ZHOU Bai-Bin *,1,2 WEI Yong-De 1 LI Zhong-Hua 1 ( 1 Department of Applied Chemistry,Ha rbin Institute of Technology ￡?Harbin￡±￡ì￡°￡°￡°￡±￡(c)( 2 Department of Chemistry,Harbin Norm...ZHOU Bai-Bin *,1,2 WEI Yong-De 1 LI Zhong-Hua 1 ( 1 Department of Applied Chemistry,Ha rbin Institute of Technology ￡?Harbin￡±￡ì￡°￡°￡°￡±￡(c)( 2 Department of Chemistry,Harbin Normal University￡?Harbin￡±￡ì￡°￡°￡?￡°￡(c) The air-solid interface reaction of Ce,Lu with K10 H 3[Gd (SiMo 4 W￡*O￡3￡1￡(c) 2]through chemistry-heated permeation is reported for the fi rst time￡(r)The permeated complex is characterized by ICP and the result shows tha t the mini mum Ce,Lu can permeate into the inner sph ere of K 10 H ￡3 ￡?Gd ￡¨SiMo ￡′ W ￡* O ￡3￡1 ￡(c) 2]The IR ,XRD patterns give the eviden ce that after permeation the comple x still keeps the Keggin structure,howe ver,its crystal structure is different from the complex before permeation￡(r)The cond uctivity of the permeated complex has been measured with the four-electr ode method and the data show that the co nductivity of the complex after permeation is 10 6 times higher than that of the sample before permeation and reaches ￡′￡(r)84 6×10 -1 S·cm -1 ￡(r)These indicate that the permeated c omplex is a good solid electrolyte and further appli cations are also expected￡(r)展开更多
Eight new complexes were synthesize d for the first time.The compounds which have the general formula K x H 2 [PM(OH 2 )Mo 7 W 2 V 2 O 39 ]·nH 2 O(M=Cr 3+ ,Mn 2+ ,Fe 3+ ,Co 3+ ,Ni 2+ ,Cu 2+ ,Zn 2+ ,Cd 2+ ;x=4or 5...Eight new complexes were synthesize d for the first time.The compounds which have the general formula K x H 2 [PM(OH 2 )Mo 7 W 2 V 2 O 39 ]·nH 2 O(M=Cr 3+ ,Mn 2+ ,Fe 3+ ,Co 3+ ,Ni 2+ ,Cu 2+ ,Zn 2+ ,Cd 2+ ;x=4or 5)were de-termined by conductance titration a nd elemental analysis.The analysis of IR,UV,XRD and ESR show that the products hold the Keggin structure a nd TG-DTA,IR,XRD at various tempera tures and water solubility test also give the evidences that the range of pyrolysis temperature is 300～350℃.T he study on the substitutional reaction of coordinated water by optical ligand quinine shows that the S N 2nucleophilic substitution occure s when Ni is con-tained in the compound and S N 1nucleophilic substitution occure s when Cu is contained.These also con firmed that the transitional metals are in the in ner sphere of the complexes.展开更多
The substitution reaction of quinin e by the 18types of heteropoly comple xes,for these formed compounds are Keggin structure and the molecular f ormulas arXM 11 O 39 M’ (OH) 2 6- (X =Si,Ge,P;M=Mo or W;M’ =Co,Ni,Cu)...The substitution reaction of quinin e by the 18types of heteropoly comple xes,for these formed compounds are Keggin structure and the molecular f ormulas arXM 11 O 39 M’ (OH) 2 6- (X =Si,Ge,P;M=Mo or W;M’ =Co,Ni,Cu),was studied by the means of phase tra nsfer.The results of characterization that were accomplished by UV and ESR indicated that the quinine does f orm the chemical bond with the hetrop oly ligands.Spectral experiment demonstrated that the structure held the same when the heteropoly comple x contained Cu 2+ was reacted with qui-nine,while the heteropoly complex c ontained Ni 2+ resulted in the changing of the structure.Such a result of op-tical rotatory opticity testified t hat quinine reacting with heteropoly acid contained transitional metals could form a kind of new complexes which were opti cal rotation.展开更多
合成了未见报道的标题配合物。通过化学分析、ICP和TG曲线确定了其化学式为K_8H_3[Y(PW_(11)O_(39))_2]·25H_2O;利用IR、UV、XRD、^(183)W-NMR、循环伏安等手段对其结构进行了表征,结果表明杂多阴离子为β_2型Keggin结构。采用稀...合成了未见报道的标题配合物。通过化学分析、ICP和TG曲线确定了其化学式为K_8H_3[Y(PW_(11)O_(39))_2]·25H_2O;利用IR、UV、XRD、^(183)W-NMR、循环伏安等手段对其结构进行了表征,结果表明杂多阴离子为β_2型Keggin结构。采用稀土多元渗的方法对配合物进行了气相热扩渗,经ICP和XPS测试表明:微量的稀土元素La和Ce可以渗入到配合物的体相,并与组份元素存在键合作用。扩渗后化合物的化学式为K_8H_6YLa_(0.11)Ce_(0.18)P_2W_4~ⅤW_(18)~ⅥO_(78)·15H_2O,其晶体属单斜晶系,晶胞参数:a=6.3775nm,b=3.6771nm,c=3.7727nm,β=90.192°,V=88.47326nm^3;导电性的测试结果表明:室温时,扩渗后试样的电导率提高了约10~3倍,且热稳定范围变宽,523K时的电导率为1.33×10^(-2)S·cm^(-1),有望成为实用化的导电材料;~1H MAS NMR测试结果表明其存在三种质子,其导电机理可能是质子导电。展开更多
文摘ZHOU Bai-Bin *,1,2 WEI Yong-De 1 LI Zhong-Hua 1 ( 1 Department of Applied Chemistry,Ha rbin Institute of Technology ￡?Harbin￡±￡ì￡°￡°￡°￡±￡(c)( 2 Department of Chemistry,Harbin Normal University￡?Harbin￡±￡ì￡°￡°￡?￡°￡(c) The air-solid interface reaction of Ce,Lu with K10 H 3[Gd (SiMo 4 W￡*O￡3￡1￡(c) 2]through chemistry-heated permeation is reported for the fi rst time￡(r)The permeated complex is characterized by ICP and the result shows tha t the mini mum Ce,Lu can permeate into the inner sph ere of K 10 H ￡3 ￡?Gd ￡¨SiMo ￡′ W ￡* O ￡3￡1 ￡(c) 2]The IR ,XRD patterns give the eviden ce that after permeation the comple x still keeps the Keggin structure,howe ver,its crystal structure is different from the complex before permeation￡(r)The cond uctivity of the permeated complex has been measured with the four-electr ode method and the data show that the co nductivity of the complex after permeation is 10 6 times higher than that of the sample before permeation and reaches ￡′￡(r)84 6×10 -1 S·cm -1 ￡(r)These indicate that the permeated c omplex is a good solid electrolyte and further appli cations are also expected￡(r)
文摘Eight new complexes were synthesize d for the first time.The compounds which have the general formula K x H 2 [PM(OH 2 )Mo 7 W 2 V 2 O 39 ]·nH 2 O(M=Cr 3+ ,Mn 2+ ,Fe 3+ ,Co 3+ ,Ni 2+ ,Cu 2+ ,Zn 2+ ,Cd 2+ ;x=4or 5)were de-termined by conductance titration a nd elemental analysis.The analysis of IR,UV,XRD and ESR show that the products hold the Keggin structure a nd TG-DTA,IR,XRD at various tempera tures and water solubility test also give the evidences that the range of pyrolysis temperature is 300～350℃.T he study on the substitutional reaction of coordinated water by optical ligand quinine shows that the S N 2nucleophilic substitution occure s when Ni is con-tained in the compound and S N 1nucleophilic substitution occure s when Cu is contained.These also con firmed that the transitional metals are in the in ner sphere of the complexes.
文摘The substitution reaction of quinin e by the 18types of heteropoly comple xes,for these formed compounds are Keggin structure and the molecular f ormulas arXM 11 O 39 M’ (OH) 2 6- (X =Si,Ge,P;M=Mo or W;M’ =Co,Ni,Cu),was studied by the means of phase tra nsfer.The results of characterization that were accomplished by UV and ESR indicated that the quinine does f orm the chemical bond with the hetrop oly ligands.Spectral experiment demonstrated that the structure held the same when the heteropoly comple x contained Cu 2+ was reacted with qui-nine,while the heteropoly complex c ontained Ni 2+ resulted in the changing of the structure.Such a result of op-tical rotatory opticity testified t hat quinine reacting with heteropoly acid contained transitional metals could form a kind of new complexes which were opti cal rotation.
文摘合成了未见报道的标题配合物。通过化学分析、ICP和TG曲线确定了其化学式为K_8H_3[Y(PW_(11)O_(39))_2]·25H_2O;利用IR、UV、XRD、^(183)W-NMR、循环伏安等手段对其结构进行了表征,结果表明杂多阴离子为β_2型Keggin结构。采用稀土多元渗的方法对配合物进行了气相热扩渗,经ICP和XPS测试表明:微量的稀土元素La和Ce可以渗入到配合物的体相,并与组份元素存在键合作用。扩渗后化合物的化学式为K_8H_6YLa_(0.11)Ce_(0.18)P_2W_4~ⅤW_(18)~ⅥO_(78)·15H_2O,其晶体属单斜晶系,晶胞参数:a=6.3775nm,b=3.6771nm,c=3.7727nm,β=90.192°,V=88.47326nm^3;导电性的测试结果表明:室温时,扩渗后试样的电导率提高了约10~3倍,且热稳定范围变宽,523K时的电导率为1.33×10^(-2)S·cm^(-1),有望成为实用化的导电材料;~1H MAS NMR测试结果表明其存在三种质子,其导电机理可能是质子导电。
