多殼中空結(jié)構(gòu)的分級孔微納米材料的可控合成及其構(gòu)效關(guān)系
發(fā)布時間：2019-05-17 05:04
【摘要】：進入21世紀(jì)以來,材料工業(yè)作為現(xiàn)代工業(yè)的支柱性產(chǎn)業(yè)之一,已經(jīng)取得了長足發(fā)展并促進社會的高速發(fā)展。中空核殼材料,特別是多殼中空結(jié)構(gòu)的微納米材料,因其具有大的比表面積、豐富的活性位點、低密度、短的傳質(zhì)路徑以及廣闊的空腔結(jié)構(gòu)等優(yōu)點,使其在電化學(xué)、生物醫(yī)藥及環(huán)境保護等領(lǐng)域有著重要發(fā)展并廣泛引起人們的關(guān)注。與此同時,分級孔材料,即一類在微納米材料表面具有不同分級孔道結(jié)構(gòu)(具有兩種或兩種以上孔道結(jié)構(gòu),如小孔-介孔、介孔-大孔等)的材料,也逐漸引起大家的關(guān)注。復(fù)雜的孔道結(jié)構(gòu)賦予材料不僅更多的活性位點和更大的比表面積,而且也大大提高了傳質(zhì)效率并降低了傳質(zhì)阻力�；诖�,既具有多殼中空結(jié)構(gòu)又具有分級孔結(jié)構(gòu)的微納米材料具有良好的發(fā)展應(yīng)用前景。本論文基于多殼中空結(jié)構(gòu)的分級孔材料的研究現(xiàn)狀,運用犧牲模板法成功地可控合成了具有多殼中空結(jié)構(gòu)的分級孔微納米材料。通過調(diào)節(jié)反應(yīng)條件樣品殼層數(shù)可控。利用X-射線衍射、場發(fā)射掃描電子顯微鏡、透射電子顯微鏡等手段對樣品的化學(xué)組分、形貌結(jié)構(gòu)以及應(yīng)用性能進行分析表征。并對樣品的形成機理進行了研究討論,為指導(dǎo)合成更多的具有多殼中空結(jié)構(gòu)的分級孔微納米材料提供堅實的理論基礎(chǔ)和實驗依據(jù)。性能研究分析了這種復(fù)合結(jié)構(gòu)微納米材料在電化學(xué)及環(huán)境保護領(lǐng)域的應(yīng)用,初步探討了其構(gòu)效關(guān)系。為進一步優(yōu)化分級孔材料的多殼中空結(jié)構(gòu)進而提高其性能提供了可靠的實驗依據(jù)。本論文主要開展以下幾項工作:(1)、可控合成具有多殼中空結(jié)構(gòu)的分級孔二氧化硅微納米材料,并研究其形成機理和電化學(xué)性能。利用犧牲模板法合成單層、雙層及三層殼中空結(jié)構(gòu)的分級孔二氧化硅微球,樣品的殼層數(shù)能夠通過前驅(qū)體的負載量控制。通過對樣品的分析表征,研究了樣品的形貌結(jié)構(gòu)及化學(xué)組成;并對樣品的形成機理進一步研究,發(fā)現(xiàn)前驅(qū)體在模板上的吸附深度對樣品形貌起到關(guān)鍵性作用。以樣品作為鋰離子電池負極材料,研究其電化學(xué)性能。結(jié)果表明,隨著二氧化硅的殼層數(shù)的增加,其充放比容量依次增加。尤其是對于具有三層殼中空結(jié)構(gòu)的分級孔二氧化硅微球,它不但具有高的充放比容量又具有良好的循環(huán)穩(wěn)定性。(2)、可控合成具有多殼中空結(jié)構(gòu)的分級孔氧化鑭微納米材料,并研究其形成機理和磷的移除性能。利用犧牲模板法合成具有單層、雙層及三層殼中空結(jié)構(gòu)的分級孔氧化鑭微球,樣品的殼層數(shù)能夠通過前驅(qū)體的負載量及煅燒梯度控制。通過對樣品的分析表征,研究了樣品的形貌結(jié)構(gòu)及化學(xué)組成;又對樣品的形成機理進行探究,提出了分段受熱原理。通過該機理的研究分析,前驅(qū)體的吸附深度及模板的分段受熱共同影響最終樣品的形貌結(jié)構(gòu)。特別是后者,更為緩慢的核殼受熱分離過程使殼層具有更好的機械性能、良好的結(jié)構(gòu)完整性和穩(wěn)定性。它也使納米顆粒堆積更為復(fù)雜進而導(dǎo)致樣品具有更豐富的活性位點�；诖�,我們提出的分段受熱機理為合成具有相似結(jié)構(gòu)的材料提供理論依據(jù)。(3)、具有三層殼中空結(jié)構(gòu)的分級孔氧化鑭微納米材料(記為THLM)作為污水處理中磷的吸附劑,研究其磷的移除性能。結(jié)果表明,樣品THLM對磷具有大的單分子層吸附能力(最大吸附量達到109.02 mg P/g),并且隨著吸附劑用量的增加其吸附性能逐級增加。同時,THLM與磷之間的吸附主要為化學(xué)作用及顆粒間的內(nèi)擴散作用,其次THLM與磷間的吸附機理(即兩者間的吸附作用關(guān)系)主要為配體轉(zhuǎn)換機制。除此之外,THLM具有良好的酸堿適應(yīng)性及循環(huán)吸附性能�；谝陨涎芯�,THLM作為磷的吸附材料用于污水處理具有良好的應(yīng)用前景。(4)、初步探討了可控合成具有多殼中空結(jié)構(gòu)的分級孔羥基磷灰石和氧化鋯微納米材料。利用犧牲模板法合成單層、雙層及三層殼中空結(jié)構(gòu)的分級孔羥基磷灰石和氧化鋯微球,其樣品的殼層數(shù)能夠通過模板用量控制。通過對樣品的分析表征,研究了樣品的形貌結(jié)構(gòu)及化學(xué)組成,并認識到前驅(qū)體在吸附于模板前的離子化作用對樣品形貌起到關(guān)鍵性作用。特別是羥基磷灰石的合成研究,對于合成類似結(jié)構(gòu)的復(fù)雜磷酸鹽具有指導(dǎo)意義。
[Abstract]:Since the 21st century, the material industry has made great progress and promoted the high-speed development of the society as one of the important industries of the modern industry. the hollow core-shell material, in particular the micro-nano material of the multi-shell hollow structure, has the advantages of large specific surface area, rich active site, low density, short mass transfer path and wide cavity structure, There are important developments in the fields of biological medicine and environmental protection, and it is of great concern to people. At the same time, the material of graded pore, that is, a class of materials with different hierarchical pore structures (with two or more pore structures, such as small pores, mesopores, meso-pores, etc.) on the surface of the micro-nano material, has also gradually attracted the attention of the people. The complex pore structure gives the material not only more active sites and larger specific surface area, but also greatly improves the mass transfer efficiency and reduces the mass transfer resistance. The micro-nano material with the multi-shell hollow structure and the hierarchical pore structure has good development and application prospect. In this paper, based on the research status of the hierarchical pore material of the multi-shell hollow structure, the hierarchical pore micro-nano-material with the multi-shell hollow structure is successfully controlled by using the sacrificial template method. And the number of the shell layers of the sample shell can be controlled by adjusting the reaction condition. The chemical composition, morphology and application of the sample were characterized by X-ray diffraction, field emission scanning electron microscope and transmission electron microscope. And the formation mechanism of the sample is studied and discussed, and a solid theoretical foundation and experimental basis for guiding the synthesis of the graded pore micro-nano material with the multi-shell hollow structure are provided. The application of the composite structure micro-nano-material in the field of electrochemical and environmental protection was analyzed and the structure-effect relationship was discussed. And provides a reliable experimental basis for further optimizing the multi-shell hollow structure of the graded pore material and further improving the performance. In this paper, the following work is carried out: (1) to control the synthesis of porous silica micro-nano-materials with multi-shell hollow structure, and to study its formation mechanism and electrochemical performance. And the shell number of the sample can be controlled by the loading amount of the precursor by using the sacrificial template method to synthesize the graded-hole silicon dioxide microsphere with the hollow structure of the single layer, the double layer and the three-layer shell. The morphology and chemical composition of the samples were studied by the analysis and characterization of the samples, and the formation mechanism of the samples was further studied. The adsorption depth of the precursor on the template was found to play a key role in the morphology of the samples. The electrochemical performance of the sample was studied as the negative electrode of Li-ion battery. The results show that with the increase of the shell number of the silica, the charge-and-discharge ratio increases in turn. In particular to a hierarchical pore silica microsphere with a three-layer shell hollow structure, which not only has high charge and discharge ratio capacity but also has good cycle stability. (2) the micro-nano-material with the hierarchical pores of the multi-shell hollow structure can be controlled and synthesized, and the forming mechanism and the removal performance of the phosphorus are studied. By using the sacrificial template method to synthesize the graded-hole oxidized polystyrene microsphere with the hollow structure of the single layer, the double layer and the three-layer shell, the shell number of the sample can be controlled by the loading of the precursor and the sintering gradient. The morphology and chemical composition of the samples were studied by the analysis and characterization of the samples, and the formation mechanism of the samples was investigated. Through the research and analysis of the mechanism, the adsorption depth of the precursor and the sectional heat of the template influence the appearance structure of the final sample. In particular the latter, the more slow core-shell heat separation process enables the shell to have better mechanical properties, good structural integrity and stability. It also makes the nanoparticle build-up more complex and results in a more abundant active site for the sample. Based on this, the proposed segmented heating mechanism provides a theoretical basis for the synthesis of materials with similar structure. And (3) a graded-hole-oxidized micro-nano-material (called THLM) with a three-layer shell hollow structure is used as an adsorbent for phosphorus in the sewage treatment, and the removal performance of the phosphorus is studied. The results show that the sample THLM has a large adsorption capacity (maximum adsorption amount of 109.02 mg P/ g) for phosphorus, and the adsorption performance of the sample is increased gradually with the increase of the amount of the adsorbent. At the same time, the adsorption between THLM and phosphorus is mainly the chemical action and the internal diffusion of the particles, and then the adsorption mechanism between the THLM and the phosphorus (that is, the relationship between the adsorption of the two) is mainly the ligand conversion mechanism. In addition, the THLM has good acid-base adaptability and cyclic adsorption performance. Based on the above research, THLM has a good application prospect as a phosphorus adsorption material for sewage treatment. (4) A preliminary study on the controllable synthesis of graded-pore hydroxyapatite and oxide micro-nano-materials with a multi-shell hollow structure. By using the sacrificial template method to synthesize the graded-hole hydroxyapatite and the oxygen-oxide microsphere of the hollow structure of the single-layer, the double-layer and the three-layer shell, the shell number of the sample can be controlled by the amount of the template. The morphology and chemical composition of the samples were studied by the analysis and characterization of the samples. In particular, the synthesis of hydroxyapatite is of great significance in the synthesis of complex phosphate with similar structure.
【學(xué)位授予單位】：河南師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TB383.1
本文編號：2478823
[Abstract]:Since the 21st century, the material industry has made great progress and promoted the high-speed development of the society as one of the important industries of the modern industry. the hollow core-shell material, in particular the micro-nano material of the multi-shell hollow structure, has the advantages of large specific surface area, rich active site, low density, short mass transfer path and wide cavity structure, There are important developments in the fields of biological medicine and environmental protection, and it is of great concern to people. At the same time, the material of graded pore, that is, a class of materials with different hierarchical pore structures (with two or more pore structures, such as small pores, mesopores, meso-pores, etc.) on the surface of the micro-nano material, has also gradually attracted the attention of the people. The complex pore structure gives the material not only more active sites and larger specific surface area, but also greatly improves the mass transfer efficiency and reduces the mass transfer resistance. The micro-nano material with the multi-shell hollow structure and the hierarchical pore structure has good development and application prospect. In this paper, based on the research status of the hierarchical pore material of the multi-shell hollow structure, the hierarchical pore micro-nano-material with the multi-shell hollow structure is successfully controlled by using the sacrificial template method. And the number of the shell layers of the sample shell can be controlled by adjusting the reaction condition. The chemical composition, morphology and application of the sample were characterized by X-ray diffraction, field emission scanning electron microscope and transmission electron microscope. And the formation mechanism of the sample is studied and discussed, and a solid theoretical foundation and experimental basis for guiding the synthesis of the graded pore micro-nano material with the multi-shell hollow structure are provided. The application of the composite structure micro-nano-material in the field of electrochemical and environmental protection was analyzed and the structure-effect relationship was discussed. And provides a reliable experimental basis for further optimizing the multi-shell hollow structure of the graded pore material and further improving the performance. In this paper, the following work is carried out: (1) to control the synthesis of porous silica micro-nano-materials with multi-shell hollow structure, and to study its formation mechanism and electrochemical performance. And the shell number of the sample can be controlled by the loading amount of the precursor by using the sacrificial template method to synthesize the graded-hole silicon dioxide microsphere with the hollow structure of the single layer, the double layer and the three-layer shell. The morphology and chemical composition of the samples were studied by the analysis and characterization of the samples, and the formation mechanism of the samples was further studied. The adsorption depth of the precursor on the template was found to play a key role in the morphology of the samples. The electrochemical performance of the sample was studied as the negative electrode of Li-ion battery. The results show that with the increase of the shell number of the silica, the charge-and-discharge ratio increases in turn. In particular to a hierarchical pore silica microsphere with a three-layer shell hollow structure, which not only has high charge and discharge ratio capacity but also has good cycle stability. (2) the micro-nano-material with the hierarchical pores of the multi-shell hollow structure can be controlled and synthesized, and the forming mechanism and the removal performance of the phosphorus are studied. By using the sacrificial template method to synthesize the graded-hole oxidized polystyrene microsphere with the hollow structure of the single layer, the double layer and the three-layer shell, the shell number of the sample can be controlled by the loading of the precursor and the sintering gradient. The morphology and chemical composition of the samples were studied by the analysis and characterization of the samples, and the formation mechanism of the samples was investigated. Through the research and analysis of the mechanism, the adsorption depth of the precursor and the sectional heat of the template influence the appearance structure of the final sample. In particular the latter, the more slow core-shell heat separation process enables the shell to have better mechanical properties, good structural integrity and stability. It also makes the nanoparticle build-up more complex and results in a more abundant active site for the sample. Based on this, the proposed segmented heating mechanism provides a theoretical basis for the synthesis of materials with similar structure. And (3) a graded-hole-oxidized micro-nano-material (called THLM) with a three-layer shell hollow structure is used as an adsorbent for phosphorus in the sewage treatment, and the removal performance of the phosphorus is studied. The results show that the sample THLM has a large adsorption capacity (maximum adsorption amount of 109.02 mg P/ g) for phosphorus, and the adsorption performance of the sample is increased gradually with the increase of the amount of the adsorbent. At the same time, the adsorption between THLM and phosphorus is mainly the chemical action and the internal diffusion of the particles, and then the adsorption mechanism between the THLM and the phosphorus (that is, the relationship between the adsorption of the two) is mainly the ligand conversion mechanism. In addition, the THLM has good acid-base adaptability and cyclic adsorption performance. Based on the above research, THLM has a good application prospect as a phosphorus adsorption material for sewage treatment. (4) A preliminary study on the controllable synthesis of graded-pore hydroxyapatite and oxide micro-nano-materials with a multi-shell hollow structure. By using the sacrificial template method to synthesize the graded-hole hydroxyapatite and the oxygen-oxide microsphere of the hollow structure of the single-layer, the double-layer and the three-layer shell, the shell number of the sample can be controlled by the amount of the template. The morphology and chemical composition of the samples were studied by the analysis and characterization of the samples. In particular, the synthesis of hydroxyapatite is of great significance in the synthesis of complex phosphate with similar structure.
【學(xué)位授予單位】：河南師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TB383.1
【參考文獻】
相關(guān)期刊論文 前1條
1 高家誠,張亞平;羥基磷灰石生物陶瓷材料的現(xiàn)狀和發(fā)展[J];材料導(dǎo)報;1991年06期
，本文編號：2478823
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