纳米氧化亚铜热力学函数的温度效应研究
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摘要
可控制备了Cu_2O纳米微晶,采用扫描电镜(SEM)、X-射线粉末衍射仪(XRD)对其形貌进行了表征。基于纳米材料与块体材料表面相的差异,采用原位微热量技术结合热动力学原理获取了纳米Cu_2O微晶体系与HNO3反应的动力学参数和热力学函数,并讨论了温度对其反应动力学和表面热力学性质的影响。结果表明,在298.15K时,纳米Cu_2O的摩尔表面Gibbs自由能为0.536kJ·mol~(-1)、摩尔表面焓为44.012kJ·mol~(-1)、摩尔表面熵为145.819J·mol~(-1)·K~(-1);块体Cu_2O和纳米Cu_2O的反应速率常数、标准摩尔反应焓、摩尔表面Gibbs自由能和摩尔表面焓均随着温度的升高而增大。
We controlled prepared cuprous oxide nanocrystalline,and characterized its morphology by SEM and XRD.On the basis of the difference of surface phase between nano materials and bulk materials,we obtained the kinetic parameters and thermodynamic functions of the reaction between nano cuprous oxide system and nitric acid by in situ microcalorimetry technique and thermodynamic principle.Furthermore,we discussed the influence of temperature on the reaction kinetics and surface thermodynamics of nano cuprous oxide.The results show that the molar surface Gibbs free energy,molar surface enthalpy,and molar surface entropy of nano cuprous oxide are 0.536 kJ·mol~(-1),44.012 kJ·mol~(-1),and 145.819 J·mol~(-1)·K~(-1) at 298.15 K,respectively.The reaction rate constants,standard molar reaction enthalpy,molar surface Gibbs free energy,and molar surface enthalpy of bulk cuprous oxide and nano cuprous oxide increase with increasing of temperature.
We controlled prepared cuprous oxide nanocrystalline,and characterized its morphology by SEM and XRD.On the basis of the difference of surface phase between nano materials and bulk materials,we obtained the kinetic parameters and thermodynamic functions of the reaction between nano cuprous oxide system and nitric acid by in situ microcalorimetry technique and thermodynamic principle.Furthermore,we discussed the influence of temperature on the reaction kinetics and surface thermodynamics of nano cuprous oxide.The results show that the molar surface Gibbs free energy,molar surface enthalpy,and molar surface entropy of nano cuprous oxide are 0.536 kJ·mol~(-1),44.012 kJ·mol~(-1),and 145.819 J·mol~(-1)·K~(-1) at 298.15 K,respectively.The reaction rate constants,standard molar reaction enthalpy,molar surface Gibbs free energy,and molar surface enthalpy of bulk cuprous oxide and nano cuprous oxide increase with increasing of temperature.
引文
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[2]宁远.纳米材料的奇异表面效应[J].有色金属工程,2001,53(3):91.
[3] LI H J.Fluorescence resonance energy transfer-based biosensor between graphene quantum dots and gold nanopaticles for optical diagnostic of staphylococcus aureus oligonucleotide[J].Journal of the American Medical Directors Association,2014,11(3):B18.
[4] NEGISHI R,HASEGAWA T,TANAKA H,et al.Size-dependent single electron tunneling effect in Au nanoparticles[J].Surface Science,2007,601(18):3907-3911.
[5]许仪,薛永强,崔子祥,等.粒度对纳米氧化镍化学反应平衡常数的影响[J].太原理工大学学报,2010,41(4):345-348.XU Y,XUE Y Q,CUI Z X,et al.Effect of the particle size of nano-NiO reaction equilibrium constant[J].Journal of Taiyuan University of Technology,2010,41(4):345-348.
[6] DAN Z H,YANG Y L,CHANG H,et al.Facile fabrication of Cu2O nanobelts in ethanol on nanoporous Cu and their photodegradation of methyl orange[J].Materials,2018,11(3):446.
[7]陆梦甜,朱长俊,师苑,等.细菌纤维素/氧化亚铜膜的抗菌性能及机制研究[J].合成纤维,2017,46(11):10-12.LU M T,ZHU C J,SHI Y,et al.Study on antibacterial properties and mechanism of bacterial cellulose/cuprous oxide membrane[J].Synthetic Fiber in China,2017,46(11):10-12.
[8] XU K,YAN H,TAN C F,et al.Hedgehog inspired CuO nanowires/Cu2O composites for broadband visible-light:driven recyclable surface enhanced Raman scattering[J].Advanced Optical Materials,2018:1701167.
[9] TU K,WANG Q,LU A,et al.Portable visible-light photocatalysts constructed from Cu2O nanoparticles and graphene oxide in cellulose matrix[J].Journal of Physical Chemistry C,2014,118(13):7202-7210.
[10]沈成灵,李原芳,祁文静,等.氧化亚铜纳米微粒与金黄色葡萄球菌的相互作用[J].中国科学:化学,2008,38(12):1100-1104.SHEN C L,LI Y F,QI W J,et al.Interaction between copper oxide nanoparticles and Staphylococcus aureus[J].Scientia Sinica:Chimica,2008,38(12):1100-1104.
[11] WANG J,CUI F L,CHU S B,et al.In situ growth of noble-metal nanoparticles on Cu2O nanocubes for surface-enhanced Raman scattering detection[J].Chempluschem,2014,79(5):619.
[12]刘晓林,王路得,黄在银,等.纳米氧化锌热力学函数的微量热法及电化学法测量[J].高等学校化学学报,2015,36(3):539-543.LIU X L,WANG L D,HUANG Z Y,et al.Thermodynamic functions of nano zinc oxide acquired by microcalorimetry and electrochemical methods[J].Chemical Journal of Chinese Universities,2015,36(3):539-543.
[13]薛永强,赵红,杜建平.纳米氧化铜的粒度对多相反应动力学参数的影响[J].无机化学学报,2006,22(11):1952-1956.XUE Y Q,ZHAO H,DU J P.Effect of particle size on kinetic parameters of heterogeneous reaction[J].Chinese Journal of Inorganic Chemistry,2006,22(11):1952-1956.
[14]王路得,黄在银,范高超,等.电化学方法测定纳米材料的热力学函数[J].中国科学:化学,2012,42(1):47-51.WANG L D,HUANG Z Y,FAN G C,et al.Determination of thermodynamic functions for nano-materials viathe electrochemical method[J].Scientia Sinica:Chimica,2012,42(1):47-51.
[15] CHEUNG W H,SZETO Y S,MCKAY G.Enhancing the adsorption capacities of acid dyes by chitosan nano particles[J].Bioresource Technology,2009,100(3):1143-1148.
[16] LI X X,WAN T,QIU J Y,et al.In-situ photocalorimetry-fluorescence spectroscopy studies of RhB photocatalysis over Zscheme g-C3N4@Ag@Ag3PO4,nanocomposites:apseudo-zeroorder rather than a first-order process[J].Applied Catalysis B:Environmental,2017,217:591-602.
[17] CHAKRABORTY I,UDAYABHASKARARAO T,PRADEEP T.Luminescent sub-nanometer clusters for metal ion sensing:a new direction in nanosensors[J].Journal of Hazardous Materials,2012,211-212(2):396-403.
[18]肖明,黄在银,汤焕丰,等.Ag3PO4表面热力学性质及光催化原位过程热动力学的晶面效应[J].物理化学学报,2017,33(2):399-406.XIAO M,HUANG Z Y,TANG H F,et al.Facet effect on surface thermodynamic properties and in-situphotocatalytic thermokinetics of Ag3PO4[J].Acta Physico-Chimica Sinica,2017,33(2):399-406.
[19]汤焕丰,黄在银,肖明.立方体纳米Cu2O表面热力学函数的粒度及温度效应[J].物理化学学报,2016,32(11):2678-2684.TANG H F,HUANG Z Y,XIAO M.Effects of particle size and temperature on surface thermodynamic functions of cubic nanoCu2O[J].Acta Physico-Chimica Sinica,2016,32(11):2678-2684.
[20]高胜利,陈三平,胡荣祖,等.化学反应的热动力学方程及其应用[J].无机化学学报,2002,18(4):362-366.GAO S L,CHEN S P,HU R Z,et al.Derivation and application of thermodynamic equations[J].Chinese Journal of Inorganic Chemistry,2002,18(4):362-366.
[21]漆德瑶.物理化学中的量、单位和符号[M].北京:科学技术文献出版社,1991.QI D Y.Quantities,Units and Symbols in Physical Chemistry[M].Beijing:Science and Technology Literature Press,1991.
[22] J·A·迪安.兰氏化学手册[M].第15版.北京:科学出版社,2003.DEAN J A.Lange′s Handbook of Chemistry[M].15th Edition.Beijing:Science Press,2003.