固体无机化学第五

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1、第五章层状与多孔材料5.1层状材料5.2多孔材料嵌入反应:客体分子或离子插入到固体晶格中而没有引起固体结构很大重组的一类固相反应:xG+x[H]Gx[H]反应条件:1)主体晶格结构包含很强的共价网络,并在反应过程中保持不变;2)结构中存在相互联系的空位,其大小适当,允许客体分子扩散进入固体.嵌入反应类型:1)离子交换或分子交换反应,骨架层电荷不变.粘土、层状硅酸盐、三元金属钛酸盐、铌酸盐等2）氧化还原反应，骨架层电荷改变xG++xe-+x[H]Gx[H]举例:1.过渡金属二硫族化合物MX2(M=Ti,Zr,

2、Hf,V,Nb,Ta,Mo,W)(X=S,Se,Te)Energygap:1.23-1.69eVMetastable:1T-MoS2(CdI2-type),3R-MoS2Stable:2H-MoS2MoS2结构Anisotropy:parallel(10cm),perpendicular(1000times)Reactivity:areservoirofbothelectricchargeandchemicalspeciesCatalysis:hydrogenationH2sensor:changeelect

3、ricalconductivityPhotoelectrochemicalpropertyLubricantpropertyIntercalation:BatteryoperationLixMoS2Intercalatedbypolymers嵌入反应:MX2+碱金属(A)AxMX2MX2+A/液NH3Ax(NH3)yMX2AMX2+H2OAx(H2O)yMX2+(1-x)A++(1-y)OH-+(1-y)/2H2NaxTiS2+H2ONa0.5(H2O)yTiS2NaxTaS2+H2ONa0.33(H2O)yT

4、aS2NaxMoS2+H2ONa0.1(H2O)yMoS2Na0.33TaS2胶体[Fe6S8(PEt3)6]xTaS2MX2+液NH3(NH3)MX2(NH3)0.5MX2TaS2+py(py)0.5TaS2TaS2+Co(-C5H5)2[Co(-C5H5)2]0.25TaS2LixTiS22.MPS3,MPSe3MPS3=M2/3(P2)1/3S2,与MX2相关物理性质:1)根据能隙大小不同,可以是半导体或绝缘体;2)过渡金属体系有磁性.嵌入反应:NiPS3+过量LiBunLixNiPS3(X<1.2)

5、xG++MPX3G+x[M2+1-x/2x/2PX3]Ni(H2O)2+6+K0.40[Mn0.80PS3].0.9H2ONi0.28Mn0.72PS33.MOCl(M=Fe,Ti,V,Cr)Intercalationreactions:FeOCl+AAxFeOCl(A=碱金属)AxFeOCl+H2OAx’(H2O)yFeOClFeOCl+FeCp2[FeCp2]xFeOClFeOCl+TTF(TTF)xFeOClFeOCl+py(py)1/3FeOCl4.层状过渡金属氧化物MoO3V2O5MOXO4(M=V,

6、Nb,Ta;X=P,As)Intercalationreactions:MoO3+H+HxMoO3H0.5MoO3+py(py)0.3H0.5MoO3Na0.5(H2O)yMoO3Na0.5-xHx(H2O)yMoO3H0.5(H2O)yMoO3H0.5MoO3V2O5+LiLixV2O5(x<2.0)V2O5+H+HxV2O5VOPO4+pyVOPO4.pyVOPO4+4,4’-bipyVOPO4.(4,4’-bipy)0.5Chem.Mater.2003,15,1941.5.LayeredDoubleHyd

7、roxides(LDHs)Mg(OH)2[M2+1-xM3+x(OH)2]An-x/n.MH2OM2+=Mg,Fe,Co,Cu,Ni,Cd,ZnM3+=Al,Cr,Ga,FeAnionsexchangable:carbonates,halides,nitrates,sulfates,bisphosphonatespolyoxometalatesanions,Fe(CN)64-,porphyrinsphthalocyanines,aminoacidsChem.Mater.2004,16,975.LDH+(NH4)

8、6[H4Co2Mo10O38]Chem.Mater.2004,16,1214.Inorg.Chem.2004,42,4243.J.-H.Choyetal.Angew.Chem.Int.Ed.2000,30,4042.D.T.Tranetal.J.Am.Chem.Soc.2002,124,3966.[Pb3F5]NO3K2CrO4第五章层状与多孔材料5.1层状材料5.2多孔材料按结构特征