不同粒度八棱柱形纳米铜的制备研究

doi:10.19964/j.issn.1006-4990.2020-0398

摘要/Abstract

摘要：

纳米铜具有优异的导电、催化、润滑、抗菌等性能,而这些性能和应用范围均与其形貌和粒度有关。八棱柱形纳米铜很有可能具有一些特殊的性能和用途,而关于不同粒度八棱柱形纳米铜的制备研究还未见报道。采用水热法,以二水合氯化铜（CuCl₂·2H₂O）为铜源,以十八胺（ODA）为还原剂,研究了八棱柱形纳米铜的制备。考察了反应物浓度、反应温度、反应时间等条件对纳米铜的八棱柱形貌及尺寸的影响。讨论了八棱柱形纳米铜的形成机理。结果表明,八棱柱形纳米铜的制备是相当困难的,只有采用具有形貌和粒度控制作用的还原剂十八胺,并严格控制实验条件,才能制备出不同粒度的八棱柱形纳米铜。制备八棱柱形纳米铜的最佳条件：十八胺与氯化铜的浓度比为（2~3）∶1,反应温度为180 ℃,反应时间为48 h。八棱柱形纳米铜的形成机理可归因于十八胺对纳米铜{100}晶面的选择性吸附。八棱柱形纳米铜的粒度随着十八胺浓度的增加而增大,通过控制十八胺的浓度可实现不同粒度八棱柱形纳米铜的可控制备,并且发现十八胺具有还原、形貌控制和粒度控制三重作用。这些结果可为制备八棱柱形其他金属纳米材料提供重要参考。

关键词: 八棱柱, 纳米铜, 十八胺, 形貌控制, 粒度控制, 形成机理

Abstract:

Nano-copper has excellent conductivity,catalysis,lubrication,antibacterial performances and so on.These proper-ties and application range are related to their morphology and particle size.The octagonal prismatic nano-copper may have some special properties and applications,but the preparation of octagonal prismatic nano-copper with different particle size has not been reported.The preparation of octagonal prismatic nano-copper was studied by hydrothermal method with CuCl ₂·2H₂O as copper source and octadecylamine（ODA） as reducing agent.The effects of reactant concentration,reaction tempera-ture and reaction time on the morphology and size of octagonal prismatic nano-copper were investigated.The formation mech-anism of octagonal prismatic nano-copper was discussed.The results showed that it was very difficult to prepare the octagonal prismatic nano-copper.Only by using the reducing agent（octadecylamine） with the function of shape control and size control and strictly controlling the experimental conditions,the octagonal prismatic nano-copper with different particle sizes could be prepared.The optimal conditions for the preparation of the octagonal prismatic nano-copper by hydrothermal method were：c（ODA）∶c（CuCl₂） was（2~3）∶1,the reaction temperature was 180 ℃,and the reaction time was 48 h.The formation mecha-nism of the octagonal prismatic nano-copper could be attributed to selective adsorption of ODA toward the{100} facets.With the increase of ODA concentration,the size of the octagonal prismatic nano-copper increased.By controlling its concentration,the controllable preparation of octagonal prismatic nano-copper with different sizes could be realized.Moreover,it was found that ODA had three functions of reduction,shape control and size control.These results could provide important references for the preparation of other octagonal prismatic metal nanomaterials.

Key words: octagonal prism, nano-copper, octadecylamine, shape control, size control, formation mechanism

中图分类号:

TQ131.21

张慧捷,常越凡,李宗儒,薛永强. 不同粒度八棱柱形纳米铜的制备研究[J]. 无机盐工业, 2021, 53(6): 145-149.

Zhang Huijie,Chang Yuefan,Li Zongru,Xue Yongqiang. Study on preparation of octagonal prismatic nano-copper with different particle sizes[J]. Inorganic Chemicals Industry, 2021, 53(6): 145-149.

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参考文献 37

[1]	Gurwich I, Sivan Y. Metal nanospheres under intense continuous-wave illumination:A unique case of nonperturbative nonlinear nano-photonics[J]. Physical Review E, 2017,96.Doi: 10.1103/physreve.96.012212.
[2]	Duque J S, Blandón J S, Riascos H. Localized plasmon resonance in metal nanoparticles using Mie theory[J]. Journal of Physics:Con-ference Series, 2017,850.Doi: 10.1088/1742-6596/850/1/012017.
[3]	Akbayrak S, Ozkar S. Metal nanoparticles in liquid phase cataly-sis[J]. Encyclopedia of Interfacial Chemistry, 2018:497-519.
[4]	Cui X, Zheng Y, Tian M, et al. Palladium nanoparticles supported on SiO₂@Fe₃O₄@m-MnO₂ mesoporous microspheres as a highly effi-cient and recyclable catalyst for hydrodechlorination of 2,4-dich-lorophenol and reduction of nitroaromatic compounds and organic dye[J]. Molecular Catalysis, 2017,433:202-211.
[5]	Nabanita P, Dattatreya K, Abhisek P, et al. Antibacterial,anticanc-er,anti-diabetic and catalytic activity of bio-conjugated metal nano-particles[J]. Advances in Natural Sciences:Nanoscience and Nano-technology, 2018,9(3).Doi: 10.1088/2043-6254/aad12d.
[6]	Mehran Alavi, Mahendra Rai. Recent advances in antibacterial applications of metal nanoparticles (MNPs) and metal nanocomposites(MNCs) against multidrug-resistant(MDR) bacteria[J]. Expert Review of Anti-infective Therapy, 2019,17(6):419-428.
[7]	Khan Z U H, Khan A, Chen Y M, et al. Biomedical applications of green synthesized Nobel metal nanoparticles[J]. Journal of Photo-chemistry and Photobiology B:Biology, 2017,173:150-164.
[8]	Del Pino González De La Higuera Pablo, Pelaz Garcia B, Polo To-bajas E, et al. Biosensor comprising metal nanoparticles:US, 10197566[P]. 2019-02-05.
[9]	Karol Kołataj, Robert Ambroziak, Mateusz Kedziora, et al. Forma-tion of bifunctional conglomerates composed of magnetic γ-Fe₂O₃ nanoparticles and various noble metal nanostructures[J]. Applied Surface Science, 2019,470:970-978.
[10]	Qi W H, Wang M P. Size and shape dependent melting temperature of metallic nanoparticles[J]. Materials Chemistry and Physics, 2004,88:280-284.
[11]	Lu H M, Li P Y, Cao Z H, et al. Size-,shape-,and dimensionality-dependent melting temperatures of nanocrystals[J]. Journal of Phy-sical Chemistry C, 2009,113(18):7598-7602.
[12]	Fu Q S, Zhu J H, Xue Y Q, et al. Size- and shape-dependent melting enthalpy and entropy of nanoparticles[J]. Journal of Materials Sci-ence, 2017,52:1911-1918.
[13]	Sun Y, Xia Y . Shape-controlled synjournal of gold and silver nano-particles[J]. Science, 2002,298(5601):2176-2179.
[14]	Rashmi Jain, Gaurav Khandelwal, Sangita Roy. Unraveling the de-sign rules in ultrashort amyloid-based peptide assemblies toward shape-controlled synjournal of gold nanoparticles[J]. Langmuir the Acs Journal of Surfaces & Colloids, 2019,35(17):5878-5889.
[15]	Wiley B J, Xiong Y J, Li Z Y, et al. Right bipyramids of silver:a new shape derived from single twinned seeds[J]. Nano Letters, 2006,6(4):765-768.
[16]	熊智淳, 张哲娟, 才滨. 控制剂(CuCl₂·2H₂O)对多元醇热法制备纳米银形貌的影响[J]. 无机盐工业, 2017,49(10):37-41.
[17]	Hoefelmeyer J D, Niesz K, Somorjai G A, et al. Radial anisotropic growth of rhodium nanoparticles[J]. Nano Letters, 2005,5(3):435-438.
[18]	Ye X, Gao Y, Chen J, et al. Seeded growth of monodisperse gold nanorods using bromide-free surfactant mixtures[J]. Nano Letters, 2013,13(5):2163-2171.
[19]	Park K, Drummy L F, Wadams R C, et al. Growth mechanism of gold nanorods[J]. Chemistry of Materials, 2013,25(4):555-563.
[20]	秦海青, 刘文平, 林峰, 等. 纳米铜粉对储氢合金电极电化学性能的影响[J]. 有色金属工程, 2016,6(1):18-21.
[21]	王鸿显, 王淼, 彭振桓, 等. 非水溶剂法制备纳米铜粉[J]. 无机盐工业, 2011,43(4):33-35.
[22]	Fan X, Mo L, Li W, et al. Synconfproc of nano-copper particles for conductive ink in gravure printing[C]//Suzhou,China:IEEE In-ternational Conference on Nano/Micro Engineered and Molecular Systems.Beijing:IEEE Committee on Nanotechnology and Peking University, 2013:775-778.
[23]	Wang X, Xu B, Xu Y, et al. Preparation of nano-copper as lubric-ation oil additive[J]. Journal of Central South University of Technology, 2005,12:203-206.
[24]	Gu C X, Zhu G J, Tian X Y, et al. Tribological effects of nano-co-pper with different diameters in lubricants[J]. Advanced Materials Research, 2010,123-125:1059-1062.
[25]	Tsoncheva T, Gallo A, Spassova I, et al. Tailored copper nanoparti-cles in ordered mesoporous KIT-6 silica:Preparation and applica-tion as catalysts in integrated system for NO removal with products of methanol decomposition[J]. Applied Catalysis A:General, 2013,464-465:243-252.
[26]	Vitulli G, Bernini M, Bertozzi S, et al. Nanoscale copper particles derived from solvated Cu atoms in the activation of molecular oxygen[J]. Chemistry of Materials, 2002,14(3):1183-1186.
[27]	Anyaogu K C, Fedorov A V, Neckers D C. Syntjournal,characteriza-terization,and antifouling potential of functionalized copper nano-particles[J]. Langmuir, 2008,24(8):4340-4346.
[28]	Filipovic N, Borrmann H, Todorovic T, et al. Copper(Ⅱ) complexes ofN-heteroaromatic hydrazones:Synjournal,X-ray structure,ma-gnetic behavior,and antibacterial activity[J]. Inorganica Chimica Acta, 2009,362(6):1996-2000.
[29]	Wang Y, Chen P, Liu M. Synjournal of well-defined copper nanocu-bes by a one-pot solution process[J]. Nanotechnology, 2006,17(24):6000-6006.
[30]	Dong H, Wang Y, Tao F, et al. Electrochemical fabrication of sh-ape-controlled copper hierarchical structures assisted by surfac-tants[J]. Journal of Nanomaterials, 2012,2012:1-6.
[31]	周全法, 蒋萍萍, 朱雯, 等. 抗氧化纳米铜粉的制备及表征[J]. 稀有金属材料与工程, 2004,33(2):179-182.
[32]	Shi Y, Li H, Chen L, et al. Obtaining ultra-long copper nanowires via a hydrothermal process[J]. Science and Technology of Advan-ced Materials, 2005,6(7):761-765.
[33]	GB/T 23413—2009 纳米材料晶粒尺寸及微观应变的测定:X射线衍射线宽化法[S].
[34]	朱红. 纳米材料化学及其应用[M]. 北京: 清华大学出版社,北京交通大学出版社, 2009.
[35]	Xia Y, Xiong Y, Lim B, et al. Shape-controlled synjournal of metal nanocrystals:Simple chemistry meets complex physics?[J]. Ange-wandte Chemie International Edition, 2009,48(1):60-103.
[36]	Wang Z L. Transmission electron microscopy of shape-controlled nanocrystals and their assemblies[J]. Journal of Physical Chemis-try B, 2000,104(6):1153-1175.
[37]	Jin M, He G, Zhang H, et al. Shape-controlled synjournal of copper nanocrystals in an aqueous solution with glucose as a reducing agent and hexadecylamine as a capping agent[J]. Angewandte Chemie International Edition, 2011,50(45):10560-10564.

实验编号	实验条件					实验结果（形貌,平均直径）
实验编号	c（CuCl₂）/ （mmol·L^-1）	c（ODA）/ （mmol·L^-1）	c（ODA）/ c（CuCl₂）	t/ h	T/ ℃	实验结果（形貌,平均直径）
1	12.50	12.50	1.00	48	180	无产物
2	12.50	25.00	2.00	48	180	八棱柱,220.6 nm
3	12.50	30.00	2.40	48	180	八棱柱,302.8 nm
4	12.50	37.50	3.00	48	180	八棱柱,472.5 nm
5	11.00	37.50	3.40	48	180	球线掺杂
6	25.00	37.50	1.50	48	180	无产物
7	50.00	37.50	0.75	48	180	无产物
8	12.50	37.50	3.00	48	160	无产物
9	12.50	37.50	3.00	48	140	无产物
10	12.50	37.50	3.00	48	120	无产物
11	12.50	25.00	2.00	36	180	无产物
12	12.50	25.00	2.00	24	180	无产物
13	12.50	37.50	3.00	36	180	无产物
14	12.50	37.50	3.00	24	180	无产物

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