The novel class of inorganic nanoclusters, \{\[AlO\-4Al\-\{12\}(OH)\-\{24\}(H\-2O)\-\{12\}\]\}\{\[SiW\-\{11\}O\-\{39\}CoCl\]\}\511H\-2O, \{\[AlO\-4Al\-\{12\}(OH)\-\{24\}(H\-2O)\-\{12\}\]\}\{\[P\-2W\-\{18\}O\-\{62\}\]\...The novel class of inorganic nanoclusters, \{\[AlO\-4Al\-\{12\}(OH)\-\{24\}(H\-2O)\-\{12\}\]\}\{\[SiW\-\{11\}O\-\{39\}CoCl\]\}\511H\-2O, \{\[AlO\-4Al\-\{12\}(OH)\-\{24\}(H\-2O)\-\{12\}\]\}\{\[P\-2W\-\{18\}O\-\{62\}\]\}Cl\533H\-2O and \{\[AlO\-4Al\-\{12\}(OH)\-\{24\}(H\-2O)\-\{12\}\]\}\-2\[NaP\-5W\-\{30\}O\-\{110\}\]\524H\-2O, consisting of Keggin cations and heteropolyoxometalates, has been synthesized and characterized by ICP, IR and NMR. It is proved that the intrinsic identities of Keggin cation and heteropolyanions of the clusters are preserved within the gels.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
Reaction of the trivacant heteropolyanions α A PW9O349- with CH3SiCl3 leads to the formation of the organosilyl derivative (TBA)3[α A PW9O34(CH3SiO)3(CH3Si)]. The crystal X ray diffraction analysis shows that the cr...Reaction of the trivacant heteropolyanions α A PW9O349- with CH3SiCl3 leads to the formation of the organosilyl derivative (TBA)3[α A PW9O34(CH3SiO)3(CH3Si)]. The crystal X ray diffraction analysis shows that the crystalbelongs to orthorhombic with space group Pca21, M=3177.09 and the unit cell parameters: a=25.761(5)?,b=14.519(3)?,c=24.396(5)?.V=9124(3)?3,Z=4,Dc=2.225g·cm-3,μ(MoKα)=11.438mm-1,F(000)=5464,R=0.0561,Rw=0.0866. The anion consists of one α A PW9O349- anion linked by three CH3SiO+ groups, whichattached to the fourth CH3Si through three Si O Si bridges.展开更多
Ainonic clays pillared by heteropolyoxometalate Zn2Al-PW11Z (Z= Cr3+ , Ti4+ and V5+) were synthesized via ion exchange reaction. The IR spectra and XRD patterns showed that the layered anions remained the integrity of...Ainonic clays pillared by heteropolyoxometalate Zn2Al-PW11Z (Z= Cr3+ , Ti4+ and V5+) were synthesized via ion exchange reaction. The IR spectra and XRD patterns showed that the layered anions remained the integrity of Keggin structure, and the gallery heights of the layered compounds were 1.01± 0.01 nm. The MAS NMR spectra of 27Al and 31P indicated the layered ahion had little effect on the Al of the octahedra center of the hydroalde, but the layer and octallydron VO6 had great effect on the P of the layered PW11V. The peak of 31P MAS NMR split to the two peaks of -11.867 ppm and -14.031 ppm whose corresponding area ratio is 2:1. All these results showed that the C2 axia of the heteropolyoxometalate in the layer was perpondicular to the brucite layer. Further experiments found that these compounds had high selectivity and activity for the esterification of acetic acid with n-butyl alcohol.展开更多
文摘The novel class of inorganic nanoclusters, \{\[AlO\-4Al\-\{12\}(OH)\-\{24\}(H\-2O)\-\{12\}\]\}\{\[SiW\-\{11\}O\-\{39\}CoCl\]\}\511H\-2O, \{\[AlO\-4Al\-\{12\}(OH)\-\{24\}(H\-2O)\-\{12\}\]\}\{\[P\-2W\-\{18\}O\-\{62\}\]\}Cl\533H\-2O and \{\[AlO\-4Al\-\{12\}(OH)\-\{24\}(H\-2O)\-\{12\}\]\}\-2\[NaP\-5W\-\{30\}O\-\{110\}\]\524H\-2O, consisting of Keggin cations and heteropolyoxometalates, has been synthesized and characterized by ICP, IR and NMR. It is proved that the intrinsic identities of Keggin cation and heteropolyanions of the clusters are preserved within the gels.
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Reaction of the trivacant heteropolyanions α A PW9O349- with CH3SiCl3 leads to the formation of the organosilyl derivative (TBA)3[α A PW9O34(CH3SiO)3(CH3Si)]. The crystal X ray diffraction analysis shows that the crystalbelongs to orthorhombic with space group Pca21, M=3177.09 and the unit cell parameters: a=25.761(5)?,b=14.519(3)?,c=24.396(5)?.V=9124(3)?3,Z=4,Dc=2.225g·cm-3,μ(MoKα)=11.438mm-1,F(000)=5464,R=0.0561,Rw=0.0866. The anion consists of one α A PW9O349- anion linked by three CH3SiO+ groups, whichattached to the fourth CH3Si through three Si O Si bridges.
文摘Ainonic clays pillared by heteropolyoxometalate Zn2Al-PW11Z (Z= Cr3+ , Ti4+ and V5+) were synthesized via ion exchange reaction. The IR spectra and XRD patterns showed that the layered anions remained the integrity of Keggin structure, and the gallery heights of the layered compounds were 1.01± 0.01 nm. The MAS NMR spectra of 27Al and 31P indicated the layered ahion had little effect on the Al of the octahedra center of the hydroalde, but the layer and octallydron VO6 had great effect on the P of the layered PW11V. The peak of 31P MAS NMR split to the two peaks of -11.867 ppm and -14.031 ppm whose corresponding area ratio is 2:1. All these results showed that the C2 axia of the heteropolyoxometalate in the layer was perpondicular to the brucite layer. Further experiments found that these compounds had high selectivity and activity for the esterification of acetic acid with n-butyl alcohol.
