本文關(guān)鍵詞： 自蔓延燃燒法 燒綠石型 Ln_2Zr_2O_7納米晶 熒光性質(zhì) 光催化性能 高氯酸銨 催化劑　出處：《南京理工大學(xué)》2015年博士論文　論文類(lèi)型：學(xué)位論文

【摘要】：制備新型納米及亞微米級(jí)材料是當(dāng)今材料領(lǐng)域研究的熱點(diǎn)之一。本文以具有高的導(dǎo)電性、高化學(xué)穩(wěn)定性、高催化活性的燒綠石型稀土鋯酸鹽(Ln2Zr2O7)為研究對(duì)象,通過(guò)尋求綠色的合成手段,在相對(duì)溫和的環(huán)境中獲得尺寸小、分散性好的納米粒子。本文將軟化學(xué)法運(yùn)用到其制備過(guò)程中,制備出了系列Ln2Zr2O7為基礎(chǔ)的摻雜納米材料,研究了其結(jié)構(gòu)、形貌以及光催化性能等,主要內(nèi)容如下:采用了一種軟化學(xué)法—鹽助甘氨酸自蔓延燃燒法,在較低的溫度下制備了系列Ln2Zr2O7(Ln = La,Nd,Sm,Eu,Dy,Er),系統(tǒng)研究了 Ln 對(duì) Ln2Zr2O7 晶體結(jié)構(gòu)的影響;初步研究了反應(yīng)機(jī)理。結(jié)果表明鹽助甘氨酸自蔓延燃燒法所制得產(chǎn)物的團(tuán)聚少,粒子粒徑分布均勻,平均粒徑在30 nm左右。對(duì)所制備的Ln2Zr2O7系列產(chǎn)物的光催化活性進(jìn)行了研究,結(jié)果發(fā)現(xiàn),合成的產(chǎn)物均有好的光催化活性,Ln的種類(lèi)對(duì)Ln2Zr2O7系列的催化活性有較大的影響,其光催化活性的順序?yàn)镈y2Zr2O7Nd2Zr2O7Er2Zr2O7Sm2Zr2O7La2Zr2O7。在這個(gè)體系中隨著原子序數(shù)的增加,納米晶的光催化活性變化規(guī)律與稀土金屬陽(yáng)離子Ln3+磁矩的變化規(guī)律一致。說(shuō)明稀土離子的光催化活性與Ln3+磁矩同源于4f電子結(jié)構(gòu)。系統(tǒng)研究了 A位的Ln部分被其他Ln取代的La_(2-x)Ln_xZr_2O_7系列化合物的制備及光催化性能,采用軟化學(xué)法—鹽助甘氨酸自蔓延燃燒法,制備了系列La2-xLnxZr7O7(Ln =La,Nd,Sm,Eu,Dy,Er)納米晶。結(jié)果表明,A位置的La可以被其他鑭系元素Ln取代,而不改變其晶型。Ln實(shí)際上代替了 La摻雜進(jìn)入其晶格中,產(chǎn)物為單一晶相的固溶體。通過(guò)鹽助甘氨酸自蔓延燃燒法制備了高分散的,粒度分布均勻,粒子尺寸約20nm～40 nm的La_(2-x)Ln_xZr_2O_7系列化合物。并對(duì)產(chǎn)物的熒光性質(zhì)及光催化性能進(jìn)行了系統(tǒng)研究。采用鹽助甘氨酸自蔓延燃燒法合成了 A位的Ln部分被過(guò)渡金屬取代的Ln_(2-x)M_xZr_2O_7系列化合物,得到了單一相的固溶體。結(jié)果表明,Ln3+可以被M3+置換,且不改變晶型,產(chǎn)物為單一相的燒綠石型固溶體。而且所制備的粒子分布均勻,形狀規(guī)則,分散性好。同時(shí)研究了其光催化活性,結(jié)果發(fā)現(xiàn)Ln_(2-x)M_xZr_2O_7系列具有好的催化活性。采用鹽助甘氨酸自蔓延燃燒法制備的A位的Ln部分被取代的La_(2-x)Ln_xZr_2O_7和Ln_(2-x)M_xZr_2O_7系列化合物,研究其對(duì)高氯酸銨(AP)熱分解的催化性能。采用DSO/TG-MS聯(lián)用技術(shù)研究了 Ln_(2-x)M_xZr_2O_7對(duì)高氯酸銨的催化。結(jié)果表明,Ln_(2-x)M_xZr_2O_7對(duì)高氯酸銨(AP)有較強(qiáng)的催化作用,添加2%的Ln_(2-x)M_xZr_2O_7使高氯酸銨的分解溫度降低,分解放熱量增大。最大程度發(fā)揮了納米催化劑的催化效能。與單純的金屬氧化物相比,摻雜燒綠石型的納米粒子均表現(xiàn)出對(duì)高氯酸銨(AP)有較好的催化性能。采用鹽助甘氨酸自蔓延燃燒法,以硝酸鏑、硝酸鈷和硝酸鈰為原料,甘氨酸為燃燒劑,KCl為反應(yīng)惰性鹽,通過(guò)變化nGlycine/nM值、鹽用量、煅燒溫度控制納米晶體的粒徑,制備了立方晶系螢石型Dy2-xCoxCe2O7納米晶。Dy3+可以被Co3+部分置換,且不改變晶型,產(chǎn)物為單一相的螢石型固溶體。所獲得的納米粒子具有良好的分散性,粒徑約為18nm。采用DSC/TG-MS聯(lián)用技術(shù)研究了 Dy1.9Co0.1Ce2O7對(duì)高氯酸銨的催化。結(jié)果表明,Dy1.9Co0.1Ce2O7對(duì)高氯酸銨(AP)有較強(qiáng)的催化作用,添加2%的Dy1.9Co0.1Ce2O7使高氯酸銨的分解溫度降低近120℃,分解放熱量從453.11 J/g增大到1337.68 J/g。說(shuō)明加入納米摻鈷鈰酸鏑催化高氯酸銨(AP)熱分解,催化效果優(yōu)于相同條件下制備的納米金屬氧化物和未慘雜的鈰酸鏑。
[Abstract]:The preparation of a new type of nano and submicron materials is one of the hot spots in the field of materials research. This paper has a high conductivity, high chemical stability, pyrochlore type rare earth zirconate high catalytic activity (Ln2Zr2O7) as the research object, by seeking the green synthesis methods, in the phase of the soft environment in size small, scattered ions. The soft chemical method is used in the preparation process, the preparation of a series of Ln2Zr2O7 based doped nano material, studied its structure, morphology and photocatalytic properties. The main contents are as follows: using a soft chemical method - glycine salt assisted self propagating combustion method at low temperature to prepare a series of Ln2Zr2O7 (Ln = La, Nd, Sm, Eu, Dy, Er), studied the influence of Ln on the crystal structure of Ln2Zr2O7; preliminary study on reaction mechanism. The results show that the combustion method for glycine salt assisted self propagating The product had a little agglomeration and the particle size distribution, the average particle size of about 30 nm. The photocatalytic activity of Ln2Zr2O7 series of prepared samples were studied, the results showed that the photocatalytic activity of the synthesized products were good, has great influence on the catalytic activity of Ln species on the Ln2Zr2O7 series, the the photocatalytic activity of the order of Dy2Zr2O7Nd2Zr2O7Er2Zr2O7Sm2Zr2O7La2Zr2O7. in this system as the atomic number increases, consistent with the variation regularity of nanocrystals and photocatalytic activity of rare earth metal cation Ln3+ magnetic moment. The photocatalytic activity of rare earth ions and Ln3+ moment homology to the electronic structure of 4f system. The effect of Ln A is replaced by Ln La_ (2-x) preparation and photocatalytic properties of Ln_xZr_2O_7 compounds, using soft chemical method - glycine salt assisted self propagating combustion method, a series of La2-xLnxZr7O7 were prepared (Ln =La Nd, Sm, Eu, Dy, and Er) nanocrystals. The results show that the location of A La can be used by other lanthanide substituted Ln, and not change the crystal type of.Ln actually replaced La doped into the lattice, the products were single phase solid solution. The salt assistant glycine SHS method preparation of highly dispersed combustion, uniform particle size distribution, particle size of about 20nm ~ 40 nm La_ (2-x) Ln_xZr_2O_7 series compounds. And fluorescence properties and photocatalytic properties of the products were studied. Using salt assistant glycine self propagating combustion synthesis of Ln A is part of a transition metal substituted Ln_ (2-x) M_xZr_2O_7 series of compounds, the single phase solid solution. The results show that Ln3+ can be M3+ replacement, and does not change the crystal type, product is single pyrochlore type solid solution. And the preparation of uniform particle size distribution, regular shape and good dispersion. At the same time on the light catalytic activity And the results showed that Ln_ (2-x) M_xZr_2O_7 has good catalytic activity. The salt assistant glycine SHS prepared by A Ln was partially substituted La_ (2-x) Ln_xZr_2O_7 and Ln_ (2-x) M_xZr_2O_7 series of compounds, the study of ammonium perchlorate (AP) thermal decomposition. The catalytic performance based on DSO/TG-MS technology Ln_ (2-x) M_xZr_2O_7 catalyst of ammonium perchlorate. The results showed that Ln_ (2-x) M_xZr_2O_7 of ammonium perchlorate (AP) has a strong catalytic effect, the addition of 2% Ln_ (2-x M_xZr_2O_7) to lower the decomposition temperature of ammonium perchlorate decomposition heat release increased. Maximize the catalytic performance of nanometer catalyst. Compared with pure metal oxide nanoparticles, doped pyrochlore type showed on ammonium perchlorate (AP) has better catalytic properties. By combustion method salt assistant glycine nitrate self propagating in dysprosium cobalt nitrate and cerium nitrate as raw The material, glycine as combustion agent, KCl as reaction inert salt, by changing the nGlycine/nM value, salt dosage and calcination temperature control of the particle size of the nanocrystals, prepared cubic fluorite type nanocrystalline Dy2-xCoxCe2O7.Dy3+ can be Co3+ replacement, and does not change the crystal type, the product is single phase fluorite type solid solution. The obtained nanoparticles have good dispersion, particle size of about 18nm. technology to study the catalytic Dy1.9Co0.1Ce2O7 of ammonium perchlorate by DSC/TG-MS. The results showed that Dy1.9Co0.1Ce2O7 of ammonium perchlorate (AP) has a strong catalytic effect, add 2% of Dy1.9Co0.1Ce2O7 so that the decomposition temperature of the ammonium perchlorate reduction of up to 120 DEG C the heat decomposition, increases from 453.11 J/g to 1337.68 J/g. nano cobalt doped cerium dysprosium acid catalytic ammonium perchlorate (AP) thermal decomposition, catalytic effect is better than that under the same conditions for preparation of nano metal oxide and doped cerium Dysprosium acid.

【學(xué)位授予單位】：南京理工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類(lèi)號(hào)】：TB383.1;O643.36

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