化学还原法合成Cu纳米粒子（英文）
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摘要
通过室温化学还原合成Cu纳米粒子(CuN Ps)。采用硼氢化钠还原Cu~(2+)离子,并用聚乙烯吡咯烷酮进行稳定化处理。考察还原剂/前驱体盐(RA/PS)比值的变化对CuN Ps粒径和形貌的影响。利用紫外-可见光谱(UV-Vis)、X射线衍射(XRD)、扫描电镜(SEM)和透射电镜(TEM)对合成的材料进行表征。UV-Vis光谱显示,569 nm处存在一Cu NPs的等离激元峰;另一峰位于485 nm处,为Cu_2O的特征峰。XRD分析表明,合成的材料为fcc-Cu相,并含有少量的fcc-Cu_2O化合物。SEM和TEM研究显示,当RA/PS比值为2.6时,得到粒径约7 nm的半球形CuN Ps微粒。过量的聚乙烯吡咯烷酮稳定剂对于防止CuN Ps的氧化至关重要。另一方面,当RA/PS比在2.0～1.84范围内时,获得较大粒径的多面体形Cu_2O颗粒,最大粒径可达150nm。此外,在RA/PS比为1.66时,得到在其尖端具有量子限域效应的星形Cu_2O粒子。
Cu nanoparticles(Cu NPs) have been synthesized through an easy route by chemical reduction at room temperature. The Cu~(2+) ions were reduced and stabilized with sodium borohydride and polyvinylpyrrolidone, respectively. The effect of the variation of the reducing agent/precursor-salt(RA/PS) ratio on the size and morphology of the Cu NPs was evaluated. The synthesized material was studied by ultraviolet-visible(UV-Vis) spectroscopy, X-ray diffraction(XRD), scanning electron microscopy(SEM), and transmission electron microscopy(TEM). The UV-Vis spectra showed a Cu NPs plasmon peak at 569 nm and another peak belonging to Cu_2O at 485 nm. XRD analysis showed the fcc-Cu phase with a small amount of fcc-Cu_2O compound. SEM and TEM studies displayed that small semispherical Cu NPs of approximately 7 nm were obtained at the RA/PS ratio of 2.6. The excess of polyvinylpyrrolidone stabilizer played an essential role in preventing Cu NPs oxidation. On the other side, Cu_2O polyhedral particles with larger sizes up to 150 nm were identified in the RA/PS ratio range of 2.0-1.84. In addition, Cu_2O particles having star morphologies with quantum confinement at their tips were obtained at the RA/PS ratio of 1.66.
Cu nanoparticles(Cu NPs) have been synthesized through an easy route by chemical reduction at room temperature. The Cu~(2+) ions were reduced and stabilized with sodium borohydride and polyvinylpyrrolidone, respectively. The effect of the variation of the reducing agent/precursor-salt(RA/PS) ratio on the size and morphology of the Cu NPs was evaluated. The synthesized material was studied by ultraviolet-visible(UV-Vis) spectroscopy, X-ray diffraction(XRD), scanning electron microscopy(SEM), and transmission electron microscopy(TEM). The UV-Vis spectra showed a Cu NPs plasmon peak at 569 nm and another peak belonging to Cu_2O at 485 nm. XRD analysis showed the fcc-Cu phase with a small amount of fcc-Cu_2O compound. SEM and TEM studies displayed that small semispherical Cu NPs of approximately 7 nm were obtained at the RA/PS ratio of 2.6. The excess of polyvinylpyrrolidone stabilizer played an essential role in preventing Cu NPs oxidation. On the other side, Cu_2O polyhedral particles with larger sizes up to 150 nm were identified in the RA/PS ratio range of 2.0-1.84. In addition, Cu_2O particles having star morphologies with quantum confinement at their tips were obtained at the RA/PS ratio of 1.66.
引文
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[17] JEONG S, WOO K, KIM D, LIM S, KIM J S, SHIN H, XIA Y,MOON J. Controlling the thickness of the surface oxide layer on Cu nanoparticles for the fabrication of conductive structures by ink-jet printing[J]. Advanced Functional Materials, 2008, 18:679-686.
[18] KUMAR S, PARLETT C M A, ISAACS M A, JOWETT D V,DOUTHWAITE R E, COCKETT M C R, LEE A F. Facile synthesis of hierarchical Cu2O nanocubes as visible light photocatalysts[J].Applied Catalysis B:Environmental, 2016, 189:226-232.
[2] DERRICK M, JEFFREY G, WANG Ling-yan, LUO Jin, ZHONG Chuan-jian. Synthesis of size controlled and shaped copper nanoparticles[J]. Langmuir, 2007, 23:5740-5745.
[3] CHEN Shao-wei, SOMMERS J M. Alkanethiolate-protected copper nanoparticles:Spectroscopy, electrochemistry, and solid-state morphological evolution[J]. The Journal of Physical Chemistry B,2001, 105:8816-8820.
[4] LIU Qing-ming, ZHOU De-bi, YAMAMOTO Y, ICHINO R,MASAZUMI O. Preparation of Cu nanoparticles with Na BH4 by aqueous reduction method[J]. Transactions of Nonferrous Metals Society of China, 2012, 22:117-123.
[5] AYESHA K, AUDIL R, RAFIA Y, REN Chong. A chemical reduction approach to the synthesis of copper nanoparticles[J].International Nano Letters, 2016, 6:21-26.
[6] RAJA M, SUBHA J, ALI FATHILAH B, RYU S H. Synthesis of copper nanoparticles by electroreduction process[J]. Materials and Manufacturing Processes, 2008, 23:782-785.
[7] BLOSI M, ALBONETTI S, DONDI M, MARTELLI C, BALDI G.Microwave-assisted polyol synthesis of Cu nanoparticles[J]. Journal of Nanoparticle Research, 2011, 13:127-138.
[8] TYURNINA A E, SHUR V Ya, KOZIN R V, KUZNETSOV D,PRYAKHINA V I, BURBAN G V. Synthesis and investigation of stable copper nanoparticle colloids[J]. Physics of the Solid State,2014, 56:1431-1437.
[9] ZHU Hai-tao, ZHANG Can-ying, YIN Yan-sheng. Novel synthesis of copper nanoparticles:Influence of the synthesis conditions on the particle size[J]. Nanotechnology, 2005, 16:3079-3083.
[10] JAIN S, JAIN A, KACHHAWAH P, DEVRA V. Synthesis and size control of copper nanoparticles and their catalytic application[J].Transactions of Nonferrous Metals Society of China, 2015, 25:3995-4000.
[11] GIUFFRIDA S, COSTANZO L L, VENTIMIGLIA G,BONGIORNO C. Photochemical synthesis of copper nanoparticles incorporated in poly(vinyl pyrrolidone)[J]. Journal of Nanoparticle Research, 2008, 10:1183-1192.
[12] GRANATA G, YAMAOKA T, PAGNANELLI F, FUWA A. Study of the synthesis of copper nanoparticles:The role of capping and kinetic towards control of particle size and stability[J]. Journal of Nanoparticle Research, 2016, 18:133.
[13] YANG Ai-ling, LI Shun-pin, WANG Yu-jin, WANG Le-le, BAO Xi-chang, YANG Ren-qiang. Fabrication of Cu2O@Cu2O core-shell nanoparticles and conversion to Cu2O@Cu core-shell nanoparticles in solution[J]. Transactions of Nonferrous Metals Society of China,2015 25:3643-3650.
[14] SAMIM M, KAUSHIK N K, MAITRA A. Effect of size of copper nanoparticles on its catalytic behaviour in Ullman reaction[J].Bulletin of Materials Science, 2007, 30:535-540.
[15] ALZAHRANI E, AHMED R A. Synthesis of copper nanoparticles with various sizes and shapes:Application as a superior non-enzymatic sensor and antibacterial agent[J]. International Journal of Electrochemical Science, 2016, 11:4712-4723.
[16] HUANG Chien-hua, WANG H P, LIAO Chang-yu. Nanosize copper encapsulated carbon thin films on a dye-sensitized solar cell cathode[J]. Journal of Nanoscience and Nanotechnology, 2010, 10:1-4.
[17] JEONG S, WOO K, KIM D, LIM S, KIM J S, SHIN H, XIA Y,MOON J. Controlling the thickness of the surface oxide layer on Cu nanoparticles for the fabrication of conductive structures by ink-jet printing[J]. Advanced Functional Materials, 2008, 18:679-686.
[18] KUMAR S, PARLETT C M A, ISAACS M A, JOWETT D V,DOUTHWAITE R E, COCKETT M C R, LEE A F. Facile synthesis of hierarchical Cu2O nanocubes as visible light photocatalysts[J].Applied Catalysis B:Environmental, 2016, 189:226-232.