环境/能源催化反应中催化剂表面微结构对其活性的影响机制研究

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英文题名：The Mechanism Study of the Effect of Catalyst Surface Microstructure on the Catalytic Reactivity in the Field of Environmental/Energy Catalysis 作者：贾传义 论文级别：博士 学科专业名称：材料学 中文关键词：理论模拟 ; 微结构调控 ; 半导体光催化 ; 催化剂负载 ; 尖晶石催化剂 英文关键词：theoretical simulation ; microstructure control ; semiconductor 英文关键词：photo-catalysis ; supported catalysts ; spinel catalysts 学位年度：2014 导师：赵显 ; 樊唯镏 学科代码：080502 学位授予单位：山东大学 论文提交日期：2014-04-07

摘要

随着环境污染和能源危机的不断加重,污染气体的消除和再转化已经成为当前最迫切的问题之一。因此,为了缓解能源危机和降低环境污染,科研工作者们正在寻找各种方式将空气中的污染物(如含C、N元素的有毒气体)转化为可利用的再生能源。近年来,随着理论计算方法和电脑科技的不断发展,已经有越来越多的科研工作者从原来盲目的实验探索转向理论模拟,因为这可以为实验研究提供合理的微观预测和理论指导。上述转化反应的主要难题之一便是高效催化剂的选择和合成。针对此难点,目前比较新颖的也是比较有效的合成方式便是表面微结构调控。在本论文中,我们将用密度泛函的方法对表面微结构调控的两种主要方式(控制暴露高效表面和负载助催化剂)来进行理论模拟研究。这也可以为实验上合成此类高效催化剂提供很好的理论指导。对控制暴露高效表面的方法,我们选择的是小分子(H2O、CO2和NH3)在两种典型的尖晶石体系(ZnGa2O4和MgAl2O4)上的吸附和降解为模型来进行研究。目的是为了探索催化剂的微观表面原子、电子结构(尤其是表面态)对催化活性的影响。对催化剂负载的方法,我们选择的是CO在Au负载Mg(OH)2催化剂上的氧化过程为模型来进行研究。此项研究是为了探究载体对催化剂团簇的催化活性的影响。我们的主要研究内容和结论如下：
     在第一章的绪论中,我们主要介绍了下本论文的研究背景和意义,其中包括半导体光催化技术的机理及研究进展、暴露表面可控催化剂和贵金属团簇负载催化剂的研究现状和不足之处等。最后,我们阐述了本论文的选题原因、研究思路和大体内容。
     在第二章中,我们主要对密度泛函理论、局域密度近似理论和广义梯度理论进行了详细阐述,并且还介绍了在论文中使用的主要量化计算软件包。
     在第三章我们用密度泛函的方法研究了H2O和CO2在尖晶石体系ZnGa2O4的三个低指数完美和有氧缺陷的表面((100)、(110)和(111)面)上的单独吸附和共吸附行为。通过计算我们发现水在化学计量比的完美表面上吸附时,最稳定的分子吸附更容易发生在能够产生氢键的位点。对解离吸附来说,在完美的(111)面上的吸附能是其他两个表面的4倍以上,这表明水的最佳解离面是(111)面。经过对此三个表面的详细比较我们发现导致上述现象的主要原因是在(111)面上的特殊表面结构。当水在(111)面上解离时,由Ga的4s和4p态杂化而成的在费米能级处的特殊表面态将会有个明显的负移。这种负移释放的能量将会促进水的解离。由于在(100)和(110)表面上O3c空位的形成能够增强解离吸附态的稳定性并且对反应能垒影响不大,因此这种空位的形成能够促进水的降解。然而在(111)面上,空位的形成将会降低水解离态的稳定性并且能够明显的增加反应能垒。因此在有缺陷的(111)面上水的解离比完美表面要差。比较完水的单独吸附之后接下来我们看下二氧化碳的吸附。在完美的(100)面上,最稳定的分子吸附发生在Zn-O-Ga的桥位上,吸附能为-0.16eV。而在(110)和(111)面上,最稳定的吸附发生在Zn-O位点,吸附能较差(分别为0.22eV和0.35eV)。此外,完美的表面只显示出对二氧化碳很强的活化能力,但是解离吸附不能发生。氧缺陷的产生会导致：(1)空位附近的金属原子所带正电荷量下降并且进一步使得在这些金属上吸附能下降；(2)形成二氧化碳分子吸附甚至解离吸附的有效位点。最稳定的分子吸附和解离吸附都发生在有缺陷的(100)面上,并且这些吸附行为都是自发吸附,吸附能分别为-0.74eV和-0.80eV。当水吸附在完美表面和缺陷表面上时,氢键的形成将会增强水和二氧化碳的共吸附态的稳定性(除了(111)-Vo3c面)使得其热力学有利。然而二者的共吸附也会增加在缺陷表面二氧化碳降解的反应能垒,使得反应动力学不利。此外,水在空位处也可以很好的吸附和降解。因此,当水和二氧化碳在表面共吸附时将会竞争表面空位,从而降低二氧化碳降解的活性位点数目,导致催化活性下降。这就意味着如果我们想合成一种镓酸锌催化剂用于水的降解,我们需要让催化剂主要暴露高活性的(111)面,并且产生较少的氧缺陷；如果我们想把镓酸锌催化剂用于二氧化碳的降解反应得到一氧化碳和氧气,我们应该把反应体系放于洁净无水的环境中；如果我们想用镓酸锌催化剂来催化二氧化碳和水重整反应得到碳氢化合物,我们需要及时的将产物与水分子分离开来以维持催化剂的高活性。因此我们的研究可以为设计合成表面可控的高效镓酸锌催化剂提供一种新颖的思路。
     在第四章中我们进一步研究了小分子NH3在另一种典型尖晶石催化剂MgAl2O4上的吸附和降解。我们用密度泛函的方法分别计算了氨分子在低指数的(100)、(110)和(111)面上的吸附和解离。在完美的和有缺陷的表面上,我们获得了氨分子在不同位点的吸附的不同构型。比较了这三个表面的吸附行为之后,我们发现在(100)和(110)面上氨分子的分子吸附比解离吸附更有利,然而在(111)面上我们却得到了相反的结果。我们进一步比较分析表明这是一个结构敏感的反应。在表面镁原子上最稳定的吸附态出现在(100)面,而在表面铝原子上最稳定的吸附态出现在(111)面。我们计算结果显示导致不同金属原子上不同吸附态稳定性不同的原因是费米能级处的特殊表面态。这个特殊表面态分别出现在(100)面的不饱和镁原子和(111)面的不饱和铝原子上。对分子吸附来说,当分子吸附在表面上时(100)面上镁的2s轨道和(111)面上铝的2s和2p轨道在费米能级处形成的特殊表面态将会发生明显的负移从而可以显著的增强氨分子的解离态的稳定性。此外在有特殊表面态的(100)面和(111)面上的氨分子的解离吸附也比没有表面态的(110)面要稳定很多。由于在(111)面的铝原子上特殊表面态是由2s和2p轨道杂化而成这就使得在(111)面上的吸附比在只由2s轨道形成的特殊表面态的(100)面上的吸附更加稳定。氧空位的形成将使得吸附变得不稳定(尤其是(111)面)。这就是说完美的(111)面是氨吸附和降解的最佳表面。我们的研究很好的模拟了氨分子在铝酸镁催化剂上的降解或合成过程,从而可以为为实验上合成用于氨分子的降解或合成的高效且形貌可控的铝酸镁催化剂提供理论指导。
     在第五章我们主要研究的是催化剂负载对催化活性的影响。通过对Au团簇负载的完美的Mg(OH)2表面上CO、O2的单独吸附以及CO氧化过程的计算,我们发现对完美的表面来说,CO和O2在Au团簇表面以及Au团簇和Mg(OH)2(0001)表面的界面处都能吸附和活化,其中CO更容易吸附在界面处,O2的分子吸附更容易发生在Au团簇上,而02的解离吸附更容易发生在界面处,当二者共吸附时,在Au团簇上的分子吸附和氧化产物的稳定性比界面处要强,导致反应能垒和C02的活化能变高。而通过对Au团簇负载的有羟基缺陷的Mg(OH)2表面上CO、02的单独吸附以及CO氧化过程的计算,我们发现对有羟基缺陷的表面,在缺陷处CO的吸附能与完美表面比都有所下降,(甚至在Vo-2位点处CO的吸附都无法发生),O2的吸附和解离在空位Vo-1和Vo-3处都有很大提升而在Vo-2和Vo-4处吸附提升不大甚至降低,二者共吸附时与02的吸附相似也是在Vo-1和Vo-3处稳定性有很大提升,在Vo-2和Vo-4处吸附提升不大甚至降低。因此,某些空位(离Au团簇较近的空位)的形成对02的吸附和CO的氧化有比较强的促进作用,而在离团簇较远的空位处影响较小甚至会产生副作用。通过对计算结果的分析,我们发现CO、O2分子的吸附和CO的氧化在Au团簇负载Mg(OH)2(0001)表面有很强的结构依赖性,并且表面羟基空位的形成对它们的吸附都有很大的影响。我们的研究对理解Au团簇负载Mg(OH)2(0001)表面的原子和电子结构以及CO、O2分子的吸附和CO的氧化过程能够起到很好的指引作用,并且能够在理论上为科研工作者合成高效的形貌可控的Au团簇负载Mg(OH)2催化剂提供很好指导。
     最后,在第六章我们对本论文的主要结论和创新点作了总结和归纳,并对此研究方向提出了展望。
As the environmental pollution and energy crisis deepening, elimination of pollutants and turns them to clean resources has become one of the most pressing problem. Therefore, in order to relieve the energy crisis and reduce the environment pollution, the scientific research workers are looking for available ways to translate the pollutants in the air (such as poisonous gas containing elements of C, N) into the renewable energy. In recent years, with the continuous development of theoretical calculation method and computer technology, there have been more and more researchers doing theory research rather than just imitating experiments, because it can provide experimental research with reasonable microcosmic forecast and theoretical guidance. One of the main problems of the transformation pollutants is the choice and synthesis of high efficiency catalysts. For this difficulty, a new and very effective synthesis method is surface microstructure control. In this work, we will use density functional theory method to study the two main ways of surface microstructure control (exposure effective surface and loading co-catalyst). It can also provide good theoretical guidance for the scientists synthesising of such high efficiency catalyst. For the method of exposure effective surface, we choose the small molecules (H2O, CO2and NH3) adsorbed and dissociated on two kinds of typical spinel catalysts (ZnGa2O4and MgAl2O4as model for research. The purpose of this work is to explore how the microcosmic surface atomic and electronic structure (especially the surface states) effect on the catalytic activity. For the method of loading co-catalyst, we choose the CO oxidation process on the Au16supported Mg(OH)2catalyst as the model for research. This study is aim at exploring the carrier's influence on the catalytic activity of catalyst. Our main research contents and conclusions are shown as follows:
     In chapter one, we mainly introduced the research background and significance of our work, including the mechanisms of semiconductor photo-catalysis technology and the present situation and deficiency of surface controllable catalysts and precious metal load catalysts etc. Finally, we elaborated the reason we select this topic, as well as the research train of thought and the general content of this work.
     In chapter two, we mainly described the density functional theory, the local density approximation theory and the generalized gradient theory in detail, and also introduced the main quantitative calculation software package used in this work.
     In chapter three, we mainly studied the H2O and CO2separate and common adsorption behaviors on the perfect and oxygen defective low index ((100),(110) and (111) surface) ZnGa2O4catalysts. Our calculations show that on the stoichiometrically perfect surface, the most stable molecular adsorption that could take place involved the generation of hydrogen bonds. For dissociative adsorption, the adsorption energy of the (111) surface was more than four times the energies of the other two surfaces, indicating it to be the best surface for water decomposition. A detailed comparison of these three surfaces showed that the primary reason for this observation was the special electronic state of the (111) surface. When water dissociated on the (111) surface, the special Ga3c-4s and4p hybridization states at the Fermi level had an obvious downshift to the lower energies. This large energy gain greatly promoted the dissociation of water. Because the generation of O3c-vcancy defects on the (100) and (110) surfaces could increase the stability of the dissociative adsorption states with few changes to the energy barrier, this type of defect would make the decomposition of water molecules more favorable. However, for the (111) surface, the generation of vacancy defects could decrease the stability of the dissociative adsorption states and significantly increase their energy barriers. Therefore, the decomposition of water molecules on the oxygen vacancy defective (111) surface would be less favorable than the perfect (111) surface. After discussed the adsorption behavior of water, now we will turn to the discussion of the adsorption behavior of CO2. On the perfect (100) surface, the most stable adsorption state involved the Zn-O-Ga bridge site, with an adsorption energy of-0.16eV. In the case of the (110) and (111) surfaces, the strongest binding occurred on the Zn-O bridge sites, with much lower adsorption energies of0.22eV and0.35eV, respectively. In addition, the perfect surfaces showed CO2activation ability, but dissociation adsorption could not proceed. The oxygen vacancies on these three surfaces (1) made the metal sites beside them carry less positive charge and further reduced the adsorption energies on these metal sites, and (2) created efficient adsorption sites that allowed even dissociative adsorption. The most favorable molecular and dissociative adsorption states both involved the O30vacancy site of the (100) surface, and these two processes were spontaneous with adsorption energies of-0.74eV and-0.80eV, respectively. When H2O molecules are present on the perfect and defective surfaces, the generation of hydrogen bonds between H2O and CO2would slightly enhance the stability of adsorption (except for that on the (111)-Vo3c surface), making it energetically favorable. However, the co-adsorption of H2O could also increase the energy barriers for the decomposition reactions on the defective surfaces, making them kinetically unfavorable. Furthermore, the oxygen vacancy defects showed good activity for H2O adsorption and decomposition, as well. Thus, when H2O and CO2were both present in the adsorption system, H2O would compete with CO2for the oxygen vacancy sites and further decrease the amount of CO2adsorption and decomposition, and further reduce the reactivity of the catalyst. This means that if we want to use ZnGa2O4catalyze the decomposition of H2O, we need to let the catalyst mainly exposed the (111) surface and generate less oxygen defects; if we want to use ZnGa2O4catalyze CO2decomposition into CO and O2, we should be sure that the reaction system is in a dry environment; if we want to use ZnGa2O4to catalyze the reaction between CO2and H2O yielding hydrocarbons, we need to separate and remove water from the product stream to maintain the high activity of the catalysts. Our research can provide a new design idea for the synthesis of high efficient and surface controllable ZnGa2O4catalysts.
     In the fourth chapter, we further studied the adsorption and decomposition behavior of small molecule NH3on another typical spinel catalyst (MgAl2O4). Adsorption and dissociation of NH3on the low-index (100),(110) and (111) surface were investigated using density functional theory. On the perfect and defective surfaces, different configurations were achieved for NH3molecules on various sites. Comparing these three surfaces, we found that on the (100) and (110) surfaces the NH3molecular adsorption is more favorable than the dissociative adsorption, while on the (111) surface we obtained the opposite consequence. Our further analysis indicates that this is a surface-structure-sensitive reaction. The most stable adsorption state on Mg atom occurs on the (100), while the most stable adsorption state on Al atom occurs on the (111) surface. Our results shows that the main reason for the different stability of the adsorption states on different metal atoms is caused by the surface special electronic states at the Fermi level which emerged on the Mg2c atom of (100) surface and the Al3c atom of (111) surface. For molecular adsorption, the special Mg2c-2s state of (100) surface and Al3c-2s and2p states of (111) surface at the Fermi level will have a distinct downshift to the lower energies and significantly enhance the stability of the adsorption states. In addition, the dissociative adsorption states on the (100) and (111) surfaces which have special surface states are much more stable than the (110) surface as well. Because the special surface state on the (111) surface is generated by the hybridization of Al3c-2s and2p states, the enhancement of the adsorption states on the (111) surface is larger than the (100) surface whose special surface state is generated by only one state (Mg2c-2s). The generation of oxygen vacancy will make the adsorption states less stable, especially for the (111) surface. This means that the perfect (111) surface will be the most favorable surface for NH3adsorption and decomposition. These findings have an important implication for the decomposition or synthesis of NH3on the MgAl2O4surfaces and can provide theoretical guidance for chemists to synthesize high-efficiency MgAl2O4catalysts. These findings have an important implication for the decomposition or synthesis of NH3on the MgAl2C4surfaces and can provide theoretical guidance for chemists to synthesize high-efficiency MgAl2O4catalysts.
     In the fifth chapter we mainly studied the catalyst load effect on the catalytic activity. Through the calculation of the separate and common adsorption of CO and O2on the Aui6supported perfect Mg(OH)2(0001) surface, we found that on the perfect surface, CO and O2can be adsorbed and activated both on the surface of the Au clusters and the interface between Au clusters and Mg(OH)2(0001) surface (CO molecule is more easily adsorbed on the interface; O2molecular adsorption is more likely to happen on the Au clusters and dissociative adsorption is more likely to happen on the interface; when they co-adsorbed, the molecule adsorption states and oxidation products on Au clusters are both stable than the that on the interface, which will make the reaction energy barrier and the CO2activation energy become higher). Through the calculation of the separate and common adsorption of CO and O2on the Aui6supported defective Mg(OH)2(0001) surface, we found that on the surface with hydroxyl defects, the defect can reduce CO adsorption compared to the perfect surface (the CO adsorption on the Vo-2sites even can not happen), O2adsorption on the Vo-1and Vo-3sites have very big improvements, however, on the Vo-2and Vo-4sites the adsorption states are much less stable than that on the perfect surface, the co-adsorption of CO and O2is similar to O2adsorption (on the Vo-1and Vo-3site the adsorption states have very big promotion and on the Vo-2and Vo-4site the adsorption states are very unstable). As a result, some hydroxyl defects (the hydroxyl defects near the Au clusters) can promote the adsorption and activation of O2and CO, but the generation of the hydroxyl defects that are far away from the Au clusters will make the adsorption state become unstable. Our results showed that the oxidation reaction of CO and the adsorption of O2and CO on the Au clusters supported Mg(OH)2(0001) surface has a strong surface-dependence, and the formation of surface hydroxyl space has great influence on it. Our research can have very good guidance for us to understand the Au clusters supported Mg(OH)2catalysts, the atomic and electronic structure of the surface and the oxidation reaction of CO, the adsorption behavior of O2and CO, and further guide the researchers to synthesis the morphology controlled Au clusters supported Mg(OH)2catalysts.
     Finally, in chapter six we summarized the main conclusions and the innovation points of our work, and put forward the outlook in this research direction.

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