热分解法制备Cu空心微球及其光热转换性能
|
摘要
以甲酸铜-辛胺配合物为前驱体,油胺为表面活性剂,在熔化液态石蜡中通过热分解法单步制备Cu空心微球。利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射仪(XRD)、导热系数仪、紫外-可见-近红外分光光度计(UV-Vis-NIR)及光热转换测试装置表征Cu球,研究其光热转换性能,分析Cu空心微球的合成机理。结果表明:反应温度为110℃、反应时间为3h、油胺物质的量为0.005mol的条件下,能够获得Cu空心微球,其平均粒径为380nm,壁厚约为70nm。Cu空心微球的形成机理:油胺吸附的Cu纳米晶在界面能最小化的驱动下,沿着前驱体热分解反应,生成的气泡和液态石蜡所形成的气-液界面聚合生长而成。Cu空心微球悬浮液的热导率、光热转换性能均优于实心Cu悬浮液的。
Cu hollow microspheres were synthesized by thermal decomposition of Cu(II) formate-octylamine complexes in molten paraffin using oleyl amine(OA) as the surfactant. The synthesized products were investigated by means of scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray diffraction(XRD), thermal constant analyzer, UV-Vis-NIR and photo-thermal conversion test device. The relevant synthesis mechanism of Cu hollow microspheres was analyzed. The results show that Cu hollow microspheres can be obtained under the conditions of reaction temperature at 110℃, reaction time at 3 h and amount of OA at 0.005 mol, the average diameter and wall thickness of Cu hollow microspheres are about 380 nm and 70 nm, respectively. The formation mechanism of Cu hollow microspheres is that the primary Cu nanocrystals driven by minimizing the interface energy may aggregate around the gas-liquid interface between liquid paraffin and bubbles. The thermal conductivity and photo-thermal conversion performance of Cu hollow microspheres suspension are better than those of solid Cu.
Cu hollow microspheres were synthesized by thermal decomposition of Cu(II) formate-octylamine complexes in molten paraffin using oleyl amine(OA) as the surfactant. The synthesized products were investigated by means of scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray diffraction(XRD), thermal constant analyzer, UV-Vis-NIR and photo-thermal conversion test device. The relevant synthesis mechanism of Cu hollow microspheres was analyzed. The results show that Cu hollow microspheres can be obtained under the conditions of reaction temperature at 110℃, reaction time at 3 h and amount of OA at 0.005 mol, the average diameter and wall thickness of Cu hollow microspheres are about 380 nm and 70 nm, respectively. The formation mechanism of Cu hollow microspheres is that the primary Cu nanocrystals driven by minimizing the interface energy may aggregate around the gas-liquid interface between liquid paraffin and bubbles. The thermal conductivity and photo-thermal conversion performance of Cu hollow microspheres suspension are better than those of solid Cu.
引文
[1] LIU Q,GUO X,LI Y,et al.Synthesis of hollow Co structures with netlike framework[J].Langmuir the ACS Journal of Surfaces & Colloids,2009,25(11):6425-30.
[2] HOU H,JING M,YANG Y,et al.Sb porous hollow microsph-eres as advanced anode materials for sodium-ion batteries[J].Journal of Materials Chemistry A,2015,3(6):2971-2977.
[3] ZHANG X,WANG K,WANG Y,et al.Galvanic synthesis of uniform Au hollow microspheres using Pb colloidal templates and their surface-enhanced raman scattering properties[J].Science of Advanced Materials,2015,7(7):1310-1318.
[4] DAO V D,KIM S H,CHOI H S,et al.Efficiency enhancement of dye-sensitized solar cell using Pt hollow sphere counter electrode[J].Journal of Physical Chemistry C,2011,115(51):25529-25534.
[5] WANG A X,CHU D Q,WANG L M,et al.Template-free hydro-thermal synthesis of copper hollow microspheres:microstructure,formation mechanism and compression plasticity[J].RSC Adva-nces,2014,4(15):7545-7548.
[6] WU S,ZHU D,ZHANG X,et al.Preparation and melting/freezing characteristics of Cu/paraffin nanofluid as phase-change material (PCM)[J].Energy & Fuels,2010,24(3):1894-1898.
[7] LIU M S,LIN C C,TSAI C Y,et al.Enhancement of thermal conductivity with Cu for nanofluids using chemical reduction me-thod[J].International Journal of Heat & Mass Transfer,2006,49(17):3028-3033.
[8] WANG H,HE S,YU S,et al.Template-free synthesis of Cu2O hollow nanospheres and their conversion into Cu hollow nanospheres[J].Powder Technology,2009,193(2):182-186.
[9] XU L Y,KUANG D,HU W B,et al.Fabrication of Cu hollow microspheres by liquid reduction method[J].Journal of Nano-materials & Molecular Nanotechnology,2014,3(2):2324-8777.
[10] XU B,WANG B,ZHANG C,et al.Synthesis and light-heat conversion performance of hybrid particles decorated MWCNTs/paraffin phase change materials[J].Thermochimica Acta,2017,652:77-84.
[11] PENG Q,DONG Y,LI Y.ZnSe semiconductor hollow micro-spheres[J].Angewandte Chemie,2003,42(26):3027-3030.
[12] CHEN X,WANG Z,WANG X,et al.Synthesis of novel copper sulfide hollow spheres generated from copper (Ⅱ)-thiourea complex[J].Journal of Crystal Growth,2004,263(1/4):570-574.
[13] SHAO W,WANG Z,ZHANG Y,et al.Controlled synthesis of SnO2 hollow microspheres via a facile template-free hydroth-ermal route[J].Chemistry Letters,2005,34(4):556-557.
[14] CHEN Y,ZHANG Y,FU S.Synthesis and characterization of Co3O4,hollow spheres[J].Materials Letters,2007,61(3):701-705.
[15] GU F,LI C Z,WANG S F,et al.Solution-phase synthesis of spherical zinc sulfide nanostructures[J].Langmuir the ACS Journal of Surfaces & Colloids,2006,22(3):1329-1332.
[16] 方晓鹏.纳米流体热质传递机理及光学特性研究[D].南京:南京理工大学,2013.FANG X P.Research on heat and mass transfer mechanisms and optical character of nanofluids[D].Nanjing:Nanjing University of Science and Technology,2013.
[17] ZAMZAMIAN A H,JAMAL-ABADI M T.Thermal conduc-tivity of Cu and Al-water nanofluids[J].International Journal of Engineering,2013,26(8):821-828.
[18] SADRI R,AHMADI G,TOGUN H,et al.An experimental study on thermal conductivity and viscosity of nanofluids contai-ning carbon nanotubes[J].Nanoscale Research Letters,2014,9(1):151.
[19] AMROLLAHI A,HAMIDI A A,RASHIDI A M.The effects of temperature,volume fraction and vibration time on the thermo-physical properties of a carbon nanotube suspension (carbon nanofluid)[J].Nanotechnology,2008,19(31):315701.
[20] JANG S P,CHOI S U S.Role of brownian motion in the enhan-ced thermal conductivity of nanofluids[J].Applied Physics Lett-ers,2004,84(21):4316-4318.
[21] 段慧玲,宣益民.等离激元纳米流体的光热特性研究[J].中国科学:技术科学,2014(8):833-838.DUAN H L,XUAN Y M.Research on photo-thermal properties of plasmonic nanofluid[J].Scientia Sinica (Technologica),2014(8):833-838.
[22] OUBRE C,NORDLANDER P.Optical properties of metallodiel-ectric nanostructures calculated using the finite difference time domain method[J].Journal of Physical Chemistry B,2004,108(46):17740-17747.
[23] CHEN L,XU C,LIU J,et al.Optical absorption property and photo-thermal conversion performance of graphene oxide/water nanofluids with excellent dispersion stability[J].Solar Energy,2017,148:17-24.
[2] HOU H,JING M,YANG Y,et al.Sb porous hollow microsph-eres as advanced anode materials for sodium-ion batteries[J].Journal of Materials Chemistry A,2015,3(6):2971-2977.
[3] ZHANG X,WANG K,WANG Y,et al.Galvanic synthesis of uniform Au hollow microspheres using Pb colloidal templates and their surface-enhanced raman scattering properties[J].Science of Advanced Materials,2015,7(7):1310-1318.
[4] DAO V D,KIM S H,CHOI H S,et al.Efficiency enhancement of dye-sensitized solar cell using Pt hollow sphere counter electrode[J].Journal of Physical Chemistry C,2011,115(51):25529-25534.
[5] WANG A X,CHU D Q,WANG L M,et al.Template-free hydro-thermal synthesis of copper hollow microspheres:microstructure,formation mechanism and compression plasticity[J].RSC Adva-nces,2014,4(15):7545-7548.
[6] WU S,ZHU D,ZHANG X,et al.Preparation and melting/freezing characteristics of Cu/paraffin nanofluid as phase-change material (PCM)[J].Energy & Fuels,2010,24(3):1894-1898.
[7] LIU M S,LIN C C,TSAI C Y,et al.Enhancement of thermal conductivity with Cu for nanofluids using chemical reduction me-thod[J].International Journal of Heat & Mass Transfer,2006,49(17):3028-3033.
[8] WANG H,HE S,YU S,et al.Template-free synthesis of Cu2O hollow nanospheres and their conversion into Cu hollow nanospheres[J].Powder Technology,2009,193(2):182-186.
[9] XU L Y,KUANG D,HU W B,et al.Fabrication of Cu hollow microspheres by liquid reduction method[J].Journal of Nano-materials & Molecular Nanotechnology,2014,3(2):2324-8777.
[10] XU B,WANG B,ZHANG C,et al.Synthesis and light-heat conversion performance of hybrid particles decorated MWCNTs/paraffin phase change materials[J].Thermochimica Acta,2017,652:77-84.
[11] PENG Q,DONG Y,LI Y.ZnSe semiconductor hollow micro-spheres[J].Angewandte Chemie,2003,42(26):3027-3030.
[12] CHEN X,WANG Z,WANG X,et al.Synthesis of novel copper sulfide hollow spheres generated from copper (Ⅱ)-thiourea complex[J].Journal of Crystal Growth,2004,263(1/4):570-574.
[13] SHAO W,WANG Z,ZHANG Y,et al.Controlled synthesis of SnO2 hollow microspheres via a facile template-free hydroth-ermal route[J].Chemistry Letters,2005,34(4):556-557.
[14] CHEN Y,ZHANG Y,FU S.Synthesis and characterization of Co3O4,hollow spheres[J].Materials Letters,2007,61(3):701-705.
[15] GU F,LI C Z,WANG S F,et al.Solution-phase synthesis of spherical zinc sulfide nanostructures[J].Langmuir the ACS Journal of Surfaces & Colloids,2006,22(3):1329-1332.
[16] 方晓鹏.纳米流体热质传递机理及光学特性研究[D].南京:南京理工大学,2013.FANG X P.Research on heat and mass transfer mechanisms and optical character of nanofluids[D].Nanjing:Nanjing University of Science and Technology,2013.
[17] ZAMZAMIAN A H,JAMAL-ABADI M T.Thermal conduc-tivity of Cu and Al-water nanofluids[J].International Journal of Engineering,2013,26(8):821-828.
[18] SADRI R,AHMADI G,TOGUN H,et al.An experimental study on thermal conductivity and viscosity of nanofluids contai-ning carbon nanotubes[J].Nanoscale Research Letters,2014,9(1):151.
[19] AMROLLAHI A,HAMIDI A A,RASHIDI A M.The effects of temperature,volume fraction and vibration time on the thermo-physical properties of a carbon nanotube suspension (carbon nanofluid)[J].Nanotechnology,2008,19(31):315701.
[20] JANG S P,CHOI S U S.Role of brownian motion in the enhan-ced thermal conductivity of nanofluids[J].Applied Physics Lett-ers,2004,84(21):4316-4318.
[21] 段慧玲,宣益民.等离激元纳米流体的光热特性研究[J].中国科学:技术科学,2014(8):833-838.DUAN H L,XUAN Y M.Research on photo-thermal properties of plasmonic nanofluid[J].Scientia Sinica (Technologica),2014(8):833-838.
[22] OUBRE C,NORDLANDER P.Optical properties of metallodiel-ectric nanostructures calculated using the finite difference time domain method[J].Journal of Physical Chemistry B,2004,108(46):17740-17747.
[23] CHEN L,XU C,LIU J,et al.Optical absorption property and photo-thermal conversion performance of graphene oxide/water nanofluids with excellent dispersion stability[J].Solar Energy,2017,148:17-24.