本文關(guān)鍵詞：摻雜對(duì)碳納米材料性質(zhì)影響的第一性原理研究　出處：《中國(guó)科學(xué)技術(shù)大學(xué)》2015年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 第一性原理 摻雜 碳納米材料 p型-n型轉(zhuǎn)變 氧氣還原反應(yīng) 催化 解離能壘

【摘要】：碳納米材料是指至少有一個(gè)維度在尺寸上達(dá)到納米量級(jí)的碳材料,主要包括幾種類型：富勒烯、碳納米粒子(碳納米球、碳納米膠囊)、碳納米管(碳納米纖維)、石墨烯以及其他的碳納米多孔材料。碳納米材料在力學(xué)、電學(xué)、磁學(xué)、光學(xué)和催化等方面均有著良好的性質(zhì)和應(yīng)用潛力,自從發(fā)現(xiàn)以來(lái)就引起了人們廣泛的研究興趣和熱潮,成為納米科學(xué)研究的重點(diǎn)對(duì)象。直到現(xiàn)在對(duì)碳納米材料性質(zhì)和技術(shù)的研究依然是科學(xué)研究的前沿。 隨著技術(shù)的發(fā)展,純的碳納米材料本身的性質(zhì)已經(jīng)滿足不了人們對(duì)新材料、新性質(zhì)的需求,人們不斷地嘗試和研究各種調(diào)制碳納米材料的性質(zhì)的新方法和新技術(shù)。實(shí)驗(yàn)上,摻雜作為一種傳統(tǒng)的方法被廣泛地用來(lái)調(diào)制碳納米材料的性質(zhì)。但是由于缺乏大量的實(shí)驗(yàn)數(shù)據(jù),僅從實(shí)驗(yàn)很難從根本上理解調(diào)制碳納米材料性質(zhì)的微觀機(jī)理。因此,理論模擬對(duì)于揭示這種摻雜調(diào)制的機(jī)理有著非常重要的作用。在納米材料的研究中,量子力學(xué)是支配這些微觀體系的基本規(guī)律,但是作為量子力學(xué)核心的薛定諤方程卻很難解析求解,因此計(jì)算化學(xué)作為近似求解薛定諤方程的一種方法應(yīng)運(yùn)而生。在采用各種近似后,薛定諤方程大大簡(jiǎn)化,通過(guò)高性能計(jì)算方法可近似求解薛定諤方程。隨著近二十年來(lái)計(jì)算機(jī)硬件的飛速發(fā)展,計(jì)算成本急劇降低,計(jì)算化學(xué)已經(jīng)在理論模擬中表現(xiàn)出越來(lái)越重要的地位。而基于密度泛函理論的第一性原理計(jì)算由于其快速而可靠的計(jì)算結(jié)果使其成為計(jì)算化學(xué)中最主流的方法之一,并且成為材料科學(xué)、凝聚態(tài)物理學(xué)中重要的理論模擬手段。在本論文中,我們主要采用第一性原理計(jì)算方法研究摻雜對(duì)碳納米材料性能的影響。 本論文分為五章。第一章我們首先簡(jiǎn)要介紹了計(jì)算化學(xué)的方法,重點(diǎn)介紹密度泛函理論的理論框架,發(fā)展過(guò)程和常用的交換相關(guān)泛函。密度泛函理論的核心是構(gòu)建單電子模型。具體實(shí)現(xiàn)是通過(guò)假想一個(gè)和真實(shí)體系同樣電荷密度的非相互作用的單電子體系,用非相互作用體系的電子的動(dòng)能和Hartree勢(shì)能來(lái)近似真實(shí)的動(dòng)能和電子之間相互作用能,差額的部分被歸結(jié)到交換相關(guān)泛函中去,所以密度泛函理論從原理上說(shuō)是精確的,其發(fā)展的核心就是找到合適的交換相關(guān)泛函,使得計(jì)算結(jié)果盡可能逼近實(shí)驗(yàn)。隨后我們介紹了固體能帶的計(jì)算方法,這些方法使得密度泛函理論在固體領(lǐng)域得到廣泛應(yīng)用。此外,我們簡(jiǎn)單介紹了采用準(zhǔn)粒子模型的GW方法以及含時(shí)密度泛函理論。由于本文中涉及到了大量化學(xué)反應(yīng)能壘的計(jì)算,所以最后簡(jiǎn)要介紹了計(jì)算化學(xué)反應(yīng)能壘的方法,并簡(jiǎn)要介紹了本論文中用到的第一性原理軟件包。 第二章中,我們主要研究氮雜富勒烯對(duì)碳納米管輸運(yùn)性質(zhì)的調(diào)制。首先簡(jiǎn)要介紹了碳納米管材料的研究進(jìn)展,隨后我們希望通過(guò)理論計(jì)算對(duì)一組矛盾的實(shí)驗(yàn)結(jié)果做出合理的解釋。對(duì)于相同的封裝了氮摻雜富勒烯分子的碳納米管(“納米豆莢”),不同的實(shí)驗(yàn)組測(cè)出了不同的單向?qū)щ娦�。通過(guò)對(duì)體系電子結(jié)構(gòu)的計(jì)算,我們從理論上解釋了這種不同輸運(yùn)性質(zhì)的原因：不同的碳納米管結(jié)構(gòu)可以導(dǎo)致不同的輸運(yùn)行為,有著類似5-8-5缺陷結(jié)構(gòu)的碳納米管封裝了摻氮富勒烯分子才能使得碳納米管從p-型半導(dǎo)體轉(zhuǎn)變?yōu)閚-型半導(dǎo)體。 第三章中,我們研究了氮摻雜的碳納米材料。作為電極材料有著良好的催化氧氣還原反應(yīng)的能力并且避免了傳統(tǒng)Pt基催化劑的缺點(diǎn),如價(jià)格較高、會(huì)對(duì)CO氣體中毒、對(duì)甲醇容忍性差和耐久性差。盡管這種材料的催化效率還沒(méi)有完全趕上Pt基催化劑,但是有潛力作為新興的電極材料,并在近年來(lái)得到了廣泛的實(shí)驗(yàn)和理論研究,因此有可能取代傳統(tǒng)Pt電極材料。由于實(shí)際催化過(guò)程的復(fù)雜性,到目前為止這種摻雜氮的碳納米材料的催化活性中心問(wèn)題依然存在爭(zhēng)論,真正的催化機(jī)理仍然有待發(fā)展。在本章中,我們通過(guò)一個(gè)簡(jiǎn)化的模型模擬了氧氣在氮摻雜的碳納米材料上的解離過(guò)程,通過(guò)解離能壘的計(jì)算來(lái)研究氧氣在不同氮摻雜結(jié)構(gòu)上的反應(yīng)活性。計(jì)算結(jié)果表明：氮摻雜可以提高碳納米材料電催化的活性；在不同的氮摻雜結(jié)構(gòu)中,類似石墨結(jié)構(gòu)的氮摻雜方式的催化活性最好。 第四章和第五章是第三章工作的深化和擴(kuò)展。由于氮摻雜的碳納米材料表現(xiàn)出良好的催化氧氣還原反應(yīng)的能力。隨著研究的深入,各種不同的元素包括硼、硫等都被摻雜到碳納米材料中。這些元素單摻雜的材料往往沒(méi)有氮摻雜材料的催化活性好,但是硼氮、硫氮以及其他形式的共摻雜卻表現(xiàn)出良好的催化氧氣還原反應(yīng)的活性。在第四章中,我們主要研究了硼摻雜和硼氮共摻雜的碳納米管作為電極材料對(duì)還原氧氣所起到的催化作用。我們計(jì)算了氧氣在這些材料上的解離能壘,計(jì)算結(jié)果表明：硼摻雜的碳納米管催化活性不高,而硼氮共摻雜的碳納米管催化活性比氮摻雜的碳納米管要好,和實(shí)驗(yàn)結(jié)果一致。在第五章中,我們簡(jiǎn)單測(cè)試了硫氮共摻雜對(duì)石墨烯催化氧氣還原反應(yīng)能力的影響,結(jié)果表明硫氮共摻雜可以有效降低氧氣還原反應(yīng)的能壘。
[Abstract]:Carbon nano material is refers to at least one dimension carbon material at nanometer scale in size, including several types: fullerene, carbon nanoparticles (nano carbon ball, carbon nano capsule), carbon nanotubes (CNFs), graphene and other carbon nano porous materials. Carbon nano materials in mechanical and electrical, magnetism, optics and catalysis has good properties and potential applications, have attracted extensive research interest and boom since the discovery, become the focus of nano science. Until now, the research on carbon nano material properties and technology is still the forefront of scientific research.
With the development of technology, properties of pure carbon nano material itself has been unable to meet the people of the new material, the new nature of the demand, new method and new technology of nature people constantly try and study the modulation of carbon nano materials. The doping, as a traditional method is widely used for modulation properties of carbon nano materials. But due to the lack of a large number of experimental data, only from the experiment is very difficult to fundamentally understand the microscopic mechanism of modulation of carbon nano materials in nature. Therefore, the theoretical simulation plays a very important role in the mechanism of doping modulation. In the research of nano materials, quantum mechanics is the basic rule of the micro system control however, as the core of the Schrodinger equation in quantum mechanics is difficult to solve, so the computational chemistry as an approximate method for solving the Schrodinger equation in the various came into being. Approximate, the Schrodinger equation is greatly simplified, approximate solution of Schrodinger equation by high performance computing method. As in the past twenty years the rapid development of computer hardware, the computational cost decreases sharply, computational chemistry has in the theoretical simulation shows more and more important role. And the first principle calculations based on density functional theory because of its rapid and reliable results make it become one of the most mainstream method in chemical calculation, and has become an important means of material science, simulation theory in condensed state physics. In this thesis, we mainly use the first principle calculation method of the effect of doping on the properties of carbon nano materials.
This paper is divided into five chapters. The first chapter, we first briefly introduce the computational chemistry method, focuses on the theoretical framework of the density functional theory, the development process and the common exchange correlation functional. The core density functional theory is to construct a single electron model. The specific implementation is through a single electronic system of non interaction of a hypothetical and real system the same charge density, non interaction system of the kinetic energy of the electrons and the Hartree potential approximation between real kinetic energy and electron interaction can be attributed to the difference, part of the exchange correlation functional, so the density functional theory from the principle that is accurate, the core of its development is to find the exchange correlation functionals right, so the calculation results can approximate experiment. Then we introduced the calculation method of solid band, this method makes the density functional theory in solid field widely Widely used. In addition, we introduce a simple method using GW quasi particle model and time-dependent density functional theory. The calculation of this paper involves a large number of chemical reaction energy barrier, so finally briefly introduces a method for calculating the energy barrier of chemical reaction, and the first principle used in the software package in brief introduction.
In the second chapter, on the transport properties of carbon nanotubes. We mainly study the modulation azafullerence. First briefly introduces the research progress of carbon nanotube materials, then we hope that through theoretical calculation to make a reasonable explanation for a set of contradictory experimental results. For the same package of nitrogen doped fullerene carbon nanotubes ("Nanopeapods"), the experimental group has been measured by different one-way conductivity different. Through the calculation of the electronic structure of the system, we explain the reason of different transport properties theoretically: carbon nanotube structure can lead to different transport behavior of different carbon nanotubes, a package similar to the 5-8-5 defect structure of nitrogen doped fullerene in order to make the transition from molecular carbon nanotubes p- type semiconductor is n- type semiconductor.
In the third chapter, we studied the nitrogen doped carbon nano materials. As the electrode material with good catalytic oxygen reduction reaction and avoid the shortcomings of traditional Pt based catalysts, such as high prices, will the CO gas poisoning, poor tolerance and poor durability of methanol. Although the catalytic efficiency of this kind of material is also not fully catch up with the Pt based catalyst, but has the potential as an electrode material emerging, and obtained the extensive experimental and theoretical studies in recent years, it is possible to replace the traditional Pt electrode materials. Because of the complexity of the actual catalytic processes, the catalytic center problem of carbon nano materials so far this nitrogen doped remains debatable true, the catalytic mechanism remains to be developed. In this chapter, we through the dissociation process of a simplified model of oxygen in nitrogen doped carbon nano materials on the solution from the energy barrier by Calculations were carried out to study the reactivity of oxygen on different nitrogen doped structures. The results show that nitrogen doping can improve the electrocatalytic activity of carbon nanomaterials, and in different nitrogen doped structures, graphite like structure has the best catalytic activity.
The fourth chapter and the fifth chapter is to deepen and expand the work of the third chapter. The nitrogen doped carbon nano materials exhibit good electrocatalytic activity for oxygen reduction reaction ability. With the in-depth study, the various elements including boron, sulfur and so on were doped into the carbon nano materials. These materials are often not single doped catalytic element the activity of nitrogen doped materials, but boron nitrogen, sulfur and nitrogen Co doped other forms but exhibited good catalytic activity for oxygen reduction reaction. In the fourth chapter, we mainly study the boron doped boron and nitrogen doped carbon nanotubes as electrode materials for catalytic reduction of oxygen plays. We calculated the oxygen dissociation in these materials on the energy barrier, the calculation results show that the catalytic activity of boron doped carbon nanotubes and carbon nanotubes is not high, the catalytic activity of boron nitrogen Co doped ratio of nitrogen doped carbon nanotubes to Well, it is consistent with the experimental results. In the fifth chapter, we simply tested the effect of sulfur and nitrogen co doping on the ability of graphene catalyzed oxygen reduction reaction. The results showed that sulfur and nitrogen co doping can effectively reduce the barrier of oxygen reduction reaction.

【學(xué)位授予單位】：中國(guó)科學(xué)技術(shù)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類號(hào)】：TB383.1;O613.71

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