修饰型杂多化合物的合成_表征及催化性能研究
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摘要
1．本文首先制备了n个Fe（n=0,1,2,3）取代的Keggin型Si-W杂多酸盐催化剂TBA_4[α-SiW_12O_40], TBA_5[α-SiW_11{Fe(OH_2)}O_39], TBA-6[γ-SiW_10{Fe(OH_2)}_2O_38]和TBA_7[α-SiW_9{Fe(OH_2)}3O37](TBA=[(C_4H_9)_4N]~+)，并通过各种表征手段对杂多化合物的结构特征进行了详细研究。并以H_2O_2为氧化剂，考察Fe中心的不同结构对环己醇催化氧化反应的影响。反应结果表明催化剂TBASiW10Fe2的催化活性最高，说明Fe取代的Keggin型硅钨酸盐的骨架结构对于催化反应活性具有重要的影响。并考察反应溶剂，反应温度，氧化剂用量，催化剂用量等影响因素对催化反应的影响，确定最佳反应条件。此外，还通过IR, UV-vis等表征手段研究了催化剂在反应体系中的稳定性。
2.制备了以季铵盐(十六烷基三甲基溴化铵(CTAB),四乙基溴化铵(TEAB),四甲基溴化铵(TMAB))作为抗衡离子，二聚体[(PW_11FeO_39)_2O]~(10-)作为杂多阴离子的催化剂，运用IR, XRD, UV-vis, SEM, BET等表征手段对所合成的催化剂的结构特征，物理化学性质进行了系统的研究。研究抗衡离子对杂多酸盐催化环己醇氧化反应的催化活性的影响，研究发现抗衡离子的碳链越长，催化剂的催化活性越高。同时还考察了催化剂在反应过程中结构的变化对其催化性能的影响，结果发现二聚体结构的杂多酸盐在反应后结构发生变化，在二聚体到单体[PW_11Fe(H_2O)O_39]~(4-)的转化过程中，环己醇的转化率快速升高，待转化过程结束后，环己醇的转化率无明显变化。因此这个转化过程是一个动态过程，可以提高催化反应活性。同时进一步探讨了其反应机制。
3.通过共沉淀法将二聚体杂多酸盐CTA_10[(PW_11FeO_39)_2O]负载于载体SiO_2上，运用IR, XRD, DRS UV-vis, TG-DTA, BET等表征手段对所合成的催化剂的结构特征，物理化学性质进行了系统的研究。表征结果说明二聚体CTA_10[(PW_11FeO_39)_2O]高度分散于SiO_2表面。以叔丁醇为溶剂，H_2O_2为氧化剂，考察负载型催化剂CTAFe_2/SiO-2对液-固相正己醇氧化反应的催化性能，发现在液固相氧化反应中，负载量为60%时，催化活性最高，反应后负载型催化剂中杂多酸盐有部分流失，但催化剂的结构稳定，没有发生改变；以O_2为氧化剂，考察负载型催化剂CTAFe_2/SiO_2对气-固相正己醇氧化反应的催化性能，在气-固相氧化反应中，负载量为60%时，催化活性最高，负载型催化剂在反应后结构发生改变，二聚体结构消失。CTA_10[(PW_11FeO_39)2O]在反应后结构发生重排，变成1:12系列Keggin型杂多阴离子[PW_12O_40]~(3-)，取代金属Fe从结构中释放出去，而处于抗衡离子的位置。
4.考察了以离子体积大的碱金属阳离子（Rb~+, Cs~+）作为抗衡离子，[SiFe(OH_2)W_11O_39]~(5-）作为杂多阴离子主体的合成和表征，研究抗衡离子对杂多酸盐的物理化学性质和结构特征的影响，以及对环己醇-H_2O_2氧化反应的反应性能的影响，并探索其简单反应机制。结果表明催化剂均具有Keggin型结构，引入不同的抗衡离子，并没有改变硅钨酸盐的Keggin型结构。随着抗衡离子半径的增大Rb 5.在杂多化合物中引入有机配体对其进行修饰，设计以及制备了一个新型的无机-有机杂化材料，以金属取代的杂多酸盐[PW_11Ni(H_2O)O_39]~(5-)作为无机物种，有机胺作为有机配体，通过杂多化合物中的取代金属Ni与有机胺中的氮原子配位成键而形成无机-有机杂化材料。通过IR, UV, XRD, XPS, TG-DTA, ICP等表征手段对杂化材料的结构进行了系统的研究，并考察了杂化材料对染料的光催化降解的能力。
Oxidation reactions constitute an important research area because they have awide range of applications in organic synthesis and fine chemical industry. Theselective oxidation of alcohols into their corresponding carbonyl compounds is one ofcrucially important and fundamental transformations from both synthetic andindustrial points of view, due to the wide-ranging utility of these products as versatileintermediates of valuable compounds such as pharmaceuticals, agricultural chemicalsand vitamins. Oxidation of alcohols has always been the research hot spot, in thepursuit of fast reaction rate and high yield, meanwhile, researchers begin to payattention to how to develop environment friendly, mild reaction conditions of alcoholoxidation process. In selective catalytic oxidation of organic compounds, hydrogenperoxide is an attractive oxygen donor as it has a high content of active oxygenspecies, and water is only byproduct. It is also much cheaper and safer to use thanorganic peroxides or peracids, making the process promising for future application.Most examples of alcohol oxidation with hydrogen peroxide employed heteropolycompounds as catalysts have been reported. Heteropoly compounds are a kind of newexcellent acid catalyst and redox catalyst due to their tunable acid and redoxproperties, a certain structure and electrons and protons move/storage capacity,hydrolytic and thermal stability, solubility in various media, and so forth. Heteropolycompounds can also be supported on carriers such as SiO2or carbon, etc, and showhigh catalytic ability and selectivity. The structure and composition of heteropolycompounds can be modified and changed, thus changing their catalytic properties.
In this paper, heteropoly compounds were modified by changing theircountercations and amount of substituted metals, introduction of organic ligands orbeing supported on suitable carriers, thus making their application in the oxidation ofalcohols. The heteropoly compounds after modification were characterized by IR,XRD, UV-vis, SEM, BET to study their structural characteristics and physicochemicalproperties such as: stability, morphology, solubility, etc. The influence of modification of heteropoly compounds on their catalytic properties was studied. The relationshipbetween countercations, structural change of heteropoly compounds and catalyticproperties was studied systematically, and the mechanism of the oxidation overmodified heteropoly compounds was studied preliminary.The main experimental results and conclusions are as follows:
1. Firstly, Fen-substituted (n=0,1,2,3) Keggin-type silicotungstates TBA4[α-SiW_12O_40],TBA_5[α-SiW_11{Fe(OH_2)}O_39], TBA_6[γ-SiW_10{Fe(OH_2)}2O_38] and TBA7[α-SiW9{Fe(OH_2)}3O37](TBA=[(C4H9)4N]~+) were synthesized and characterized by IR, UV-vis and XRD. Theresults illuminated that the amount of Fe did not affect the Keggin-type structure ofsilicotungstates. But TBA4[α-SiW_12O_40], TBA_5[α-SiW_11{Fe(OH_2)}O_39] and TBA7[α-SiW_9{Fe(OH_2)}3O37] were α-isomer, diiron-substituted TBA_6[γ-SiW_10{Fe(OH_2)}2O_38] wasγ-isomer.With H_2O_2as oxidant, the influence of Fe-center on the catalytic oxidation ofcyclohexanol was studied. Non-substituted Keggin anion [α-SiW_12O_40]4-was inactive.Only when Fe was on the coordination site, the catalytic activity of silicotungstateswas increased. These results showed that Fe was the active center of catalytic system.The catalyst TBA_6[γ-SiW_10{Fe(OH_2)}2O_38] showed the highest catalytic reactivity. Thisresult showed that the skeleton structure of Keggin-type silicotungstates played animportant role in catalytic reactivity, and diiron site of γ-Keggin silicotungstates waseffective for the oxygenation with H_2O_2. With TBA_6[γ-SiW_10{Fe(OH_2)}2O_38] as catalyst,the optimal condition: acetonitrile as solvent, temperature at70oC, n(H_2O_2)=160mmol, n (catalyst)=0.3mmol,89.2%conversion of cyclohexanol was achieved. IRand UV-vis spectra of TBA_6[γ-SiW_10{Fe(OH_2)}_2O_38] after reaction showed thatγ-Keggin structure was stable and the catalyst was not deactivated under the reactionconditions used.
2. The dimeric mono-Fe(III)-substituted phosphotungstates [CTA]_10[(PW_11FeO_39)_2O],[TEA]10[(PW_11FeO_39)_2O] and [TMA]_10[(PW_11FeO_39)_2O](cetytrimethyl ammonium bromide(CTAB), tetraethylammonium bromide (TEAB) and tetramethy lammonium bromide(TMAB)) were synthesized and characterized by IR, XRD, UV-vis, SEM and BET.The results showed that the longer alkyl chains of the organic countercations was, theless compact the particles showed, thus the specific surface area was bigger and thecatalyst was more accessible to the substrate. The catalytic activities of thesephosphotungstates were tested in the oxidation of cyclohexanol using H_2O_2as oxidantand tert-Butanol as solvent.[CTA]_10[(PW_11FeO_39)_2O] showed to be the most efficient catalyst, the result indicated that longer alkyl chains of the organic countercations wasfavorable to enhancing the catalytic activity of the catalysts.
In addition, IR spectra of the recovered catalyst at different reaction temperatureand at different reaction time at70oC, showed that the catalyst [CTA]10[(PW_11FeO_39)_2O]was not stable at70oC and decomposed completely with the formation of monomeric[CTA]_4PW_11Fe(H_2O)O_39after3h of the reaction. But there was still dimeric[CTA]10[(PW_11FeO_39)_2O] partially existing in the catalytic system at the first3h of thereaction. During the first3h of the reaction, the dimeric [CTA]10[(PW_11FeO_39)_2O]gradually decomposed into monomeric [CTA]4PW_11Fe(H_2O)O_39, this dynamic processfacilitated catalytic oxidation of cyclohexanol.
3. SiO_2-supported CTA_10[(PW_11FeO_39)_2O] was synthesized by a co-precipitationmethod. IR, XRD, DRS UV-vis, TG-DTA and BET results proved that CTA_10[(PW_11FeO_39)_2O]could be finely dispersed on the SiO_2, and the dimeric structure was stable in thesupported catalysts. All samples had evenly distributed mesoporous channel.
With H_2O_2as oxidant and tert-Butanol as solvent, the catalytic activity ofCTAFe2/SiO_2was tested in the liquid-solid phase oxidation of hexanol. The resultsshowed that SiO_2had no catalytic reactivity. The conversion of hexanol increasedafter [CTA_10[(PW_11FeO_39)_2O] supported on SiO_2. The yield of hexanal and hexanoicacid all increased with the load of CTAFe2/SiO_2increasing. From the selectivity andactivity into consideration, the optimal load was60%. A little leaching of the activespecies occurred during the reaction, but the dimeric structure of CTAFe2/SiO_2was stable.
With O_2as oxidant, the catalytic activity of CTAFe2/SiO_2was tested in thegas-solid phase oxidation of hexanol. The results showed that their reactivity wasenhanced after CTA_10[(PW_11FeO_39)_2O] supported on SiO_2. When the load was60%,the catalytic activity of CTAFe2/SiO_2reached highest. IR spectra and XRD patterns ofthe catalysts after reaction showed that the structure of the catalysts changed anddimeric structure disappeared. The structure of CTA_10[(PW_11FeO_39)_2O] changed aftergas-solid phase oxidation of hexanol and rearranged into1:12Keggin anion[PW12O40]3-. That’s because organic cations decomposed from250oC to400oC, whichdrived the release of Fe from the Keggin anion [(PW_11FeO_39)_2O]10-yielding Fe ascountercation. The remained lacunary [PW_11FeO_39]4-was unstable and rearrangedinto [PW12O40]3-.
4. The mono-iron-substituted Keggin-type silicotungstates Rb5SiFe(OH_2)W_11O_39·7H_2O and Cs5SiFe(OH_2)W_11O_39·6H_2O were synthesized, which were characterized by IR,XRD, UV-vis, SEM, BET, and TG-DTA. The results showed that the preparedsilicotungstates were of Keggin structure and Keggin unit of heteropoly anion[SiFe(OH_2)W_11O_39]5-did not change by introducing different countercations. Butcountercations could change the morphology, specific surface area and dissolubility ofthe silicotungstates. The specific surface area increased gradually and the particlesaccumulated loosen gradually and dissolubility in water decreased gradually with theradius of countercations increasing in the order of Rb With H_2O_2as oxidant, cyclohexanol was efficiently oxidized to cyclohexanone overthese two silicotungstates. The results showed that the catalyst Rb5SiFe(OH_2)W_11O_39·7H_2Oshowed the highest catalytic reactivity. For organic liquid phase oxidation with H_2O_2asoxidant, the catalyst with good dissolubility could form water-oil biphasic reactionsystem, thus making it better catalytic reactivity. The catalyst Rb5SiFe(OH_2)W_11O_39·7H_2Ocould dissolved in H_2O_2and presented as liquid state in the reaction process. Thus thecontact area between the catalyst and organic substrate magnified and the conversionof cyclohexanol was increased. Moreover, water-oil biphasic system allowed easyrecovery of catalyst. The catalyst could be reused three times without appreciable lossof activity. With Rb5SiFe(OH_2)W_11O_39·7H_2O as catalyst and tert-Butanol as solvent,the optimal conditions: temperature at80oC, n(H_2O_2)/n(cyclohexanol) was1.5,n(catalyst) was0.4mmol,52.1%conversion of cyclohexanol was achieved.
5. Introducing organic ligand into heteropoly compound, a new inorganic-organichybrid material Na(ANIH)4ANI[PW_11Ni(ANI)O_39]·12H_2O (ANI=aniline) was prepared basedon transition-metal monosubstituted Keggin type anion [PW_11Ni(H_2O)O_39]5-as inorganicspecies and aniline as organic ligand by a covalent bonding of Ni-N. The as-preparedhybrid material was characterized by elemental analysis, IR，UV-vis, XRD, TG-DTA,ICP and XPS. The results approved that the Keggin structure of the hybrid materialstill remained and the Ni-N covalent bond is formed between the transition-metal inthe Keggin-type anion [PW_11Ni(H_2O)O_39]5-and the nitrogen atom of ANI, whichilluminated that heteropoly anions reacted chemically with organic ligand, andelectrons transferred from the nitrogen atom to the transition metal Ni center. Also theanion [PW_11Ni(ANI)O_39]5-was surrounded by five ANI containing species: four ofthem were protonated ANIH~~+as countercations and one was noncoordinated ANImolecule. Photocatalytic degradation of dye RB indicated that the as-prepared hybrid material Na(ANIH)4ANI[PW_11Ni(ANI)O_39]·12H_2O showed higher photocatalyticactivity. Therefore, the hybrid material has great potential for application in practicalphotodegradation.
2.制备了以季铵盐(十六烷基三甲基溴化铵(CTAB),四乙基溴化铵(TEAB),四甲基溴化铵(TMAB))作为抗衡离子，二聚体[(PW_11FeO_39)_2O]~(10-)作为杂多阴离子的催化剂，运用IR, XRD, UV-vis, SEM, BET等表征手段对所合成的催化剂的结构特征，物理化学性质进行了系统的研究。研究抗衡离子对杂多酸盐催化环己醇氧化反应的催化活性的影响，研究发现抗衡离子的碳链越长，催化剂的催化活性越高。同时还考察了催化剂在反应过程中结构的变化对其催化性能的影响，结果发现二聚体结构的杂多酸盐在反应后结构发生变化，在二聚体到单体[PW_11Fe(H_2O)O_39]~(4-)的转化过程中，环己醇的转化率快速升高，待转化过程结束后，环己醇的转化率无明显变化。因此这个转化过程是一个动态过程，可以提高催化反应活性。同时进一步探讨了其反应机制。
3.通过共沉淀法将二聚体杂多酸盐CTA_10[(PW_11FeO_39)_2O]负载于载体SiO_2上，运用IR, XRD, DRS UV-vis, TG-DTA, BET等表征手段对所合成的催化剂的结构特征，物理化学性质进行了系统的研究。表征结果说明二聚体CTA_10[(PW_11FeO_39)_2O]高度分散于SiO_2表面。以叔丁醇为溶剂，H_2O_2为氧化剂，考察负载型催化剂CTAFe_2/SiO-2对液-固相正己醇氧化反应的催化性能，发现在液固相氧化反应中，负载量为60%时，催化活性最高，反应后负载型催化剂中杂多酸盐有部分流失，但催化剂的结构稳定，没有发生改变；以O_2为氧化剂，考察负载型催化剂CTAFe_2/SiO_2对气-固相正己醇氧化反应的催化性能，在气-固相氧化反应中，负载量为60%时，催化活性最高，负载型催化剂在反应后结构发生改变，二聚体结构消失。CTA_10[(PW_11FeO_39)2O]在反应后结构发生重排，变成1:12系列Keggin型杂多阴离子[PW_12O_40]~(3-)，取代金属Fe从结构中释放出去，而处于抗衡离子的位置。
4.考察了以离子体积大的碱金属阳离子（Rb~+, Cs~+）作为抗衡离子，[SiFe(OH_2)W_11O_39]~(5-）作为杂多阴离子主体的合成和表征，研究抗衡离子对杂多酸盐的物理化学性质和结构特征的影响，以及对环己醇-H_2O_2氧化反应的反应性能的影响，并探索其简单反应机制。结果表明催化剂均具有Keggin型结构，引入不同的抗衡离子，并没有改变硅钨酸盐的Keggin型结构。随着抗衡离子半径的增大Rb
Oxidation reactions constitute an important research area because they have awide range of applications in organic synthesis and fine chemical industry. Theselective oxidation of alcohols into their corresponding carbonyl compounds is one ofcrucially important and fundamental transformations from both synthetic andindustrial points of view, due to the wide-ranging utility of these products as versatileintermediates of valuable compounds such as pharmaceuticals, agricultural chemicalsand vitamins. Oxidation of alcohols has always been the research hot spot, in thepursuit of fast reaction rate and high yield, meanwhile, researchers begin to payattention to how to develop environment friendly, mild reaction conditions of alcoholoxidation process. In selective catalytic oxidation of organic compounds, hydrogenperoxide is an attractive oxygen donor as it has a high content of active oxygenspecies, and water is only byproduct. It is also much cheaper and safer to use thanorganic peroxides or peracids, making the process promising for future application.Most examples of alcohol oxidation with hydrogen peroxide employed heteropolycompounds as catalysts have been reported. Heteropoly compounds are a kind of newexcellent acid catalyst and redox catalyst due to their tunable acid and redoxproperties, a certain structure and electrons and protons move/storage capacity,hydrolytic and thermal stability, solubility in various media, and so forth. Heteropolycompounds can also be supported on carriers such as SiO2or carbon, etc, and showhigh catalytic ability and selectivity. The structure and composition of heteropolycompounds can be modified and changed, thus changing their catalytic properties.
In this paper, heteropoly compounds were modified by changing theircountercations and amount of substituted metals, introduction of organic ligands orbeing supported on suitable carriers, thus making their application in the oxidation ofalcohols. The heteropoly compounds after modification were characterized by IR,XRD, UV-vis, SEM, BET to study their structural characteristics and physicochemicalproperties such as: stability, morphology, solubility, etc. The influence of modification of heteropoly compounds on their catalytic properties was studied. The relationshipbetween countercations, structural change of heteropoly compounds and catalyticproperties was studied systematically, and the mechanism of the oxidation overmodified heteropoly compounds was studied preliminary.The main experimental results and conclusions are as follows:
1. Firstly, Fen-substituted (n=0,1,2,3) Keggin-type silicotungstates TBA4[α-SiW_12O_40],TBA_5[α-SiW_11{Fe(OH_2)}O_39], TBA_6[γ-SiW_10{Fe(OH_2)}2O_38] and TBA7[α-SiW9{Fe(OH_2)}3O37](TBA=[(C4H9)4N]~+) were synthesized and characterized by IR, UV-vis and XRD. Theresults illuminated that the amount of Fe did not affect the Keggin-type structure ofsilicotungstates. But TBA4[α-SiW_12O_40], TBA_5[α-SiW_11{Fe(OH_2)}O_39] and TBA7[α-SiW_9{Fe(OH_2)}3O37] were α-isomer, diiron-substituted TBA_6[γ-SiW_10{Fe(OH_2)}2O_38] wasγ-isomer.With H_2O_2as oxidant, the influence of Fe-center on the catalytic oxidation ofcyclohexanol was studied. Non-substituted Keggin anion [α-SiW_12O_40]4-was inactive.Only when Fe was on the coordination site, the catalytic activity of silicotungstateswas increased. These results showed that Fe was the active center of catalytic system.The catalyst TBA_6[γ-SiW_10{Fe(OH_2)}2O_38] showed the highest catalytic reactivity. Thisresult showed that the skeleton structure of Keggin-type silicotungstates played animportant role in catalytic reactivity, and diiron site of γ-Keggin silicotungstates waseffective for the oxygenation with H_2O_2. With TBA_6[γ-SiW_10{Fe(OH_2)}2O_38] as catalyst,the optimal condition: acetonitrile as solvent, temperature at70oC, n(H_2O_2)=160mmol, n (catalyst)=0.3mmol,89.2%conversion of cyclohexanol was achieved. IRand UV-vis spectra of TBA_6[γ-SiW_10{Fe(OH_2)}_2O_38] after reaction showed thatγ-Keggin structure was stable and the catalyst was not deactivated under the reactionconditions used.
2. The dimeric mono-Fe(III)-substituted phosphotungstates [CTA]_10[(PW_11FeO_39)_2O],[TEA]10[(PW_11FeO_39)_2O] and [TMA]_10[(PW_11FeO_39)_2O](cetytrimethyl ammonium bromide(CTAB), tetraethylammonium bromide (TEAB) and tetramethy lammonium bromide(TMAB)) were synthesized and characterized by IR, XRD, UV-vis, SEM and BET.The results showed that the longer alkyl chains of the organic countercations was, theless compact the particles showed, thus the specific surface area was bigger and thecatalyst was more accessible to the substrate. The catalytic activities of thesephosphotungstates were tested in the oxidation of cyclohexanol using H_2O_2as oxidantand tert-Butanol as solvent.[CTA]_10[(PW_11FeO_39)_2O] showed to be the most efficient catalyst, the result indicated that longer alkyl chains of the organic countercations wasfavorable to enhancing the catalytic activity of the catalysts.
In addition, IR spectra of the recovered catalyst at different reaction temperatureand at different reaction time at70oC, showed that the catalyst [CTA]10[(PW_11FeO_39)_2O]was not stable at70oC and decomposed completely with the formation of monomeric[CTA]_4PW_11Fe(H_2O)O_39after3h of the reaction. But there was still dimeric[CTA]10[(PW_11FeO_39)_2O] partially existing in the catalytic system at the first3h of thereaction. During the first3h of the reaction, the dimeric [CTA]10[(PW_11FeO_39)_2O]gradually decomposed into monomeric [CTA]4PW_11Fe(H_2O)O_39, this dynamic processfacilitated catalytic oxidation of cyclohexanol.
3. SiO_2-supported CTA_10[(PW_11FeO_39)_2O] was synthesized by a co-precipitationmethod. IR, XRD, DRS UV-vis, TG-DTA and BET results proved that CTA_10[(PW_11FeO_39)_2O]could be finely dispersed on the SiO_2, and the dimeric structure was stable in thesupported catalysts. All samples had evenly distributed mesoporous channel.
With H_2O_2as oxidant and tert-Butanol as solvent, the catalytic activity ofCTAFe2/SiO_2was tested in the liquid-solid phase oxidation of hexanol. The resultsshowed that SiO_2had no catalytic reactivity. The conversion of hexanol increasedafter [CTA_10[(PW_11FeO_39)_2O] supported on SiO_2. The yield of hexanal and hexanoicacid all increased with the load of CTAFe2/SiO_2increasing. From the selectivity andactivity into consideration, the optimal load was60%. A little leaching of the activespecies occurred during the reaction, but the dimeric structure of CTAFe2/SiO_2was stable.
With O_2as oxidant, the catalytic activity of CTAFe2/SiO_2was tested in thegas-solid phase oxidation of hexanol. The results showed that their reactivity wasenhanced after CTA_10[(PW_11FeO_39)_2O] supported on SiO_2. When the load was60%,the catalytic activity of CTAFe2/SiO_2reached highest. IR spectra and XRD patterns ofthe catalysts after reaction showed that the structure of the catalysts changed anddimeric structure disappeared. The structure of CTA_10[(PW_11FeO_39)_2O] changed aftergas-solid phase oxidation of hexanol and rearranged into1:12Keggin anion[PW12O40]3-. That’s because organic cations decomposed from250oC to400oC, whichdrived the release of Fe from the Keggin anion [(PW_11FeO_39)_2O]10-yielding Fe ascountercation. The remained lacunary [PW_11FeO_39]4-was unstable and rearrangedinto [PW12O40]3-.
4. The mono-iron-substituted Keggin-type silicotungstates Rb5SiFe(OH_2)W_11O_39·7H_2O and Cs5SiFe(OH_2)W_11O_39·6H_2O were synthesized, which were characterized by IR,XRD, UV-vis, SEM, BET, and TG-DTA. The results showed that the preparedsilicotungstates were of Keggin structure and Keggin unit of heteropoly anion[SiFe(OH_2)W_11O_39]5-did not change by introducing different countercations. Butcountercations could change the morphology, specific surface area and dissolubility ofthe silicotungstates. The specific surface area increased gradually and the particlesaccumulated loosen gradually and dissolubility in water decreased gradually with theradius of countercations increasing in the order of Rb
5. Introducing organic ligand into heteropoly compound, a new inorganic-organichybrid material Na(ANIH)4ANI[PW_11Ni(ANI)O_39]·12H_2O (ANI=aniline) was prepared basedon transition-metal monosubstituted Keggin type anion [PW_11Ni(H_2O)O_39]5-as inorganicspecies and aniline as organic ligand by a covalent bonding of Ni-N. The as-preparedhybrid material was characterized by elemental analysis, IR，UV-vis, XRD, TG-DTA,ICP and XPS. The results approved that the Keggin structure of the hybrid materialstill remained and the Ni-N covalent bond is formed between the transition-metal inthe Keggin-type anion [PW_11Ni(H_2O)O_39]5-and the nitrogen atom of ANI, whichilluminated that heteropoly anions reacted chemically with organic ligand, andelectrons transferred from the nitrogen atom to the transition metal Ni center. Also theanion [PW_11Ni(ANI)O_39]5-was surrounded by five ANI containing species: four ofthem were protonated ANIH~~+as countercations and one was noncoordinated ANImolecule. Photocatalytic degradation of dye RB indicated that the as-prepared hybrid material Na(ANIH)4ANI[PW_11Ni(ANI)O_39]·12H_2O showed higher photocatalyticactivity. Therefore, the hybrid material has great potential for application in practicalphotodegradation.
引文
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