本文選題：magadiite + 超大微孔-介孔　； 參考：《北京化工大學(xué)》2015年碩士論文

【摘要】：二維層狀粘土材料因其良好的離子交換性、吸附性及層間膨脹性而廣泛應(yīng)用于催化、吸附及新型功能材料領(lǐng)域。本文以自制的純硅基粘土水合硅酸鈉麥羥硅鈉石(magadiite)為主體,采用共表面活性劑導(dǎo)向二維層間TEOS原位水解-縮聚法制備了magadiite基多級孔異質(zhì)結(jié)構(gòu)(PMH)。以PMH為基質(zhì),采用后嫁接鋁法合成系列鋁摻雜PMH催化劑,使用XRD、SEM/EDS、HRTEM、BET、27Al和29Si MAS NMR、 NH3-TPD與吡啶FT-IR等表征系統(tǒng)研究催化劑的結(jié)構(gòu)、組成、形貌與表面酸性,深入探討催化劑的傅-克烷基化活性。以十六烷基三甲基銨根(CTMA+)插層magadiite為基體,首次采用層間嫁接法制備出羅丹明B修飾magadiite基"OFF-ON"熒光傳感器并研究其裸眼檢測Hg2+-性能。論文的主要結(jié)論與創(chuàng)新點如下：(1)通過共模板劑導(dǎo)向TEOS在二維粘土magadiite層間原位水解-縮聚法制備了多級孔magadiite基異質(zhì)結(jié)構(gòu)(PMH)；層間介孔氧化硅與粘土層板的有機結(jié)合使PMH材料兼具超大比表面積(729 m2/g)、高的熱穩(wěn)定性及獨特的超大微孔-介孔結(jié)構(gòu)(0.80-1.96nm)。分別采用PMH后嫁接鋁法和Al-magadiite前體法制備出鋁摻雜PMH催化劑(xAl-PMH, x為Al/Si摩爾比,x=0.2、0.4、0.6、)和Al-magadiite基多級孔異質(zhì)結(jié)構(gòu)(PAMH, Al/Si摩爾小學(xué)=0.03)催化劑。xAl-PMH保持了良好的層狀超大微孔-介孔多級孔結(jié)構(gòu)(0.78-1.90±0.02 nm)和大的比表面積(282 m2/g),鋁主要以四面體形式嫁接于PMH層間硅骨架內(nèi),顯示出強的Lewis酸性與新生成的Bronsted酸性,而PMH僅有極弱的Lewis酸性。PAMH中鋁則以層狀骨架外八面體鋁為主,因而導(dǎo)致了略微提高的Lewis酸性和微量Bronsted酸性。(2)以鄰苯二酚(CAT)與叔丁醇(TBA)液相傅-克烷基化為目標反應(yīng)考察催化劑的活性。優(yōu)化的反應(yīng)條件為反應(yīng)溫度138℃、TBA/CAT投料摩爾比2.0、反應(yīng)時間4小時。在最優(yōu)實驗條件下,0.4A1-PMH給出了高達93.4%的CAT轉(zhuǎn)化率、最高的對叔丁基鄰苯二酚(4-TBC)選擇性(80.4%)及最高的4-TBC收率(75.1%),歸因為該催化劑較大的比表面積、最小的微孔體積和最多的表面Bronsted酸性位及其與保持良好的層狀超大微孔-介孔結(jié)構(gòu)間的強協(xié)同效應(yīng)。(3)以CTMA+插層magadiite為基體,以羅丹明B-乙二胺內(nèi)酰胺衍生物SRhB與異氰酸酯丙基三乙氧基硅烷反應(yīng)得到的SRhB-IPTS為熒光探針,采用層間嫁接法將不同含量的SRhB-IPTS固載在CTMA-maga上,制備出新型羅丹明B修飾,magadiite基"OFF-ON"熒光傳感器(SRhB-maga-X,X為SRhB-IPTS/CTMA-maga投料摩爾比,X=1或6、)。(4) SRhB-maga-6顯示出較優(yōu)的裸眼檢測Hg2+性能,可在2分鐘內(nèi)檢測出Hg2+,檢測限為6.2×10-7M,并且對Hg2+檢測性能在pH 5.0-12.0范圍內(nèi)不受環(huán)境pH干擾。SRhB-maga-6可從包括堿金屬、堿土金屬、第一周期過渡金屬和重金屬的多種金屬離子中選擇性識別Hg2+。使用過的SRhB-maga-6可在四丙基氫氧化銨溶液中簡便再生、重復(fù)使用。該新型熒光傳感器優(yōu)異的Hg2+檢測性能歸因為其高的熒光探針SRhB-IPTS含量及其與基體以Si-O-Si鍵有序的鏈接和開闊的層間通道。
[Abstract]:Two-dimensional layered clay materials are widely used in catalysis, adsorption and new functional materials due to their good ion exchange, adsorption and interlaminar expansion. In this paper, magadiite based multilevel pore heterostructure was prepared by co-surfactant guided two-dimensional TEOS in-situ hydrolysis-Polycondensation method, based on self-made silicon-based clay hydrated sodium silicate sodium silicate. A series of Al-doped PMH catalysts were synthesized by post-grafting aluminum method with PMH as the substrate. The structure, composition, morphology and surface acidity of the catalysts were studied by using XRD-SEM- EDM / EDSE-HRTE-BET-27Al and 29Si MAS NMRs, NH3-TPD and pyridine FT-IR. The activity of catalyst for Friedel-g alkylation was discussed. Using cetyltrimethylammonium trimethylammonium (magadiite) intercalated magadiite as substrate, Rhodamine B modified magadiite based "OFF-ON" fluorescence sensor was prepared by interlaminar grafting for the first time, and its open-eye detection of Hg2-was studied. The main conclusions and innovations of this paper are as follows: (1) TEOS was synthesized by in-situ hydrolysis-Polycondensation method of two-dimensional clay magadiite, and the organic combination of interlaminar mesoporous silica and clay laminates resulted in the synthesis of multilevel porous magadiite based heterostructure by in-situ hydrolysis-Polycondensation method. The PMH materials have a high specific surface area of 729m2 / g / g, high thermal stability and unique ultra-large microporous mesoporous structure of 0.80-1.96nmm. Aluminum-doped PMH catalyst (x = Al/Si molar ratio, x = Al/Si = 0.2n 0.4U 0.6G) and Al-magadiite based multilevel pore heterostructure (Pam H, Al/Si Mohr 0.03) were prepared by PMH and Al-magadiite precursor methods respectively. The catalyst. XAl-PMH kept a good layer super large micropore and many mesoporous pores. The mesoporous structure is 0.78-1.90 鹵0.02 nm) and the large specific surface area is 282 m2 / g / g. Aluminum is grafted mainly in the form of tetrahedron into the PMH interlaminar silicon skeleton. The results showed that the strong acidity of Lewis and the acidity of newly formed Bronsted showed that the aluminum in PMH was mainly octahedral aluminum with outer layered skeleton, which was only very weak in Lewis acidity. This led to a slight increase in the acidity of Lewis and a slight increase in the acidity of Bronsted. The activity of the catalyst was investigated by focusing on the liquid-phase Friede-gram alkylation of catechol (catechol) with tert-butanol (TBA). The optimum reaction conditions were as follows: reaction temperature 138 鈩，

本文編號：1794193