金、铂基催化剂催化若干重要化学反应的理论研究

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英文题名：Theoretical Study on Several Important Reactions Catalyzed by Gold-based and Platinum-based Catalysts 作者：钟文辉 论文级别：博士 学科专业名称：理论与计算化学 中文关键词：金、铂基催化剂 ; 甲醇、甲酸氧化 ; 密度泛函理论 英文关键词：Au-based ; Pt-based catalysts ; methanol and formic acid oxidation ; Density functional theory 学位年度：2012 导师：张冬菊 学科代码：0703 学位授予单位：山东大学 论文提交日期：2012-05-29

摘要

能源与资源问题是21世纪人类所面临的主要挑战之一,为缓解能源危机、减少环境污染,世界各国均将开发高效、清洁新能源作为高新技术研发的重点.燃料电池(Fuel Cell)是一种纯正的绿色清洁能源,被认为是21世纪能源之星,美国《时代周刊》将其列为高科技之首.近年来,在全球低碳经济的背景下,燃料电池的研发和商业化进程有加快趋势.
     直接甲醇燃料电池(Direct Methanol Fuel Cell, DMFC)和直接甲酸燃料电池(Direct Formic Acid Fuel Cell, DFAFC),由于各方面的优良性能日益受到广泛关注,作为一种可行的潜在能源可应用于许多领域。Pt和Pt族贵金属被认为是甲醇和甲酸氧化最有效的电催化剂,被广泛用作DMFC和DFAFC阳极和阴极电极材料。然而,众所周知的是纯Pt催化剂通常存在两个主要缺点,一是催化剂成本高、资源有限,二是甲醇、甲酸在低温氧化过程中,容易被CO组分中毒,致使催化剂不能重复使用。这些缺点是制约DMFC/DFAFC规模化应用的重要瓶颈,因此寻找催化活性好、稳定性高、抗中毒能力强的新型阳极催化剂已成为DMFC/DFAFC研究中迫切需要解决的关键性科学问题。
     最近的研究表明,在Pt的基础上加入第二种金属形成的二元复合双金属催化剂,其性能明显好于纯Pt催化剂,能够显著增加对甲酸电化学氧化的催化活性,并且减少了贵金属Pt的用量,降低了催化剂成本.这为DFAFC催化剂的设计提供了新的思路,使人们认识到利用金属之间的增效作用、开发Pt、Pd基双金属或多金属催化剂,是改进甲酸电化学氧化性能的重要手段之一.但有关的分子机理尚不十分清楚,一些实验现象尚不能得以合理解释。
     本论文追踪国际研究前沿,瞄准DMFC/DFAFC研究中迫切需要解决的关键科学问题,着眼于在原子分子水平上理解铂基催化剂催化甲酸电化学氧化的微观机理。通过密度泛函理论计算研究了Au、Pt单金属和双金属团簇及表面的结构和性能,阐明了它们与CH3OH、HCOOH等小分子相互作用的微观机制,探讨了CH3OH、HCOOH催化氧化的各种反应路径,分析了反应的热力学和动力学性质,识别了甲酸氧化过程中各种活性中间体和过渡态结构的相对稳定性,阐明了控制催化剂活性的关键因素,完善了甲酸电化学氧化的理论模型,从而为DMFC/DFAFC新型阳极催化剂的开发和设计奠定了一定的理论基础、提供了一定的理论指导.
     主要研究内容及创新性研究结果归纳如下：
     1.研究了纯铂团簇Pt3和金、铂二元团簇PtAu2催化的甲醇脱氢反应,结果表明Pt3催化的反应,其最优路径是CH3OH→CH2OH→CH2O→CHO→CO,氧化过程需要2个Pt原子的协同作用,决速步骤的能垒是12.99kcal/mol;而PtAu2催化的反应,最优路径是CH3OH→CH3O→CH2O→CHO→CO,决速步骤的能垒是21.42kcal/mol在PtAu2中,Pt是活性中心,CO在PtAu2上比Pt3上更容易移除,从而在一定程度上解释了为什么二元的PtAu催化剂对甲醇的氧化具有改进的催化活性。
     2.研究了甲醇在中性的、负电荷和正电荷的Au3团簇上的裂解反应。结果表明,Au3和Au3+催化的反应通过4个连续的脱氢步骤进行,即CH3OH→CH3O→CH2O→CHO→CO,而Au3-催化的反应通过2个脱氢步骤进行,即CH30H→CH2O→CO。负电荷的团簇明显地减少了CO(甲醇完全脱氢的产物)在团簇上的结合能力,而中性和正电荷的团簇与CO有强的相互作用,容易使催化剂中毒。此外,正电荷团簇催化的反应比中性和负电荷团簇催化的反应的能垒高。因此,选择能够使Au纳米粒子带负电荷的底物可以改进催化剂催化性能,增强其抗中毒能力。
     3.研究了甲醇在PtAu(11l)二元金属表面上催化氧化的CO路径和非CO路径。结果表明,在PtAu(111)面上的CO比其在纯Pt(111)面上拥有更大的吸附能,并且在二元的PtAu(111)金属面上的非CO路径比CO路径在能量上更有利。以上这些计算的结果说明PtAu二元金属催化剂对甲醇氧化改进的电催化性能应该归因于主要反应路径从纯Pt面上的CO路径转变成PtAu二元金属面上的非CO路径,而不是归因于在PtAu催化剂上的CO比其在纯Pt催化剂上更容易移除。
     4.研究了甲酸(HCOOH)在水溶液中PtAu(111)表面上的氧化机理,计算了直接路径和间接路径的微观机理,并与纯Pt表面的结果进行了比较。直接路径涉及HCOOH脱氢形成CO2,相应的能垒是15.5kcal/mol;间接路径涉及HCOOH脱水形成CO中间体,相应的能垒是99.2kcal/mol。在Pt(111)面上直接路径和间接路径计算的能垒分别是58和32.9kcal/mol。理论计算的结果表明,二元的PtAu(111)表面明显地增加了两个路径的能垒差,从Pt(111)面上的27.1kcal/mol增加到83.7kcal/mol,因此PtAu(111)表面可以阻碍间接路径的发生,从而减少CO的形成几率。理论计算的结果合理地解释了实验现象,二元的PtAu催化剂比纯Pt催化剂对HCOOH氧化显示出更高的催化活性和抗中毒能力。
     5.建立了甲酸氧化的新的理论模型。由于甲酸分子可以通过分子间氢键形成各种稳定的二聚体结构,稳定化能可达15kcal/mol,我们猜测甲酸的电化学氧化可能与其二聚体结构有关,因此设计了甲酸电化学氧化的“二聚体模型”和“水助质子桥模型”。计算结果表明,一方面,吸附在催化剂表面的二聚体可以通过分子间脱水形成CO中间体,导致催化剂中毒；另一方面,甲酸分子的羰基和羟基可与溶剂中的水分子通过氢键形成氢键网络,这些分子间氢键可能对甲酸分子的电化学氧化起重要作用,水分子通过搭建质子桥协助催化反应的进行,降低反应能垒.新的理论模型改进了人们对甲酸催化氧化机理的认识,合理地解释了Pt基催化剂容易CO中毒的现象。
The problem of energy and resources challenges human in the21th century. In order to relieve energy crisis and reduce environment pollution, many countries in the world devote to exploring efficient and clean energy. Fuel cell is the green and clean energy, which is the energy star of the21th century. Time in America treat it as the most important technology. In recent years, the low carbon economy promotes development and commercialization of fuel cell.
     Direct methanol fuel cells (DMFCs) and direct formic acid fuel cells (DFAFCs), as a viable power sources with potential applications in many systems, have attracted tremendous attention because of their excellent performance in all aspects. Pt and Pt-group metals are known as the most excellent electrocatalysts for methanol and formic acid oxidation, so they are extensively used as electrode materials of both the anode and cathode of DMFCs and DFAFCs. However, it is well known that pure Pt catalysts usually suffer from two major disadvantages,(ⅰ) high cost and limited resources, and (ⅱ) poor performance durability resulted from the poisoning of CO and CO-like species produced during methanol and formic acid oxidation at low temperatures. These disadvantages are the important bottlenecks of DMFC/DFAFC's scale applications. Therefore, searching for the catalysts that are of excellent catalytic activity, good stability and improved tolerance towards CO-poisoning is becoming a challenging issue in the study of DFAFCs.
     The recent studies show that alloying Pt with another transition metal or noble metal that is generally less expensive than Pt could address these two challenging problems due to their significantly improved tolerance towards CO-poisoning and enhanced electrocatalytic activity for methanol oxidation as compared to pure Pt catalysts. This provides new thought for designing efficient catalysts used in DFAFCs, which is using the synergism among the metals and exploring the Pt-and Pd-based catalysts. However, the relevant mechanism behind the phenomenon remains unclear, and some experimental observations are still not well understood.
     The dissertation traces international research frontier, and aims at the challenging issue in the study of DMFCs/DFAFCs. This proposal aims to elucidate the molecular mechanism of formic acid electro-oxidation promoted by a series of Pt-based catalysts based on the results of the density functional theory (DFT) calculations. Our studies will pay substantial attentions on the following several aspects:(ⅰ) Au, Pt mono-metal and bimetallic clusters and surfaces'structure and performance,(ⅱ) microscopic mechanism of catalysts and CH3OH, HCOOH'interactions,(ⅲ) the mechanism details of formic acid oxidation along various possible pathways,(ⅳ) the thermodynamic and dynamical properties of the formic acid oxidation,(ⅴ) the relative stability of various activate intermediates and transition states involved along each pathway,(ⅵ) key factors controlling the catalytic activity of Pt-based catalysts, and the new and reasonable theoretical model describing the electro-oxidation of formic acid. We believe that the theoretical results would provide valuable guidance and assist for the rational design of efficient Pt-based electrocatalysts of DMFCs/DFAFCs.
     The valuable results in this dissertation can be summarized as follows:
     1. The density functional theory (DFT) calculations are carried out to study the mechanism details and the ensemble effect of methanol dehydrogenation over Pt3and PtAu2clusters, which present the smallest models of pure Pt clusters and bimetallic PtAu clusters. The energy diagrams are drawn out along both the initial O-H and C-H bond scission pathways via the four sequential dehydrogenation processes, respectively, i.e. CH3OH→CH2OH→CH2O→CHO→CO and CH3OH→CH3O→CH2O→CHO→CO, respectively. It is revealed that the reaction kinetics over PtAu2is significantly different from that over Pt3. For the Pt3-mediated reaction, the C-H bond scission pathway, where an ensemble composed of two Pt atoms is required to complete methanol dehydrogenation, is energetically more favorable than the O-H bond scission pathway, and the maximum barrier along this pathway is calculated to be12.99kcal/mol. In contrast, PtAu2cluster facilitates the reaction starting from the O-H bond scission, where the Pt atom acts as the active center throughout each elementary step of methanol dehydrogenation, and the initial O-H bond scission with a barrier of21.42kcal/mol is the bottom-neck step of methanol decomposition. Importantly, it is shown that the complete dehydrogenation product of methanol, CO, can more easily dissociate from PtAu2cluster than from Pt3cluster. The calculated results over the model clusters provide assistance to some extent for understanding the improved catalytic activity of bimetal PtAu catalysts towards methanol oxidation in comparison with pure Pt catalysts.
     2. By performing density functional theory calculations, we studied the methanol decomposition promoted by neutral, anionic, and cationic Au trimers, which represent three simplest prototypes of Au-cluster-based catalysts with different charge states. The theoretical results show that the Au3-and Au3+-mediated reactions proceed via the four successive single dehydrogenation steps CH3OH→CH3O→CH2O→CHO→CO, while Au3--mediated reaction occurs through two double dehydrogenation steps CH3OH→CH2O→CO. The additional negative charge remarkably reduces the binding capability of CO (the completely dehydrogenated product of methanol) on the cluster, and thus is favorable for reducing the catalyst poisoning by CO. In contrast, the neutral and positively charged clusters present strong interaction with CO, making the catalyst is easily poisoned by CO. Furthermore, the reaction promoted by the cationic cluster shows a much higher energy barrier than those by the neutral and anionic clusters. So selecting suitable substrates that make Au nanoparticles negatively charged may be a promising strategy for promoting methanol oxidation.
     3. By performing density functional theory calculations, we have studied the CO pathway and non-CO pathway of the methanol oxidation on the PtAu(111) bimetallic surface. CO is shown to possess larger adsorption energy on the PtAu(111) surface than that on the pure Pt(111) surface, and the non-CO pathway on the bimetallic surface is found to be energetically more favorable than the CO pathway. These calculated results propose that the improved electrocatalytic activity of PtAu bimetallic catalysts for methanol oxidation should be attributed to the alternation in the major reaction pathway from the CO pathway on pure Pt surface to the non-CO pathway on the PtAu bimetallic surface rather than the easier removal of CO on PtAu catalysts than that on pure Pt catalysts.
     4. By performing density functional theory calculations, we have studied the dual-path mechanism of formic acid (HCOOH) oxidation on the PtAu(111) surface in the continuum water solution phase. The direct pathway involving the dehydrogenation of HCOOH to form CO2occurs with a barrier of15.5kcal/mol, which is in contrast to the much higher barrier of99.2kcal/mol in the indirect pathway involving the dehydration of HCOOH to form CO intermediate. In comparison, the calculated barriers on Pt(111) surface in direct and indirect pathways are5.8and32.9kcal/mol, respectively. The theoretical results emphasize that bimetallic PtAu(111) surface significantly increases the barrier difference between the two pathways to83.7kcal/mol from27.1kcal/mol on the Pt(111) surface, and thus can hinder remarkably the indirect pathway. The theoretical results rationalize well the experimental finding that bimetallic PtAu catalysts show higher catalytic activity towards HCOOH oxidation than pure Pt catalysts.
     5. We establish the new and reasonable theoretical model. HCOOH molecules can form stable dimers through a variety of hydrogen-bonded structures with a formation energy up to15kcal/mol, so we conjecture that HCOOH electro-oxidation is relative with dimers'structure. We design dimer model and water assistance proton bridge model of HCOOH electro-oxidation. The theoretical results show that (ⅰ) the HCOOH dimer which adsorbs on the Pt(111) surface forms CO intermediate via intermolecular dehydration and leads to catalysts'CO-poisoning,(ⅱ) the carbonyl and hydroxyl group of HCOOH can form hydrogen bonds with surrounding water molecules, which may play an important role to HCOOH electro-oxidation, and water assistance proton bridge can promote the reaction and reduce the energy barrier. The newly proposed mechanism improves our understanding for the mechanism of catalytic HCOOH oxidation and rationalizes the easy CO poisoning of Pt-based catalysts.

引文

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