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1、物理化學(xué)學(xué)~(WuliHuaxueXuebao1AugustActaP.一C..2013,29(8),1705—17111705[Article]doi:10.3866/PKU.WHXB201306043www.whxb.pku.edu.cnCMPO-離子液體萃取分離鈾(V1)體系的電化學(xué)性質(zhì)吳京珂沈興海弋陳慶德(北京大學(xué)化學(xué)與分子工程學(xué)院,放射化學(xué)與輻射化學(xué)重點學(xué)科實驗室,北京分子科學(xué)國家實驗室,北京100871)摘要:研究了辛基(苯基)一N,~_二異丁基胺甲酰基甲基氧化膦(CMPO).離子液體(1L)從硝酸鈾酰水溶液中萃取鈾(V1)的電化學(xué)行為,離子液體(1L)為1一丁基-3一甲基咪唑雙三
2、氟甲基磺酰亞胺鹽(CmimNTf2).用等摩爾系列法測得萃取過程中CMPO與u(vi)形成摩爾比為3:1的配合物.用循環(huán)伏安法研究了萃取液中u(v1).CMPO配合物的電化學(xué)性質(zhì),結(jié)果表明,在CmimNTf2中u(vo-CMPO配合物經(jīng)過準(zhǔn)可逆還原生成U(V).CMPO配合物,u(vi)/u(v)電對的表觀氧化還原電勢(Ee,VSFc/Fc)為(一0.885~0.008)對萃取液進(jìn)行控制電位電解,發(fā)現(xiàn)在鉑片上有沉淀析出.X射線光電子能譜(XPS)測試結(jié)果表明,沉積物中只含有u(vi)、u(iv)~u氧,而CMPO和C4mimNTf2沒有被夾帶析出.關(guān)鍵詞:鈾:離子液體:萃?。貉h(huán)伏安:電沉積中
3、圖分類號:0646ElectrochemicalBehavioroftheSystemofUranium(VI)ExtractionwithCMPO-IonicLiquidWUJing—KeSHENXing—HaiCHENQing—De(BeijingNationalLaboratoryfo,MolecularSciences,RadiochemistryandRadiationChemistryKeyLaboratoryofFundamentalScience,CollegeofChemistryandMolecularEngineering,PeMngUniversity,Beijing1
4、00871,PR.China)Abstract:TheelectrochemicaIbehaviorofu(vl1extractedfromanaqueoussolutionofuranylnitratebyoctyl(pheny1)-N,N-diisobutylcarbamoylmethylphosphineoxide(CMPO)inanionicliquidwasinvestigated.Thehydrophobicionicliquid1-butyl一3一methylimidazoliumbis(trifluoromethylsulfony1)imide(C4mimNTf2)wasuse
5、dinthisstudy.Usinganequimolarseriesmethod,wefoundthatCMPOandu(vI)formeda3:1molarcomplexduringtheextractionprocess.CyclicvoltammetrywasusedtoinvestigatetheelectrochemicalbehavioroftheU(V1).CMPOcomplexinC4mimNTf2.Theu(vI).CMPOcomplexwasfoundtobequasireversiblyreducedtoaU(V).CMP0complex.Theformalredoxp
6、otential(,VSFc/Fc)fortheu(vi)/U(V)couplewasdeterminedtobe(一0.885~0.008)Controlled.potentialelectrolysisoftheextractgaveadepositonthesurflaceofaplatinumplate.X-rayphotoelectronspectroscopyshowedthatthedepositcontainedonlyu(vi),u(iv),andoxygen,andtheCMPOextractantandtheionicliquidwerenottrappedinthede
7、posit.KeyWords:Uranium:Ionicliquid;Extraction;Cyclicvoltammetry;Electrodeposition1引言有機鹽類,具有不揮發(fā)性、不可燃性、熱及化學(xué)穩(wěn)定離子液體(IL)是一類由有機陽離子和有機或無性高、電化學(xué)窗口寬以及離子電導(dǎo)率高等諸多特機陰離子構(gòu)成的,在室溫或室溫附近呈液體狀態(tài)的性.離子液體用于核燃料后處理過程,可以解決使Receiv