层状双羟基阴离子粘土的合成及其对NO_x的吸附性能研究
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摘要
对于具有层状结构的材料和性能研究是近年来的研究热点。水滑石是一种典型的层状阴离子粘土，其结构和水镁石(Mg(OH)_2)相似，水镁石中的Mg~(2+)部分地被Al~(3+)同晶取代而形成的衍生物称作水滑石。类水滑石化合物通式可表示为：[M_(1-x)~ⅡM_x~Ⅲ(OH)_2]~(x+)(A~(n-))_(x/n)·mH_2O，由于M~(2+)与M~(3+)的比例在一定范围内可以调变，不仅可以维持其层状结构，而且可以调节它的酸碱性，甚至氧化还原性质。因此水滑石被众多的催化研究者所青睐。
本论文采用共沉淀法合成出了各类类水滑石样品，通过FT-IR，TG-DTA，XRD等表征手段，并在常温下对NOx的静态吸附进行了研究，以确定各类水滑石样品的制备条件，得到如下的研究结果。
合成了二元金属类水滑石化合物。经表征，样品具有典型的水滑石层状结构；作为前驱体对NO_x均具有良好的吸附性能，其中锌铝型类(Zn／Al摩尔比为3)水滑石对NO_x饱和吸附量最大，可达1851mg／g。
合成了铜钴铝等三元的不同摩尔投料比的碳酸根型水滑石，Cu／Co／Al摩尔之比分别为1：1：1～1：7：1，用XRD、IR、TG-DTA分析对它们进行了表征，测定了对氮氧化物的吸附性能。结果表明，Cu-Co-Al的摩尔之比在1：1：1～1：7：1时合成的化合物都具有水滑石结构，Co的含量增加，水滑石层间高度略有增加，热稳定性减弱热重-差热分析结果显示合成样品的分解均有两个过程。二元的Co_3Al-HTlc吸附NO_x优于三元的CuCoAl-HTlcs，三元的CuCo_3Al-HTlc对NO_x吸附性能优于其它三元的类水滑石化合物，二元的Co_3Al-HTlc和三元的CuCo_3Al-HTlc吸附容量分别为1781mg／g、1286mg／g。
采用离子交换法，将具有Keggin结构的磷钨酸、硅钨酸引入到Mg-Al、Mg-Al-Cu类水滑石(Hydrotalcite-like compounds，HTlcs)层间，成功制备了层有序度高，结晶度好的杂多酸阴离子柱撑类水滑石，得到了通道高度达1.15nm的大层间的催化材料，并用红外、XRD表征了材料的结构．测定了对NOx的吸附性能．
The research on the structure and properties of laminated structure materials has become a hotspot recently. Hydrotalcite is a kind of negative ion clay with typical laminated structure. Its structure is similar with brucite Mg(0H)2, in which Mg2+ could be isomorphously replaced by Al3+ partly. The general formulas Hydrotalcite-like compounds are usually written as [MIIVxMIIIx(OH)2]x+ (An-)x/n mH2O. The ratio of M2+ and M3+ could be adjusted in wide range, which can not only maintain its laminated structure but also adjust its acidity and basicity, even oxidation-reduction nature. So hydrotalcites are widely used for numerous catalysis pursuers.
This research work in this paper is mainly about that numerous hydrotalcite-like compounds were synthesized by co-precipitation. The samples were characterized by XRD, IR,TG-DTA; and the adsorption capacity of the samples after calcination at 500 ℃ for nitrogen oxides was measured. At last, optimal preparation condition is decided and some meaning conclusions are drawed.
Diatomic metal hydrotalcite-like compounds were synthesized. The results show that the samples had typical layer hydrotalcite structure via characterization. The adsorption capacity of Zn3Al-HTlc for NOX was maximal, and the static saturation adsorption capacity was 1851mg/g.
Carbonate pillared hydrotalcite-like compounds ( CuCoAl-HTlcs ) with different Cu/Co/Al molar ratios were synthesized by coprecipitation and characterized by XRD, IR, TG-DTA. The abilities of their adsorption on NOX were also measured. The results showed that the samples with Cu/Co/Al molar ratios of 1 : 1 : 1~1 : 7 : 1 have hydrotalcite structure and layer spacings increased with Co amount increase. The TG-DTA results showed that the materials decomposed in two stages and the thermal stability of the hydrotalcites decreased with increasing Co amount. The adsorption ability of the Co3Al-HTlc for NOX was much better than that of the CuCoAl-HTlcs,
the adsorption ability of CuCO3Al-HTIC was better than the other the other CuCoAl-HTlcs. The adsorption capacities of the Co3Al-HTlc and CuCo3Al-HTlc were 1781mg/g and 1286mg/g respectively.
The preparation of Mg-Al-hydrotalcite(WP-keggin, WSi-keggin) Mg-Al-Cu-hydrotalcite (WP-keggin, WSi-keggin) was studied. The POM-HTLs was synthesized using ion-exchange by introducing POM (heteropolyanions) into the layer of HTLcs. The POM-HTLcs was synthesized with high crystallization and high-order layers with the layered height of approximate 1.15nm successfully. The absorption ability of samples for NOx was also measured.
本论文采用共沉淀法合成出了各类类水滑石样品，通过FT-IR，TG-DTA，XRD等表征手段，并在常温下对NOx的静态吸附进行了研究，以确定各类水滑石样品的制备条件，得到如下的研究结果。
合成了二元金属类水滑石化合物。经表征，样品具有典型的水滑石层状结构；作为前驱体对NO_x均具有良好的吸附性能，其中锌铝型类(Zn／Al摩尔比为3)水滑石对NO_x饱和吸附量最大，可达1851mg／g。
合成了铜钴铝等三元的不同摩尔投料比的碳酸根型水滑石，Cu／Co／Al摩尔之比分别为1：1：1～1：7：1，用XRD、IR、TG-DTA分析对它们进行了表征，测定了对氮氧化物的吸附性能。结果表明，Cu-Co-Al的摩尔之比在1：1：1～1：7：1时合成的化合物都具有水滑石结构，Co的含量增加，水滑石层间高度略有增加，热稳定性减弱热重-差热分析结果显示合成样品的分解均有两个过程。二元的Co_3Al-HTlc吸附NO_x优于三元的CuCoAl-HTlcs，三元的CuCo_3Al-HTlc对NO_x吸附性能优于其它三元的类水滑石化合物，二元的Co_3Al-HTlc和三元的CuCo_3Al-HTlc吸附容量分别为1781mg／g、1286mg／g。
采用离子交换法，将具有Keggin结构的磷钨酸、硅钨酸引入到Mg-Al、Mg-Al-Cu类水滑石(Hydrotalcite-like compounds，HTlcs)层间，成功制备了层有序度高，结晶度好的杂多酸阴离子柱撑类水滑石，得到了通道高度达1.15nm的大层间的催化材料，并用红外、XRD表征了材料的结构．测定了对NOx的吸附性能．
The research on the structure and properties of laminated structure materials has become a hotspot recently. Hydrotalcite is a kind of negative ion clay with typical laminated structure. Its structure is similar with brucite Mg(0H)2, in which Mg2+ could be isomorphously replaced by Al3+ partly. The general formulas Hydrotalcite-like compounds are usually written as [MIIVxMIIIx(OH)2]x+ (An-)x/n mH2O. The ratio of M2+ and M3+ could be adjusted in wide range, which can not only maintain its laminated structure but also adjust its acidity and basicity, even oxidation-reduction nature. So hydrotalcites are widely used for numerous catalysis pursuers.
This research work in this paper is mainly about that numerous hydrotalcite-like compounds were synthesized by co-precipitation. The samples were characterized by XRD, IR,TG-DTA; and the adsorption capacity of the samples after calcination at 500 ℃ for nitrogen oxides was measured. At last, optimal preparation condition is decided and some meaning conclusions are drawed.
Diatomic metal hydrotalcite-like compounds were synthesized. The results show that the samples had typical layer hydrotalcite structure via characterization. The adsorption capacity of Zn3Al-HTlc for NOX was maximal, and the static saturation adsorption capacity was 1851mg/g.
Carbonate pillared hydrotalcite-like compounds ( CuCoAl-HTlcs ) with different Cu/Co/Al molar ratios were synthesized by coprecipitation and characterized by XRD, IR, TG-DTA. The abilities of their adsorption on NOX were also measured. The results showed that the samples with Cu/Co/Al molar ratios of 1 : 1 : 1~1 : 7 : 1 have hydrotalcite structure and layer spacings increased with Co amount increase. The TG-DTA results showed that the materials decomposed in two stages and the thermal stability of the hydrotalcites decreased with increasing Co amount. The adsorption ability of the Co3Al-HTlc for NOX was much better than that of the CuCoAl-HTlcs,
the adsorption ability of CuCO3Al-HTIC was better than the other the other CuCoAl-HTlcs. The adsorption capacities of the Co3Al-HTlc and CuCo3Al-HTlc were 1781mg/g and 1286mg/g respectively.
The preparation of Mg-Al-hydrotalcite(WP-keggin, WSi-keggin) Mg-Al-Cu-hydrotalcite (WP-keggin, WSi-keggin) was studied. The POM-HTLs was synthesized using ion-exchange by introducing POM (heteropolyanions) into the layer of HTLcs. The POM-HTLcs was synthesized with high crystallization and high-order layers with the layered height of approximate 1.15nm successfully. The absorption ability of samples for NOx was also measured.
引文
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3. 李蕾，张春英，矫庆泽等．Mg-Al-CO_3~(2-)与Zn-Al-CO_3~(2-)水滑石热稳定性差异的研究．无机化学学报，2001，17(1)：113～116
4. 陈银飞．浙江大学博士学位论文，2000
5. 段雪，矫庆泽，李蕾．均分散超细阴离子层状材料的新合成方法．中国专利，9911385，1999-09-14
6. 卢永定．新型矿物材料—水滑石．无机盐工业，1998，30(3)：8～9，31
7. 胡长文等．新型微孔材料杂多阴离子柱撑Zn-Al型阴离子粘土的合成、表征及其催化反应活性的研究．中国科学(B辑)，1995，25(9)：916-922
8. 徐征，贺鹤鸣，蒋大振等．低碳烃类在杂多酸柱水滑石上的烷基化．物理化学学报，1994，39(15)：1392-1395
9. Dimotaki E.D.,Pinnavaia T .J.. Inorg.Chem. 1990,29(13)2393～2394
10. Prinetto F.,Ghiotti G.,Graffin P.,et al. Synthesis and characterization of sol-gel Mg/Al and Ni/Al layered double hydroxides and comparison with co-precipitated samples. Microporous Mesoporous Mater. 2000, 39(1-2):229～247
11. 杜以波，李峰，何静等．影响水滑石晶体结构的因素．燃料化学学报，1997，25：449
12. 李兴林，佘益民，郭军等．杂多阴离子柱撑水滑石层柱相互作用．应用化学，1997，14：105
13. 刘继广，郭军，孙铁等．杂多阴离子柱撑水滑石类层柱材料中层柱相互作用研究．高等学校化学学报，1995，16：1329
14. Kwon T., Tsigdinos G.A., Pinnavaia T.J.. Pillaring of Layered Double Hydroxides by Polyoxometalate Anions. Am. Chem. Soc. 1988,110:3653
15. Kwon T..Pinnavaia T.J..Synthesis and properties of anions clays pillared by [XM_(12)O_(40)]~(n-) Keggin ions. J. Catal. 1992,74:23
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