorods. and was severely agglomerated and ununiformed. Uniform flower-shaped cluster (or bundle) copper hydroxide particles obtained with high ammonia concentrations (corresponding to 6-9 mol/L, 3-3.5 mol/L, 2.5-3 mol/L) were assembled from nanowires of 20-30 nm in diameter and 0.5-2 μm in length. This flower-like cluster paticles had uniform particle size, good dispersibility and high purity, with high specific surface area up to 83.3 m2/g.(4) Preparation of copper hydroxide by surfactant-coordination precipitation method was studied. SDS, PEG 6000 and PVP 40000 had great influences on copper hydroxide morphology. Among them, SDS could reduce the length of nanowires while reducing the diameter of the bundled paitcles, but it was easy to introduce impurities. Different concentrations of PEG 6000 which could reduce the length of nanowires and increase the diameter of flower-shaped cluster particles, could obtained a nearly spherical flower-like cluster particles with diameter of about 1μm. PVP 40000 mainly affected copper hydroxide morphology by reducing the diameter of flower-like clusters (or bundles).(5) Copper hydroxide dispersible granules were studied. The specific surface area of the copper hydroxide obtained by the coordination precipitation method was much higher than that of the purchased copper hydroxide. This was because the former nanowires were not as dense as the latter, and the dispersion of bundles (or clusters) was also better. The suspension of water dispersible granules made of copper hydroxide obtained by the coordination precipitation method was superior to the water dispersible granules made of nano-copper hydroxide purchased from Suzhou. And they basically met the requirements of particle size, suspension rate and pH

Language中文
Document Type学位论文
Identifierhttp://ir.ipe.ac.cn/handle/122111/26868
Collection中国科学院过程工程研究所
研究所(批量导入)
Recommended Citation
GB/T 7714
徐爽. 杀菌剂用纳米氢氧化铜的制备及应用性能研究[D]. 中国科学院研究生院,2018.
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