Synthesis of New Layered Double Hydroxide Intercalates

新型层状双氢氧化物插层物的合成

基本信息

批准号：
04045054
负责人：
NARITA Eiichi
金额：
$ 0.64万
依托单位：
Hachinohe National College of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for international Scientific Research
财政年份：
1992
资助国家：
日本
起止时间：
1992 至无数据
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-04045054/
关键词：
Layerd Double Hydroxide Hydrotalcite Intercalation Coprecipitation Intercalate Layered Compound Heteropolyoxometallate Silicate

项目摘要

Layered Double Hydroxides (LDHs),[NM^<2+>_xM^<3+>_<1-x>(OH)_2][A^<n->_<x/n>・yH_2O], consist of positively charged brucite-like layers separated by charge-balancing hydrated gallery anions A^<n->. In this study, polyoxometallate (POM)-pillared LDHs have been prepared by the new techniques.1. Preparation and characterization of silicate-intercalated LDHs via carboxylate-pillared precursorsIntercalation of silicate anions in gallery space of carboxylate-pillared LDH with different layer distance has been investigated by ion exchange method. The intercalation was carried out by adding a starting parent LDH in NaOH solution containing silicic acid granulas with vigorous stirring and by refluxing the reaction mixture at 100 ﾟCSilicate anions were found to be intercalated to from the silicated LDH with basal spacing of 11.4-12.1A^^ﾟ at the conditions of > O.O5 M NaOH and reaction time of 2.5 h. However, the interlayer structure of the silicated LDH was influenced with initial gallery height o … More f the parent LDH and the adipate-pillared LDH having a little bigger basal spacing [d_<003>=13.9A^^ﾟ) has givern the most well-ordered LDH product with two-dimensional silicate anions as the interlayer guest. The crystallinity of the sillicated LDH products was in order: adipate-pillared LDH [d_<003>=13.9A^^ﾟ) > terephthalate-pillared LDH (14.5A^^ﾟ) > sebacate-pillared LDH (16.8A^^ﾟ)> chlorinated LDH (7.8A^^ﾟ) > > laurate-pillared LDH (31.5A^^ﾟ). The silicated LDHs were also investigated by XRD, IR, TG-DTA, MAS-NMR etc.2. Direct synthesis of a polyoxometallate-pillared layered double hydroxide by copreciptationA new method for the preparation of POM-pillared LDH has been accomplished by using the corecipitation reaction as follows. First, alpha-[SiW_<11>O_<39>]^<8-> was dissolved in water and pH the POM solution was adjusted to6.0. Then, the mixed solution of Zn^<2+> and Al^<3+> ions was added drop-wise to the vigorously stirred POM solution at 100 ﾟC. The coprecipita-tion reaction of Zn^<2+> and Al^<3+> ions in moderately acidic alpha-[SiW_<11>O_<39>]^<8-> solution directly was found to afford a LDH derivative with an approxi-mate composition of [Zn_<24>Al_8(OH)_<64>][alpha-SiW_<11>O_<39>] and an exceptionally well-ordered gallery height of 9.8A^^ﾟ. Less

分层的双羟基（LDHS），[NM^<2+> _ Xm^<3+> _ <1-x>（OH）_2] [a^<n-> _> _ <x/n> yh_2o]，由带电的带电荷的水合水合的油化油化的油化油管分离为阳性带电的brucite brucite like层。在这项研究中，通过新技术制备了多氧金属酸盐（POM） - 斑点LDH。通过离子交换方法研究了通过羧酸盐 - 柱状LDH的画廊空间中硅胶阴离子的羧酸盐前体进行硅酸盐前体分裂的制备和表征。通过在含有剧烈搅拌的NaOH溶液中添加含有硅酸颗粒的NaOH溶液中的起始母体LDH，并通过在100 csilicate阴离子中反应混合物在NaOH溶液中添加硅酸颗粒，并在100 csilicate阴离子中反应混合物在> 11.4-12.1a^^^na^^^na^o.ohoh的条件下的基本间距中从硅胶LDH插入到硅胶LDH中。然而，硅化的LDH的层间结构受到初始画廊的高度o…更多的是，父母LDH和adipate-pillared LDH具有一个小的基本间距[d_ <003> = 13.9a ^^ ﾟ）具有最有序的LDH产品，具有二维硅胶式的layricone silicone Anions in Interlaylaylaylayeres reveres。 The crystallinity of the sillicated LDH products was in order: adipate-pillared LDH [d_<003>=13.9A^^ﾟ) > terephthalate-pillared LDH (14.5A^^ﾟ) > sebacate-pillared LDH (16.8A^^ﾟ) > chlorinated LDH (7.8A^^ﾟ) > > laurate-pillared LDH （31.5a ^^ ﾟ）。还通过XRD，IR，TG-DTA，MAS-NMR等研究了硅化的LDH。通过使用以下方式，通过使用cOM-PILLARED LDH的新方法直接合成多氧金属柱分层双氢氧化氢氧化物的新方法，已通过使用以下的归化反应来实现。首先，将alpha- [siw_ <11> o_ <39>]^<8->溶解在水中，然后将POM溶液调整为6.0。然后，将Zn^<2+>和Al^<3+离子的混合溶液从滴度上添加到100°C的剧烈搅拌的POM溶液中。 Zn^<2+>和Al^<3+>离子在适度酸性α-[SIW_ <11> o_ <39>]^<8->溶液中的转化反应，可直接发现具有LDH衍生物，具有[Zn__ <24> al_8> al_8（OH）的近似组成排序良好的画廊高度为9.8a ^^ ﾟ。较少的