水合肼化学还原硫酸铜制备纳米铜粉的研究
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摘要
为了制备颗粒尺寸在纳米级、大小分布均匀的纳米铜粉,采用水合肼化学还原硫酸铜的方法,并利用扫描电镜(SEM),Image-Pro Plus软件、铜离子浓度测定仪等测方法测量纳米铜粉的颗粒尺寸和铜离子的转化率。结果表明,碱性条件下,水合肼化学还原硫酸铜制备纳米铜粉满足化学反应的热力学和动力性条件;制备纳米铜粉最佳的实验参数,水合肼浓度为1.5 mol/L、CuSO_4·5H_2O的浓度为0.5 mol/L、EDTA和PVP质量比为3∶2(EDTA浓度为30 g/L、PVP浓度为20 g/L)、反应溶液的pH值为12、反应温度为60℃、反应时间为30 min;在此条件下,获得颗粒大小均匀、颗粒尺寸为50.2 nm的纳米铜粉,Cu~(2+)的转化率达到98.2%。
The nano-sized copper powders with uniform size distribution were prepared by chemical reduction of copper sulfate with hydrazine hydrate. The copper particle size and percent conversion of Cu~(2+) were measured by scanning electron microscopy(SEM), Image-Pro Plus software and concentration analyzer of Cu~(2+). The results show that the nano-copper powders were prepared by chemical reduction of copper sulfate with hydrazine hydrate in alkaline condition, and the optimum preparation conditions were obtained. The concentration of hydrazine hydrate was 1.5 mol/L, the concentration of CuSO_4·5 H_2O was 0.5 mol/L, the mass ratio of EDTA and PVP was 3∶2(the concentration of EDTA and PVP was 30 g/L and 20 g/L, respectively), the pH value of reaction solution was 12, the reaction temperature was 60 ℃, and the reaction time was 30 min. Under these conditions, the nano-copper powders were with equable size and the particle size was 50.2 nm, and the conversion rate of Cu~(2+) reached 98.2%.
The nano-sized copper powders with uniform size distribution were prepared by chemical reduction of copper sulfate with hydrazine hydrate. The copper particle size and percent conversion of Cu~(2+) were measured by scanning electron microscopy(SEM), Image-Pro Plus software and concentration analyzer of Cu~(2+). The results show that the nano-copper powders were prepared by chemical reduction of copper sulfate with hydrazine hydrate in alkaline condition, and the optimum preparation conditions were obtained. The concentration of hydrazine hydrate was 1.5 mol/L, the concentration of CuSO_4·5 H_2O was 0.5 mol/L, the mass ratio of EDTA and PVP was 3∶2(the concentration of EDTA and PVP was 30 g/L and 20 g/L, respectively), the pH value of reaction solution was 12, the reaction temperature was 60 ℃, and the reaction time was 30 min. Under these conditions, the nano-copper powders were with equable size and the particle size was 50.2 nm, and the conversion rate of Cu~(2+) reached 98.2%.
引文
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[2] Wonterghem J V,M?rup S,Koch C J W,et al.Formation of ultra-fine amorphous alloy particles by reduction in aqueous solution.Nature,1986,322(6080):622-623.
[3] Issaabadi Z,Nasrollahzadeh M,Sajadi S M.Green synthesis of the copper nanoparticles supported on bentonite and investigation of its catalytic activity[J].Journal of Cleaner Production,2017,142:3584-3591.
[4] Peng Runling,Han Shaoxing,Zeng Qunfeng,et al.Synthesis and characterization of vacuum freeze-dried copper nano-powder[J].Chinese Journal of Vacuum Science and Technology,2016,36(2):217-222 (in Chinese).彭润玲,韩少星,曾群锋,等.真空冷冻干燥法制备纳米铜粉的实验研究[J].真空科学与技术学报,2016,36(2):217-222.
[5] Wang H,Zhang Z,Hu Z,et al.Synergistic strengthening effect of nanocrystalline copper reinforced with carbon nanotubes[J].Scientific Reports,2016,6(1):26258.
[6] Lu L,Shen Y F,Chen X H,et al.Ultrahigh strength and high electrical conductivity in copper[J].Science,2004,304(5669):422-426.
[7] Yang J,Okamoto T,Ichino R,et al.A simple way for preparing antioxidation nano-copper powders[J].Chemistry Letters,2006,35(6):648-649.
[8] Khanna P K,Gaikwad S,Adhyapak P V,et al.Synthesis and characterization of copper nanoparticles[J].Materials Letters,2007,61(25):4711-4714.
[9] Zhang Xiaomin,Zhang Zhenzhong,Lin Feng,et al.Preparation of copper nano-particles and dispersion technics in alcohol[J].Journal of Materials Engineering,2013,1:25-29 (in Chinese).张小敏,张振忠,林峰,等.纳米铜粉制备及其在乙醇中的分散工艺研究[J].材料工程,2013,1:25-29.
[10] Meyers M A,Mishra A,Benson D J.Mechanical properties of nanocrystalline materials[J].Progress in Materials Science,2006,51(4):427-556.
[11] Wang Yumian,Yu Mengjiao.Effects of surfactants on hydrazine synthesis of nanocrystalline copper powders under ultrasonic condition[J].Powder Metallurgy Technology,2008,26(4):296-298 (in Chinese).王玉棉,于梦娇.超声条件下表面活性剂对水合肼还原制备纳米铜粉的影响[J].粉末冶金技术,2008,26(4):296-298.
[12] Zhang Q L,Yang Z M,Ding B J,et al.Preparation of copper nanoparticles by chemical reduction method using potassium borohydride[J].Transactions of Nonferrous Metals Society of China,2010,20(S1):240-244.
[13] Lee Y,Choi J,Lee K J,et al.Large-scale synthesis of copper nanoparticles by chemically controlled reduction for applications of inkjet-printed electronics[J].Nanotechnology,2008,19(41):415604.
[14] Xu Jianlin,Chen Jidong,Wang Zhiping,et al.Effect of surface dispersants on nano-copper powders prepared by electrochemical method[J].Materials Science & Technology,2011,19(1):116-120 (in Chinese).徐建林,陈纪东,王智平,等.表面分散剂对电化学制备纳米铜粉的影响[J].材料科学与工艺,2011,19(1):116-120.
[15] Khan A,Rashid A,Younas R,et al.A chemical reduction approach to the synthesis of copper nanoparticles[J].International Nano Letters,2016,6(1):21-26.
[16] Sreeju N,Rufus A,Philip D.Microwave-assisted rapid synthesis of copper nanoparticles with exceptional stability and their multifaceted applications[J].Journal of Molecular Liquids,2016,221:1008-1021.
[17] Xu Rui,Zhou Kanggen,Hu Minyi.Reaction mechanism of silver-coated ultra-fine copper powders by reduction reaction using hydrazine as reducing agent[J].Rare Metal Materials and Engineering,2008,37(5):905-908 (in Chinese).徐锐,周康根,胡敏艺.水合肼液相还原法制备银包覆超细铜粉反应机理研究[J].稀有金属材料与工程,2008,37(5):905-908.
[18] Wen Jin,Du Yong,Yi Dan.Preparation of ultrafine copper powder by hydrazine hydrate[J].Guangdong Chemical Industry,2013,40(21):41-42 (in Chinese).文瑾,杜勇,易丹.水合肼还原制备超细铜粉[J].广东化工,2013,40(21):41-42.
[19] Yu Mengjiao,Wang Yumian,Hou Xingang.Preparation of copper nanoparticles by chemical reduction with hydrazine under ultrasonic action[J].Powder Metallurgy Technology,2007,17(6):19-23 (in Chinese).于梦娇,王玉棉,侯新刚.超声条件下水合肼还原制备纳米铜粉[J].粉末冶金工业,2007,17(6):19-23.