發(fā)布時間：2018-01-02 09:06

  本文關鍵詞：系列鉍基金屬有機框架材料的制備、表征及其光催化性能的研究　出處：《山東大學》2016年碩士論文　論文類型：學位論文

  更多相關文章： 鉍 金屬有機框架材料 晶體結構 光催化性能

【摘要】：金屬有機框架(Metal-Organic Frameworks, MOFs)材料是一類利用金屬離子或者金屬氧化物團簇與有機配體之間的配位鍵作用組裝成的具有網狀框架結構的多孔固體材料。近年來,MOFs材料由于其比表面積大,高孔隙度以及結構-功能的多樣可調性等結構性質,在多個領域如氣體儲存、選擇性吸附與分離、催化、發(fā)光材料以及藥物載體等各方面具有很好的應用前景。其中,光催化能夠將太陽能轉換為電能、化學能,進而用來分解水產生可再生氫能,降解污染物,還原C02等,成為解決能源短缺及環(huán)境污染等問題的有效途徑,因此MOFs材料在光催化領域的應用受到廣泛關注。MOFs材料在光催化上有其獨特的優(yōu)勢,主要表現在兩個方面：(1)結構-功能的可調性；(2)大的孔隙度和排列有序的孔道結構。利用MOFs材料結構-功能的可調性,通過對金屬位點和有機配體的改變或者修飾等手段,實現對材料光催化性能的調節(jié)。具體在光催化上,表現為調節(jié)材料光吸收范圍；提高載流子分離效率；暴露的不飽和金屬位點促進光催化反應。此外,MOFs材料具有大的孔隙度、比表面積以及排列有序的孔道結構,有利于一些客體分子的引入,使其能夠直接與MOFs上的活性位點進行接觸,縮短了電子傳輸距離,提高了載流子的傳輸效率,進而促進光催化反應的進行。迄今為止,已經發(fā)現一些MOFs材料具有高效的光催化性能,并且被分別應用在光催化降解污染物、光解水產氫以及還原C02等方面。但是這些光催化MOFs材料大多是基于Ti, Zr, Fe等過渡金屬元素的,對其他金屬基MOFs材料的光催化研究還很少,因此探究一些由主族金屬或其他金屬組成的光催化MOFs材料是很有必要的。鉍系無機半導體表現出優(yōu)異的光催化性能,成為光催化領域的一大研究熱點。對鉍系光催化材料的研究已成體系,而且我們課題組研究了一系列鉍系光催化材料,如Bi2O3, BiOX (X=C1, Br, I), Bi2O2CO3, BiVO4, Bi2SiO5等,積累了豐富的實踐和理論經驗。同時鉍系材料儲量豐富,環(huán)境友好無毒,穩(wěn)定性好,而且鉍離子具有靈活多變的配位構型,有利于構建結構多樣的MOFs�；谝陨戏治�,我們推測鉍基MOFs材料在光催化降解有機染料、光解水產氫、產氧等方面具有很好的應用。因此,在本論文中,我們開發(fā)了幾種新型的鉍基MOFs光催化材料,并研究了它們的光催化反應機理,具體內容分為五章：第一章首先介紹了MOFs材料的相關背景知識、合成方法以及主要應用領域。其次就MOFs材料在光催化領域的研究進展做了簡單的概述,總結了MOFs材料在光催化上的優(yōu)勢以及主要的光催化機理理論。接著介紹了鉍基MOFs材料在光催化領域的研究進展。最后闡述了本論文的選題意義、研究思路和主要內容。第二章主要包括MOF材料Bi-mna的制備以及光催化性能、機理的研究。利用簡單的溶劑熱方法制備了MOF材料Bi-mna的粉末,對其進行了XRD, TG/DTA等基本的表征,證明了樣品的純度,并對材料的結構特點進行簡單介紹。通過測定光電流響應和交流阻抗譜,發(fā)現Bi-mna具有優(yōu)異的光電化學性質。然后利用光降解有機物染料和光解水產氧能力來表征Bi-mna的光催化性能,結果顯示Bi-mna能夠在可見光照射下高效降解有機染料RhB和MB,并且在6h內持續(xù)不斷分解水產生氧氣,表現出了高效的光催化活性。通過對Bi-mna的能帶結構和電子分布等進行理論計算,我們提出了一種新型的光催化機理理論,即配體到配體電子轉移(LLCT)過程,并用實驗驗證了這一理論。LLCT過程的發(fā)生,能夠延長材料中光生載流子的壽命,從而促進光生載流子的有效分離,提高材料的光催化效率。在第三章中,我們選用有機配體均苯三酸(H3BTC),制備兩種鉍基MOFs材料并對其光物理和光催化性能進行研究。(1)首先合成了一種新型鉍基MOF材料Bi-BTC的單晶,并通過X射線單晶衍射技術得到了Bi-BTC的晶體結構信息。Bi-BTC中具有二聚體{Bi2014｝,這些{Bi2014｝基團之間由配體BTC3-連接形成了三維的框架結構。同時,沿b軸方向,{Bi2014｝基團通過配體的連接分別形成兩種不同的螺旋鏈,這兩種螺旋鏈交替排列,相鄰的螺旋鏈共享一組{Bi2014｝二聚體,以一定的夾角組裝在一起。漫反射光譜研究結果表明Bi-BTC的光吸收主要由配體引起,同時配體與鉍的鍵合使其配位環(huán)境改變,引起了漫反射光譜和熒光發(fā)射光譜中的紅移現象。初步研究發(fā)現,Bi-BTC具有在全光照射下分解水產生氧氣的光催化活性。(2)我們在嘗試合成Bi-BTC單晶的過程中,獲得了Bi-BTC的一種同素異構體BiO-BTC。BiO-BTC是以甲酸氧鉍(BiOHCOO)和H3BTC作為原料進行溶劑熱反應獲得的。根據BiOHCOO的離子交換性質我們推測這種材料是一種層狀的有機無機雜化材料,由BTC陰離子替代BiOHCOO中HCOO-層獲得的。通過對材料進行EXAFS,XRD,FT-IR以及熱分析等測試對以上推測進行了驗證。BTC陰離子的引入并沒有改變原來的層狀結構,僅僅使Bi2022+層發(fā)生結構的扭曲。研究其光催化活性,發(fā)現這種材料在全光下的光催化降解RhB活性相對于BiOHCOO有明顯的提高,還有一定的光解水產氧活性。我們推測由于BTC陰離子的引入,引起B(yǎng)i2022+層發(fā)生結構的扭曲,影響了電子轉移過程,從而提高了光生載流子的存活壽命,提高了材料光催化活性。第四章主要是對基于其他有機配體的鉍基MOFs材料的制備以及光催化等性質進行探究。首先制備了一種基于3,5-吡啶二羧酸(3,5-H2PYDC)的MOFBi-PYDC,并對其結構進行了介紹。通過探究Bi-PYDC的光催化性能,發(fā)現其在全光照射下能夠降解RhB染料分子。此外,還發(fā)現Bi-PYDC具有離子交換的性質,與有機配體H3BTC進行離子交換,能夠得到上章提到的有機無機雜化材料BiO-BTC。之后,我們選用2-氨基對苯二甲酸(NH2-H2BDC)為有機配體,借鑒第三章中的離子交換方法,得到有機無機雜化材料BiO-BDC(NH2)。通過對其光物理和光催化性能的研究,發(fā)現BiO-BDC(NH2)具有可見光響應,而且能夠在可見光照射下高效的降解有機染料RhB,具有良好的光催化活性。第五章為總結與展望。我們主要是對論文中的工作和得出的理論進行了總結,列出了論文的創(chuàng)新點,并提出了工作中存在的問題和不足,以及未來工作的計劃。總體來說,通過本論文對一系列鉍基MOFs材料的研究及其光催化性能、機理的探究,充分說明鉍基MOFs材料對于光催化領域具有重要意義,可發(fā)展為一種新型的光催化材料體系。
[Abstract]:Metal organic frameworks (Metal-Organic, Frameworks, MOFs) material is a porous solid materials with mesh frame structure between a class of using metal ions or metal oxide clusters and organic ligand bond assembled. In recent years, the MOFs materials due to its large surface area, high porosity and structural functional diversity adjustability the structure properties in many fields such as gas storage, selective adsorption and separation, catalysis, and has good application prospects in all aspects of luminescent materials and drug carriers. Among them, the photocatalytic conversion to solar energy into electrical energy, chemical energy, and then used to decompose water to produce renewable hydrogen energy, degradation of pollutants, such as reduction of C02 that is an effective way to solve the energy shortage and environmental pollution problems, so the application of MOFs material in the field of photocatalysis has attracted wide attention in the photocatalytic material.MOFs has its unique The advantages, mainly in two aspects: (1) the structure and function of the adjustable; (2) the porosity and pore structure ordered by MOFs material. The structure function is obtained, based on the metal sites and organic ligands change or modification and other means to achieve the regulation of photocatalytic properties specific in photocatalysis, appears to regulate the material light absorption range; improve carrier separation efficiency; exposure of unsaturated metal sites to promote the photocatalytic reaction. In addition, the MOFs material has high porosity, specific surface area and Kong Daojie ordered the introduction to some guest molecules, which can directly contact with the active site of MOFs, shorten the electronic transmission distance, improve the transmission efficiency of the carrier, and then promote the photocatalytic reaction. So far, MOFs has found some material with high light. The performance, and are respectively applied in photocatalytic degradation of pollutants, photocatalytic hydrogen and the reduction of C02 and so on. But these MOFs photocatalytic materials are mostly based on Ti, Zr, Fe and other transition metal elements, on the photocatalytic studies of other metal based MOFs material is very few, therefore some inquiry is composed of a main group metal or other metal MOFs photocatalytic material is very necessary. Bismuth inorganic semiconductors exhibit excellent photocatalytic properties, has become a hot topic in the field of photocatalysis. Research on bismuth based photocatalytic materials has become a system, and our research group studied a series of bismuth based photocatalytic materials, such as Bi2O3. BiOX (X=C1, Br, I), Bi2O2CO3, BiVO4, Bi2SiO5 etc., has accumulated rich experience on theory and practice. At the same time, bismuth material is abundant, environmentally friendly non-toxic, good stability, and bismuth ion has flexible configuration, there are To construct a variety of MOFs. based on the above analysis, we speculate that the bismuth based MOFs material in the photocatalytic degradation of organic dye, photolysis of hydrogen, has good application for oxygen production and so on. Therefore, in this thesis, we developed a bismuth based MOFs photocatalytic materials of several novel, the photocatalytic reaction mechanism of their and study, the specific content is divided into five chapters: the first chapter introduces the related background knowledge of MOFs materials, synthesis methods and main application fields. Then MOFs materials research progress in the field of photocatalysis were summarized briefly, summarizes the advantages of MOFs materials in photocatalysis and photocatalytic mechanism of the main theory. Then introduced the research progress of bismuth based MOFs materials in the field of photocatalysis. Finally, this paper expounds the significance of the topic, research ideas and main content. The second chapter mainly includes MOF material Bi-mna preparation and photocatalysis The performance and mechanism research. MOF material Bi-mna powder prepared by a simple solvothermal method, has carried on the characterization of XRD, basic TG/DTA, proved that the purity of the samples, and the structural characteristics of the materials are briefly introduced. By measuring the photocurrent response and AC impedance spectroscopy, Bi-mna has found photoelectrochemical properties of excellent photocatalytic performance. Then the light degradation of organic dyes and photocatalytic oxygen ability to characterize Bi-mna, the results showed that Bi-mna under visible light irradiation, the degradation of organic dye RhB and MB, and continuously decompose water to produce oxygen in 6h, showed a high photocatalytic activity. Based on the band structure of Bi-mna and the electron distribution of the theoretical calculation, we propose a novel photocatalytic mechanism theory, namely the ligand to ligand charge transfer (LLCT) process, and verified this theory by experiment On the.LLCT process, can prolong the lifetime of photocarriers materials, so as to promote the effective separation of the photogenerated carriers and improve the photocatalytic efficiency of the material. In the third chapter, we use the organic ligand trimesic acid (H3BTC), the preparation of two bismuth based MOFs material and Study on its physical and light photocatalytic performance. (1) firstly synthesized a novel single crystal bismuth based MOF material Bi-BTC, and through X ray diffraction technique was obtained with two dimers {Bi2014} crystal structure information.Bi-BTC Bi-BTC, {Bi2014} between these groups by ligand BTC3- connected to form a 3D frame structure. At the same time, along with B the direction of the axis of {Bi2014} groups respectively form two helical chains through different ligands connect the two helical chains are arranged alternately, adjacent helical chains share a set of {Bi2014} two dimers, with a certain angle of diffuse reflection light are assembled together. The results show that the spectrum of the light absorption of Bi-BTC is mainly composed of ligand-induced, while ligand with bismuth bonding to the coordination environment change caused by diffuse reflection spectra and fluorescence emission spectra red shift. The preliminary study found that Bi-BTC has photocatalytic activity in optical irradiation decomposition of water to produce oxygen (2) process. We attempt to synthesize Bi-BTC single crystals, obtained a BiO-BTC.BiO-BTC Bi-BTC isomer is formic acid bismuth oxide (BiOHCOO) and H3BTC as raw materials obtained by solvothermal reaction. According to the BiOHCOO ion exchange properties we speculate this material is a kind of layered organic-inorganic hybrid materials by BTC anion substitution HCOO- layer BiOHCOO. Through EXAFS, the material of XRD, FT-IR and thermal analysis test of the above conjecture to introduce verification.BTC anion does not change the original lamellar structure only. Only the Bi2022+ layer structure distortion. Study on its photocatalytic activity, found that the photocatalytic degradation of RhB activity of this material in full sunlight compared to BiOHCOO has increased significantly, and the photocatalytic activity. We speculate that the oxygen anion caused by introducing BTC, Bi2022+ layer structure distortion, the effect of electron transfer. In order to improve the photocarrier lifetime of material is improved photocatalytic activity. The fourth chapter is to explore the preparation and photocatalytic properties of bismuth based MOFs materials of other organic ligands. The system is based on the first prepared a two 3,5- pyridine carboxylic acid (3,5-H2PYDC) based on MOFBi-PYDC, and the structure of introduced in this paper. The photocatalytic performance of Bi-PYDC, can be found in all optical irradiation degradation of RhB dye molecules. In addition, also found that Bi-PYDC has the property of ion exchange, and organic ligand H3 BTC ion exchange, then can get the chapter on organic inorganic hybrid material BiO-BTC. mentioned above, we selected the 2- amino acid (NH2-H2BDC) as organic ligand model in Chapter third ion exchange method, obtained the organic inorganic hybrid materials BiO-BDC (NH2). Through the study on the photophysical and photocatalytic properties, found BiO-BDC (NH2) with visible light response and RhB efficient degradation of organic dyes under visible light irradiation, with good photocatalytic activity. The fifth chapter is the summary and outlook. We mainly summarizes the thesis work and the theory, list the innovation of the paper, and put forward the existing in the work the problems and deficiencies, and plans for future work. In general, the research and the light of a series of bismuth based MOFs composite catalytic performance and mechanism of the inquiry, full description of bismuth based MOFs materials It is of great significance for the field of photocatalysis and can be developed into a new type of photocatalytic material system.

【學位授予單位】：山東大學
【學位級別】：碩士
【學位授予年份】：2016
【分類號】：O643.36

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