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：2012-12-05。：2013-01-17。(No.21077050,21277069)、“”(No.IRT1019)、“863”(No.2012AA062607)。＊。E-mail：zhaoyixu@nju.edu.cnTel：(025)89680370-宗恩敏魏丹还中科彭渡万海勤郑寿荣许昭怡*(南京大学环境学院，污染控制与资源化研究国家重点实验室，南京210023)：-，。，；。，，，。-Freundlich，，。pH，，F-＞NO3-≈SO42-，F-，NO3-SO42-。：；；；：O613.71；O613.62:A:1001-4861(2013)05-0965-08DOI：10.3969/j.issn.1001-4861.2013.00.154AdsorptionofPhosphatebyZirconiaFunctionalizedMulti-walledCarbonNanotubesZONGEn-MinWEIDanHUANZhong-KePENGDuWANHai-QinZHENGShou-RongXUZhao-Yi＊(StateKeyLaboratoryofPollutionControlandResourceReuse,andSchooloftheEnvironment,NanjingUniversity,Nanjing210023,China)Abstract:Zirconiafunctionalizedmulti-walledcarbonnanotubesweresuccessfullysynthesizedbyhydrothermalmethodandtheiradsorptionbehaviorforphosphatewerealsoinvestigated.CharacterizedresultsshowedthattheBETsurfaceareasandthetotalporevolumesofMWNTsdecreasedgreatlyafterZrO2functionalization.TheaverageparticlesizeofzirconiathatuniformlydispersedonthesurfaceofMWNTsincreasedwithincreasingZrO2content.PhosphateadsorptionexperimentalresultsshowedthatdecreasingZrO2particlesizewasbeneficialtoimprovetheZrO2content-normalizedadsorptionamountandtheadsorptionrate.TheadsorptionisothermcouldbewellfittedbyFreundlichequationwhichsuggestedapreferentialadsorption,whilekineticsfollowedthepseudo-second-ordermodel.LowerionicstrengthandpHwerefavorabletotheremovalofphosphate.Andtheeffectofco-existinganionswasintheorderofF-＞NO3-≈SO42-.Keywords:multi-walledcarbonnanotube;phosphate;adsorption;ZrO20，[1-2]。，[3-6]、[7-8][9-12]，、、。[13-14]、[15-16]、[17-19]。，。Liu[16]，ZrO229520135Vol．29No．5965-972CHINESEJOURNALOFINORGANICCHEMISTRY29，，。，，，(、、)，，Long[20]Fe-Zr；Sarkar[21]Fe3O4@mZrO2；Zhu[22]；Tang[19]SBA-15，。，，。、[23-24]，，，。-，，，、、pH、。，。11.1(MWNT，95%，20~40nm，)；(C6H8O6，AR，)；(NaClO)、(HNO3)、(ZrOCl2·8H2O)、(HCl)、(NaOH)、(NaCl)、(KH2PO4)、((NH4)6Mo7O24·4H2O)、(KSbC4H4O7·0.5H2O)，，。，110℃2h，；。1.21.2.1：5.0g350℃1h，；，250mL70%，0.5h，85℃4h，，。1.0g，1h，140℃8h，，MWNT-0。：100mg80mL(2、4、10mmol·L-1)，0.5h，150℃15h，，，，110℃12h，MWNT-2、MWNT-4、MWNT-10。1.2.2JEOLJEM-200CX，X(XRD)ARLXTRAX(CuKα，λ=1.540562nm，40kV，40mA，2θ=10°~70°)，UIVAC-PHIPHI5000VersaProbe；-MicromeriticsASAP2020，BET(Brunauer-Emmett-Teller)，P/P0=0.05~0.35，BJH。1.31.3.1：2.1971g，1L，500mg·L-1。(20.0±0.1)mg40mLEPA，，。，，pH(6.0±0.2)，24h。，Ce[25]UnicoUV-2000，700nm，Qe：Qe=(C0-Ce)×Vm(1)，C0Ce，mg·L-1；V，L；m，g。9665：-1.3.2(200.0±0.1)mg500mL，400mLpH(6.0±0.2)，，，1.5mL。QtQt=(C0-Ct)×Vm(2)，C0Ctt，mg·L-1；V，L；m，g。1.3.3pH(0、0.05、0.50mg·L-1)NaCl，1.3.1，50mgP·L-1，MWNT-10，(20.0±0.1)mg，pH0.1mol·L-1HCl0.1mol·L-1NaOH2~11。1.3.40~900mg·L-1(F-、NO3-、SO42-)，0.5g·L-1，25℃24h。，，(1)。22.11(MWNT)TEM。1(a)，，。，，，1(b)(c)；，，，，1(d)。1TEM：(a)MWNT-0；(b)MWNT-2；(c)MWNT-4；(d)MWNT-10Fig.1TEMimagesfor(a)MWNT-0;(b)MWNT-2;(c)MWNT-4;(d)MWNT-10[26]，：ds=Σnidi3Σnidi2(3)，ds，nm；nidi；dii，nm。，Σni100。，MWNT-22.56~2.84nm，MWNT-43.58~3.90nm，MWNT-104.52~5.24nm。1，，，，MWNT-21Table1StructuralpropertiesofthesamplesSamplesds/nmZrO2contenta/wt%BETsurfacearea/(m2·g-1)Totalporevolumeb/(cm3·g-1)MWNT-0--198.690.55MWNT-22.7716.40186.150.52MWNT-43.7425.60184.200.43MWNT-104.9145.60175.540.35aDeterminedbyX-rayfluorescence;bObtainedatP/P0=0.99967292.77nmMWNT-104.91nm；；，，，。2/，，IV，P/P0=0.5~1.0，H1，，。，，，。3XRD。3(a)，2θ=26.2°(002)[27]，2θ=43.5°。，2θ=26.2°，2θ=43.5°，，；，2θ=30°[28]。2.22.2.125℃4。，，，；，，MWNT-10MWNT-4MWNT-2，。72.4mg·L-1，MWNT-10、MWNT-4、MWNT-217.60、13.8410.38mg·g-1，XRF，Q′=Qew，Q′，mg·g-1ZrO2；Qe，mg·g-1；w，%。338.60mg·g-1ZrO2、54.06mg·g-1ZrO263.29mg·g-1ZrO2，[16]，。，MWNT-10＜MWNT-4＜MWNT-2，MWNT-2，。MWNT-2，，；MWNT-102/Fig.2N2adsorption-desorptionisothermsofsamples(a)MWNT-0;(b)MWNT-2;(c)MWNT-4;(d)MWNT-103XRDFig.3XRDpatternsofsamples4-Fig.4PhosphateadsorptionisothermsonZrO2functionalizedMWNTs96852Table2ParametersofphosphateadsorptionisothermsonZrO2functionalizedMWNTsSamplesLangmuirmodelb/(L·mg-1)Qm/(mg·g-1)Kf/(mg1-n·Ln·g-1)R2MWNT-20.0511.601.030.9680MWNT-40.1511.402.270.9815MWNT-100.2413.023.480.9658Freundlichmodeln1.812.332.74R20.97870.87950.85765MWNT-10Fig.5PhosphateadsorptionisothermsonMWNT-106-Fig.6PhosphateadsorptionkineticsonZrO2functionalizedMWNTs：-，，，，。LangmuirFreundlich，Langmuir，：1Qe=1QmbCe+1Qm(4)，Qe，mg·g-1；Qm，mg·g-1；bLangmuir；Ce，mg·L-1。Freundlich，：lgQe=1nlgCe+lgKf(5)，Qe，mg·g-1；n；Ce，mg·L-1；KfFreundlich，。2。2，Freundlich(R20.9)，3；，n1，[29]，MWNT-10Kf，。，，MWNT-10，5。5，MWNT-10；，；，MWNT-10；，。，MWNT-10，[30]。，，，；，，，MWNT-10。2.36-，38.3mg·L-1。，3200min，969294MWNT-10Table4SimulationresultsofPhosphateadsorptionkineticsonMWNT-10atdifferentinitialconcentrationsC0/(mg·L-1)Qexp/(mg·g-1)FirstorderkineticsSecondorderkineticsk1/(min-1)Qe/(mg·g-1)k2/(g·mg-1·min-1)Qe/(mg·g-1)R217.76.660.71×10-20.770.066.680.999938.39.961.52×10-20.960.099.98147.411.190.53×10-20.520.1111.201R20.61370.70540.40403-Table3SimulationresultsofphosphateadsorptionkineticsonZrO2functionalizedMWNTsSamplesQexp/(mg·g-1)FirstorderkineticsSecondorderkineticsk1/min-1Qe/(mg·g-1)k2/(g·mg-1·min-1)Qe/(mg·g-1)R2MWNT-25.361.57×10-20.280.525.351MWNT-48.231.54×10-20.770.198.241MWNT-109.961.52×10-20.960.099.981R20.69320.67740.70547MWNT-10Fig.7PhosphateadsorptionkineticsonMWNT-10atdifferentinitialconcentrationsMWNT-10＞MWNT