新型杂多酸类水滑石插层材料的制备和吸附、光催化性能研究
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摘要
多酸插层水滑石层柱状化合物(LDHs-POMs)是一类多功能型复合材料。它利用水滑石层间阴离子的可交换性，将多酸离子插入层间。本论文利用共沉淀法合成了镁铝水滑石，锌铝水滑石和新型锌铝铁三元水滑石。以其为前体，通过离子交换法合成了多种杂多酸、杂多蓝插层类水滑石化合物。通过元素分析、XRD、IR、电化学、TG-DTA等多种手段对化合物的结构及组成进行了表征。对化合物的染料吸附性能、光催化活性、氧化催化活性进行了探索。
1、利用离子交换法合成了新型杂多蓝插层类水滑石[Zn2Al(OH)6]5[α–PW10Mo2O40](Zn2Al-PW10Mo2)，通过元素分析， XRD，IR，电化学对其进行了表征。研究了该材料对阳离子染料MB的吸附性能。研究结果表明，杂多蓝阴离子的引入，大大的提高了ZnAl类水滑石对阳离子染料MB的吸附能力。
2、通过共沉淀法探索合成了ZnAlFe三元类水滑石化合物，层板中Zn/Al/Fe元素比为1:1:0.2。测试了这种新型三元水滑石的可见光光催化降解阳离子染料MB溶液的能力。以其为前体，通过离子交换法，将Keggin型杂多酸CoW12，Dawson型缺位杂多酸P2W17引入三元层板。多酸阴离子的引入，大大提高了三元层板对阳离子染料的吸附能力，同时这种LDH-POM化合物具有可见光催化降解染料的能力。
3、以ZnAl-NO3为前体，通过离子交换法合成了Waugh型杂多酸阴离子[MnMo9O32]6-插入了阴离子层板间，合成了插层水滑石ZnAl-MnMo9。通过ICP，XRD，IR对ZnAl-MnMo9进行了表征。测试了ZnAl-MnMo9在可见光条件下，对阴离子染料甲基橙的光催化降解效果。
4、通过离子交换法，以MgAl-NO3为前驱体，制备了三取代keggin型杂多酸SiW9Ni3插层的类水滑石材料(MgAl-SiW9Ni3)。采用粉末X-射线衍射、红外光谱和元素分析等手段，研究了MgAl-SiW9Ni3的结构及其性质，并且通过苯甲醛的H2O2液-固相氧化反应测试了其氧化催化性质。
Polyoxometalates-intercalated layered double hydroxides (LDHs-POMs) is a class ofclay materials with positively charged metal-oxide layers, and the layer surface charges isbalanced by polyoxometalates anions. In this paper, we synthesized several new LDHs-POMsby aqueous ion exchange of a Mg-Al LDH, Zn-Al LDH and Zn-Al-Fe LDH precursor innitrate form. The physicochemical properties of the product were characterized by themethods of ICP, XRD, IR, TG-DTA and cyclic voltammetry. LDHs-POMs have been used forthe remocal of dye from aqueous solutions via adsorption and photocatalysis.
1. Heteropoly blue-intercalated layered double hydroxide (HB-LDH) was obtained byaqueous ion exchange of a Zn-Al LDH precursor in nitrate form with the reducedpolyoxometalate anions [PW10Mo2O40]5-. The physicochemical properties of the product werecharacterized by the methods of powder X-ray diffraction, infrared spectroscopy, and cyclicvoltammetry. The HB-LDH has been used for the removal of cationic dye methylene blue(MB) from aqueous solutions via adsorption. The intercalation of large cluster anion[PW10Mo2O40]5-into LDH could induce the adsorption to cationic dye of MB, obviously. TheHB-LDH shows much higher cationic dye adsorption capacity than pure LDH and themaximum adsorption capacity Qmaxof MB onto ZnAl-PW10Mo2is30.87mg/g.
2. ZnAlFe layered double hydroxides (ZnAlFe-NO3) with Zn:Al:Fe ratio (1:1:0.2) wasobtained by the coprecipitation method and tested as photocatalysts for methylene blue (MB)degradation.[CoW12O40]5-and [P2W17O62]10-were been intercalated in ZnAlFe-NO3byionexchange. The intercalation of large cluster anion into ZnAlFe-LDH could induce theadsorption to cationic dye of MB. The ZnAlFe-NO3and ZnAlFe-CoW12were goodphotocatalysts for methylene blue (MB) degradation.
3. Waugh type polyoxometalates [MnMo9O32]6--intercalated layered double hydroxidewas obtained by aqueous ion exchange of a Zn-Al LDH precursor in nitrate form with thereduced polyoxometalate anions [MnMo9O32]6-. The physicochemical properties of theproduct were characterized by the methods of ICP, XRD, IR. ZnAl-MnMo9was tested asphotocatalysts for methylene orange (MO) degradation.
4. We report the preparation and characterization of anion-pillared layered doublehydroxide MgAl-SiW9Ni3. The physicochemical properties of the product were characterizedby the methods of ICP, XRD, IR. The investigation of catalytic performance on this sampleexhibits high activity for the oxidation of benzaldehyde by hydrogen peroxide.
1、利用离子交换法合成了新型杂多蓝插层类水滑石[Zn2Al(OH)6]5[α–PW10Mo2O40](Zn2Al-PW10Mo2)，通过元素分析， XRD，IR，电化学对其进行了表征。研究了该材料对阳离子染料MB的吸附性能。研究结果表明，杂多蓝阴离子的引入，大大的提高了ZnAl类水滑石对阳离子染料MB的吸附能力。
2、通过共沉淀法探索合成了ZnAlFe三元类水滑石化合物，层板中Zn/Al/Fe元素比为1:1:0.2。测试了这种新型三元水滑石的可见光光催化降解阳离子染料MB溶液的能力。以其为前体，通过离子交换法，将Keggin型杂多酸CoW12，Dawson型缺位杂多酸P2W17引入三元层板。多酸阴离子的引入，大大提高了三元层板对阳离子染料的吸附能力，同时这种LDH-POM化合物具有可见光催化降解染料的能力。
3、以ZnAl-NO3为前体，通过离子交换法合成了Waugh型杂多酸阴离子[MnMo9O32]6-插入了阴离子层板间，合成了插层水滑石ZnAl-MnMo9。通过ICP，XRD，IR对ZnAl-MnMo9进行了表征。测试了ZnAl-MnMo9在可见光条件下，对阴离子染料甲基橙的光催化降解效果。
4、通过离子交换法，以MgAl-NO3为前驱体，制备了三取代keggin型杂多酸SiW9Ni3插层的类水滑石材料(MgAl-SiW9Ni3)。采用粉末X-射线衍射、红外光谱和元素分析等手段，研究了MgAl-SiW9Ni3的结构及其性质，并且通过苯甲醛的H2O2液-固相氧化反应测试了其氧化催化性质。
Polyoxometalates-intercalated layered double hydroxides (LDHs-POMs) is a class ofclay materials with positively charged metal-oxide layers, and the layer surface charges isbalanced by polyoxometalates anions. In this paper, we synthesized several new LDHs-POMsby aqueous ion exchange of a Mg-Al LDH, Zn-Al LDH and Zn-Al-Fe LDH precursor innitrate form. The physicochemical properties of the product were characterized by themethods of ICP, XRD, IR, TG-DTA and cyclic voltammetry. LDHs-POMs have been used forthe remocal of dye from aqueous solutions via adsorption and photocatalysis.
1. Heteropoly blue-intercalated layered double hydroxide (HB-LDH) was obtained byaqueous ion exchange of a Zn-Al LDH precursor in nitrate form with the reducedpolyoxometalate anions [PW10Mo2O40]5-. The physicochemical properties of the product werecharacterized by the methods of powder X-ray diffraction, infrared spectroscopy, and cyclicvoltammetry. The HB-LDH has been used for the removal of cationic dye methylene blue(MB) from aqueous solutions via adsorption. The intercalation of large cluster anion[PW10Mo2O40]5-into LDH could induce the adsorption to cationic dye of MB, obviously. TheHB-LDH shows much higher cationic dye adsorption capacity than pure LDH and themaximum adsorption capacity Qmaxof MB onto ZnAl-PW10Mo2is30.87mg/g.
2. ZnAlFe layered double hydroxides (ZnAlFe-NO3) with Zn:Al:Fe ratio (1:1:0.2) wasobtained by the coprecipitation method and tested as photocatalysts for methylene blue (MB)degradation.[CoW12O40]5-and [P2W17O62]10-were been intercalated in ZnAlFe-NO3byionexchange. The intercalation of large cluster anion into ZnAlFe-LDH could induce theadsorption to cationic dye of MB. The ZnAlFe-NO3and ZnAlFe-CoW12were goodphotocatalysts for methylene blue (MB) degradation.
3. Waugh type polyoxometalates [MnMo9O32]6--intercalated layered double hydroxidewas obtained by aqueous ion exchange of a Zn-Al LDH precursor in nitrate form with thereduced polyoxometalate anions [MnMo9O32]6-. The physicochemical properties of theproduct were characterized by the methods of ICP, XRD, IR. ZnAl-MnMo9was tested asphotocatalysts for methylene orange (MO) degradation.
4. We report the preparation and characterization of anion-pillared layered doublehydroxide MgAl-SiW9Ni3. The physicochemical properties of the product were characterizedby the methods of ICP, XRD, IR. The investigation of catalytic performance on this sampleexhibits high activity for the oxidation of benzaldehyde by hydrogen peroxide.
引文
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