离子热法构筑多金属氧酸盐的研究
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摘要
在过去的几十年里,多酸化合物已引起了广泛的吸引力,由于他们组成的多样性及在催化、光化学、磁性及电化学的潜在应用。多酸结构的发展是多酸化学进展的基础。而多酸合成的发展的挑战则主要集中于其用不同的合成方法合成新的化学结构。本文分别以离子热合成法及水热法构筑了六种新的多酸化合物,通过元素分析、热重分析、红外、紫外、固体漫反射和X-射线单晶衍射方法对晶体结构进行了表征,对一些化合物的热稳定性及溶液中的稳定性、磁性、电化学、和光催化性质进行了初步研究。并且研究了这些化合物的性质,适宜的合成方法,反应过程中的影响因素及反应规律。
用离子热方法构筑合成多金属氧酸盐(POM),在离子液体[EMIM]Br合成得到了三个新的化合物: [EMIM]8Na9[WFe9(μ_3-O)_3(μ2-OH)_6O_4H_2O(SiW_9O_34)_3]·7H_2O (1) [EMIM]4[SiW_(12)O_(40)](2) and [EMIM]6[P2W18O62]·4H_2O(3).化合物1是高核过渡金属取代的多金属氧酸盐,及阴离子是由三个[α-SiW9O_34]10-Keggin阴离子通过｛WFe9｝簇连接而成。化合物2-_3则分别是由Keggin型阴离子及Dowson型阴离子构成。
在不同的pH值下通过水热合成得到了三个含铜-咪唑的多酸化合物(HIm)_2{[Cu(Im)_2(PMo_(12)O_(40))]}(Im)_2·_3H_2O (4) (Im = imidazole), {[Cu(Im)_2](PMo_(12)O_(40))}[Cu(Im)_2]_2(Im)·4H_2O (5) and {[Cu(Im)_2]_3(PMoⅤ2MoⅥ10O40)}[Cu(Im)_3]_2 (6).化合物4是由一个Keggin型阴离子[PMo_(12)O_(40)]_3-,与一个[Cu(Im)_2]+单元相连;化合物5是由一个Keggin型阴离子[PMo_(12)O_(40)]_3-,三个[Cu(Im)_2] +单元相连;将该溶液的pH调为5时得到化合物6,由一个Keggin型阴离子[PMo_(12)O_(40)]_3-,三个[Cu(Im)_2]+单元,两个[Cu(Im)_3]_2+单元相连,三个化合物都是从相同的反应体系在不同的pH值中得到。
Over the past decades, polyoxometalates (POMs) have attracted large interest because of their impressive compositional diversity and series of potential applications in catalysis, photochemistry, magnetism and electrochemistry. The evolution of POMs chemistry is dependent upon exploring suitable methods to synthesize novel POMs. The evolution of POMs chemistry is dependent upon exploring suitable methods to synthesize novel POMs. In this paper, five new polyoxometalates have been synthesized employing ionothermal and hydrothermal synthesis, and also structurally characterized by elemental analyses, TG-DTA, IR, UV-Vis, , diffuse reflectance UV-vis spectra and single crystal X-ray diffractions. The thermal stabilities and the stabilities in solutions, magnetic properties, electrochemical and electrochemical activities of these compounds have been investigated.
Using ionothermal synthetic method with ionic liquid EmimBr (Emim = 1-ethyl-_3-methylimidazolium) as solvent has resulted in three novel polyoxometalates (POMs) [Emim]8Na9[WFe9(μ_3-O)_3(μ2-OH)_6O_4H_2O(SiW_9O_34)_3]·7H_2O (1) [EMIM]4[SiW_(12)O_(40)] (2) and [EMIM]6[P2W18O62]·4H_2O (_3).
Three copper-imidazole-containing polyoxometalates (POMs), (HIm)_2{[Cu(Im)_2(PMo_(12)O_(40))]}(Im)_2·_3H_2O (4) (Im = imidazole), {[Cu(Im)_2](PMo_(12)O_(40))}[Cu(Im)_2]_2(Im)·4H_2O (5) and {[Cu(Im)_2]_3(PMo~Ⅴ2Mo~Ⅵ_(10)O_(40)}[Cu(Im)_3]_2 (6), have been hydrothermally synthesized at different pH values. Compound 4, consisting of a Keggin-type polyoxoanion [PMo_(12)O_(40)] decorated by one [Cu(Im)_2] complex; Compound 5 is composed of a Keggin-type polyoxoanion [PMo_(12)O_(40)] and three [Cu(Im)_2] complexes; compound 6, composed of a Keggin-type polyoxoanion [PMo_(12)O_(40)], three [Cu(Im)_2]+ and two [Cu(Im)_3]_2+ units, was synthesized from the similar reaction system.
用离子热方法构筑合成多金属氧酸盐(POM),在离子液体[EMIM]Br合成得到了三个新的化合物: [EMIM]8Na9[WFe9(μ_3-O)_3(μ2-OH)_6O_4H_2O(SiW_9O_34)_3]·7H_2O (1) [EMIM]4[SiW_(12)O_(40)](2) and [EMIM]6[P2W18O62]·4H_2O(3).化合物1是高核过渡金属取代的多金属氧酸盐,及阴离子是由三个[α-SiW9O_34]10-Keggin阴离子通过｛WFe9｝簇连接而成。化合物2-_3则分别是由Keggin型阴离子及Dowson型阴离子构成。
在不同的pH值下通过水热合成得到了三个含铜-咪唑的多酸化合物(HIm)_2{[Cu(Im)_2(PMo_(12)O_(40))]}(Im)_2·_3H_2O (4) (Im = imidazole), {[Cu(Im)_2](PMo_(12)O_(40))}[Cu(Im)_2]_2(Im)·4H_2O (5) and {[Cu(Im)_2]_3(PMoⅤ2MoⅥ10O40)}[Cu(Im)_3]_2 (6).化合物4是由一个Keggin型阴离子[PMo_(12)O_(40)]_3-,与一个[Cu(Im)_2]+单元相连;化合物5是由一个Keggin型阴离子[PMo_(12)O_(40)]_3-,三个[Cu(Im)_2] +单元相连;将该溶液的pH调为5时得到化合物6,由一个Keggin型阴离子[PMo_(12)O_(40)]_3-,三个[Cu(Im)_2]+单元,两个[Cu(Im)_3]_2+单元相连,三个化合物都是从相同的反应体系在不同的pH值中得到。
Over the past decades, polyoxometalates (POMs) have attracted large interest because of their impressive compositional diversity and series of potential applications in catalysis, photochemistry, magnetism and electrochemistry. The evolution of POMs chemistry is dependent upon exploring suitable methods to synthesize novel POMs. The evolution of POMs chemistry is dependent upon exploring suitable methods to synthesize novel POMs. In this paper, five new polyoxometalates have been synthesized employing ionothermal and hydrothermal synthesis, and also structurally characterized by elemental analyses, TG-DTA, IR, UV-Vis, , diffuse reflectance UV-vis spectra and single crystal X-ray diffractions. The thermal stabilities and the stabilities in solutions, magnetic properties, electrochemical and electrochemical activities of these compounds have been investigated.
Using ionothermal synthetic method with ionic liquid EmimBr (Emim = 1-ethyl-_3-methylimidazolium) as solvent has resulted in three novel polyoxometalates (POMs) [Emim]8Na9[WFe9(μ_3-O)_3(μ2-OH)_6O_4H_2O(SiW_9O_34)_3]·7H_2O (1) [EMIM]4[SiW_(12)O_(40)] (2) and [EMIM]6[P2W18O62]·4H_2O (_3).
Three copper-imidazole-containing polyoxometalates (POMs), (HIm)_2{[Cu(Im)_2(PMo_(12)O_(40))]}(Im)_2·_3H_2O (4) (Im = imidazole), {[Cu(Im)_2](PMo_(12)O_(40))}[Cu(Im)_2]_2(Im)·4H_2O (5) and {[Cu(Im)_2]_3(PMo~Ⅴ2Mo~Ⅵ_(10)O_(40)}[Cu(Im)_3]_2 (6), have been hydrothermally synthesized at different pH values. Compound 4, consisting of a Keggin-type polyoxoanion [PMo_(12)O_(40)] decorated by one [Cu(Im)_2] complex; Compound 5 is composed of a Keggin-type polyoxoanion [PMo_(12)O_(40)] and three [Cu(Im)_2] complexes; compound 6, composed of a Keggin-type polyoxoanion [PMo_(12)O_(40)], three [Cu(Im)_2]+ and two [Cu(Im)_3]_2+ units, was synthesized from the similar reaction system.
引文
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