PdZn合金催化甲醇水蒸气重整反应的理论研究
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摘要
由于化石能源的日益匮乏,可再生能源越来越引起人们的注意。作为一种极具前景的有效替代能源,氢能具有高效、高密度和零排放等优点。甲醇作为一种理想的能源载体可为车(船、飞机等)的燃料电池提供现场的氢气来源。其中一种制氢的方法即是甲醇水蒸气催化重整反应(MSR, CH3OH+H2O→CO2+H2)。
Iwasa等发现Pd/ZnO催化剂表现出很好的热稳定性,且对MSR具有相当高的活性和选择性。相当有趣的是,在纯Pd表面,MSR反应却基本上仅产生CO。为了深入理解Zn添加导致选择性的这一差异,有必要弄清MSR在PdZn合金上的反应机理。传统的观点认为1:1PdZn合金是这一体系的活性相。然而,近来有人认为1：1PdZn可能对MSR不具有活性,掺入0.03-0.06ML Zn的Pd(111)可能最具活性。这一推测使得我们在机理研究之前,首要任务是研究Zn对Pd表面活性的影响并评估低Zn浓度下的Zn/Pd(111)体系是否对MSR具有催化活性。
水是MSR过程的主角之一,彻底弄清楚水在PdZn合金表面的行为是全面认识MSR反应的前提。过去的理论研究曾报道,水在PdZn(111)体相合金表面的吸附能仅为23kJ/mol.如此小的吸附能预示着水在PdZn(111)表面的解离非常困难或PdZn(111)表面不是水解离的活性相。近来的实验研究指出1：1PdZn单层合金不能活化水而1：1多层合金可有效的活化。这一实验结论看起来与上述理论结果相矛盾。我们不禁会问,在PdZn合金上水能解离这一结论对吗?如果是对的,为什么多层和单层合金表现出如此大的差异?如果不对,水到底是在什么地方活化的?
带着这些疑问,在本论文中我们主要运用密度泛函理论(DFT)结合蒙特卡罗(MC)技术研究Zn对Pd(111)表面吸附和反应的影响,评估低Zn浓度的Pd(111)表面对MSR的活性并最终揭示MSR过程的微观机理。
论文的主要内容简要地介绍如下。
首先我们考察了CO在PdZn表面合金上的吸附,对Zn的掺入如何影响Pd表面的性质作了系统的研究。结果表明,位于表层的Zn对CO吸附的影响远小于在次表层的Zn。这一现象在CO位于穴位吸附时尤为明显。引起这一现象的原因源于Zn的引入导致合金表面出现两种作用相反的效应：有利于CO吸附的应变效应和不利于其吸附的电子效应。当Zn原子掺入表层时,应变效应基本上与电子效应相互抵消；当Zn原子位于次表层时,应变效应很弱,不能有效地抵消电子效应。
为进一步弄清Zn对Pd(111)表面化学性质的影响,我们系统地研究了甲醇在系列Pd-Zn表面合金模型上的解离。结果表明,吸附能在不同底物的变化规律可以归结为Zn在不同位置的分布。即表层Zn有利于增强依靠O与底物作用的物种,如CH3O等。随着表层Zn浓度的增加,这类物种的吸附能增大；对于那些主要通过C-Pd作用在表面吸附的物种,如CH2O、CHO等,其吸附能随次表层Zn的增加而减小。添加Zn减小了CH3OH/CHO的O-H/C-H键断裂的活化能,增加了CH3O和CH2O的脱氢能垒。与过去的DFT结果比较,第三层Zn对表面的吸附和反应影响甚微。
Jeroro等在TDP实验中观察到甲醛在沉积有0.03-0.06ML Zn浓度Pd(111)表面有两个脱附峰,其中一个峰中心位于210K,另一个位于360K。根据Redhead公式,后者对应的吸附能约为1.0eV。我们首先采用了MC模拟,结果表明,当沉积少量Zn时,Pd(111)表面形成含3-5个原子的表面团簇。随着沉积量的增加,这种小团簇数量急剧减少。基于MC的结果,我们构建了系列表面团簇模型并考察了作为“机理指示剂”的甲醛在其上的吸附和化学行为。结果表明,360K脱附峰可能来源于CH2O吸附在Pd和(或)Zn形成的表面团簇。由于CH2O在Zn团簇上脱氢困难,预示着该结构可能会对MSR具有一定的选择性。另一方面,计算得到CH2O+O反应的活化能低于CH2O脱氢,因此,如果沉积有～0.05ML Zn的Pd(111)表确对MSR具有活性,那么表面Zn团簇将最有可能是MSR的活性相。但我们的计算和分析还表明,在这种团簇上不仅CH3O脱氢形成CH2O难于1：1合金,而且其热力学稳定性也很差,因此,这种结构即便在实际催化体系中存在,其对MSR的贡献也是很小的。
对水的吸附和解离研究表明,不论多层还是单层PdZn合金均可以活化水。在平整的PdZn(111)表面,水形成六聚体时有利于解离；在(221)阶梯表面,水可以形成一维水链并易于在Zn暴露的阶梯处解离。我们的结果与文献的观点矛盾,值得进一步研究。此外,我们还发现在OH-H2O/PdZn(111)体系中,传统意义上共价键与氢键的区别变得模糊,这一重要发现仍有待于进一步探讨。
基于上述研究和相关的实验,我们采用1:1PdZn合金模型模拟Pd/ZnO催化剂并据此系统地研究了MSR反应机理。结果显示,CH3OH先逐步脱氢得到CH2O,随后CH2O可以和表面OH或O反应生成H2COOH或H2COO物种。这些产物再经逐步脱氢产生CO2。整个过程的决速步骤是CH3O的C-H断裂。OH的参与在热力学上对C-H和O-H断裂均有利,但在动力学上共存的OH只有利于O-H断裂而对C-H键断裂不仅没有促进作用反而抑制其发生。这些结果清楚地给出了在MSR过程的微观图像,提供了MSR过程详细的热力学和动力学参数,对解释实验现象、优化MSR反应条件和设计催化剂具有一定的参考价值。
总之,本论文阐述了Zn对Pd(111)表面化学的影响；提出低Zn浓度的Zn/Pd(111)体系对催化MSR反应并不重要；水在单层表面合金上的分解比多层合金更有利；并最终给出MSR反应在PdZn(111)表面的完整机理。
With fossil fuels becoming rare everyday, renewable energy attracts more and more attention. As one of the most promising substitutions, hydrogen energy has many merits such as high-efficiency, condensed-density and zero-emission etc. Methanol is an ideal energy carrier which can produce hydrogen in situ for on-board fuel cells. One proposed method is the methanol steam reforming (MSR, CH3OH+H2O→CO2+H2).
Iwasa et al. discovered that Pd/ZnO catalyst displays good stability and exhibits high activity and selectivity towards MSR reaction. Quite interesting, on pure Pd metal, MSR produces exclusively CO. To gain insight into understanding the selectivity difference with Zn modification, it is necessary to make clear the reaction mechanism of MSR on PdZn alloy. Traditional point of view believed that1:1Pd-Zn alloy is the active components. However, recent study proposed that the1:1PdZn alloy might have no activity toward MSR, whereas Pd(111) surface deposited with0.03-0.06ML Zn may be most active. This speculation makes us before MSR reaction mechanism exploration, primary task is to investigate the effect of Zn on the activity of Pd(111) surface and evaluate the activity of Pd(111) surface with low Zn deposition towards MSR.
As a participator among the MSR process, a thorough understanding of the behavior of water on PdZn alloy is a prerequisite for obtaining comprehensive knowledge of MSR. Previous theoretical study reported an adsorption energy of water to be only23kJ/mol on the (111) surface of PdZn bulk alloy. Such small adsorption energy implies that water dissociation is difficult on the PdZn(111) or the PdZn(111) is not the active sites for water activation. Recent experiments demonstrate that while water keeps intact on1:1PdZn monolayer alloy, dissociation of water takes place on multilayer of1:1PdZn alloy actively. This experimental conclusion seems to contradict the abovementioned theoretical predictions. We cannot help but asking:is the conclusion that water dissociation occurs on PdZn multilayer correct? If yes, why the multilayer and monolayer PdZn display such striking different behavior toward H2O activation? If not, where can H2O be activated?
With these questions in mind, in this dissertation we mainly use density functional theory (DFT) combined with Monte-Carlo (MC) technique to investigate the effect of Zn on the adsorption and reaction of Pd(111), to evaluate the activity on Pd(111) surface with low Zn deposition towards MSR and finally to reveal the microcosmic mechanism of the MSR process.
The primary investigation contents are briefly introduced as follows.
Firstly we present a systematic theoretical study of the change of surface reactivity induced by incorporation of Zn by examining the CO adsorption on PdZn surface alloy. The results show that Zn atoms in the topmost layer have smaller effect on CO adsorption than the Zn in the second layer, especially for hollow sites. The reason for this phenomenon originates from the strain effect and ligand effect that have different influences on CO adsorption. When Zn atoms are doped on the topmost layer of Pd(111), the strain effect that favors the bonding of CO to the surface alloy offsets almost completely the ligand effect which is unfavorable for CO adsorption. At variance, when Zn atoms are deposited on the subsurface, the strain effect is much weak and cannot standoffs the ligand effect which, in this case, dominates the CO adsorption.
To further understand the modification of Zn on the reactivity of Pd(111), we carried out a systematic study of methanol dehydrogenation on a series of Pd-Zn surface alloys using DFT. We find that the variation of binding energy on different substrates can be well rationalized with distribution of Zn:the top-layer Zn enhances the interaction of species like CH3O that binds to the substrate via the oxygen atom. For such species the binding energy increases with the increase of the surface Zn content. For those adsorbates that adsorb on the substrate mainly through the C-Pd interaction, the binding energy decreases with the increase of subsurface Zn concentration. Addition of Zn reduces the activation energy of O-H/C-H bond breaking of CH3OH/CHO whereas it raises the energy barriers of dehydrogenation of CH3O and CH2O. Compared with previous DFT results, we suggest that Zn atoms beyond the third layer have essentially no influence on the adsorption and reaction at the surface.
Jeroro et al. observed in the TPD experiment two desorption peaks of CH2O on Pd(111) surface on which low Zn is deposited. One peak centers at210K which is derived from CH2O adsorbed on Pd(111) or normal PdZn alloy surface, and the other at360K. The latter peak corresponds to a binding energy of1.0eV estimated with Redhead formula. To gain the knowledge of surface structure, we performed MC simulation. The results demonstrated that at very low zinc coverage, small surface ensembles of3to5atoms exist preferentially on the surface. Based on these findings, we constructed a series of surface cluster models to mimic the adsorption and reaction of CH2O,"an indicator of MSR mechanism". The results reveal that the360K desorption peak is originated from the formaldehyde adsorbed on the small surface clusters with Pd and/or Zn content. Investigations of CH2O dehydrogenation to CHO and formation of H2COO from CH2O and O show that the supported Zn clusters (very likely as well as clusters dominated with Zn) are most likely the speculated active phases if the Pd(111) surface deposited with0.03to0.06ML Zn is really active for MSR reaction. However, on the surface Zn clusters dehydrogenation of CH3O to CH2O is harder than on1:1alloy surface. Further, the stability of such surface clusters is much lower. Hence, surface Zn clusters, even though they exist in realistic catalysis system, they will not contribute significantly to MSR reaction
Investigations of water adsorption and dissociation in various aggregation forms on multi-and monolayer surface alloy of both flat and stepped surfaces reveal that both the PdZn multi-and mono-layer can activate H2O. On multi-flat PdZn(111) surface, aggregation favors H2O dissociation. In most cases, monolayer surface alloy is more active for water dissociation than the multilayer. On stepped PdZn(221) surfaces, H2O is favorably dissociated on exposed Zn step. Contrary to the point of view of the Austria research groups that the PdZn monolayer cannot activate H2O, our first-principles results clearly demonstrate that as long as the multilayer surfaces are able to dissociate water, water dissociate can take place on the monolayer surface without question. This discrepancy needs further studies from both experimental and theoretical sides. Furthermore, we find that the traditional distinction between covalent and hydrogen bonds is faint in OH-H2O overlayers on PdZn substrate which we have highlighted.
Based on the above theoretical studies and the pertinent experiments, we employed the1:1PdZn alloy model to mimic Pd/ZnO catalyst and explored systematically the MSR mechanism. Calculations show that the MSR reaction proceeds from dehydrogenation of CH3OH to CH2O via CH3O, subsequently CH2O facilely reacts with OH or O to yield H2COOH or H2COO species. The yielded products experience stepwise dehydrogenation to produce CO2. The rate-determining step is the dehydrogenation of CH3O. The presence of OH always makes the C-H and O-H bond breaking more exothermic or less endothermic. However, kinetically, the coadsorbed OH reduces the O-H scission barrier, but does not facilitate or even inhibits the C-H rupture. Our results present a vivid microscopic picture of the MSR reaction. They are deemed to shed light on experimental observations, provide detailed thermodynamic and kinetic parameters for further microkinetic simulation of MSR process, and are informative for optimizing the MSR reaction condition and for designing new MSR catalysts of high quality.
To recap, this dissertation elucidates the modification of Zn on the chemistry of Pd(111). The Pd(111) surface modified with low Zn concentration is demonstrated to be unimportant for MSR reaction. We show that monolayer surface alloy is more active for water dissociation than the multilayer alloy surface. Finally we furnished a complete energy profile of the MSR process on PdZn(111) surface.
Iwasa等发现Pd/ZnO催化剂表现出很好的热稳定性,且对MSR具有相当高的活性和选择性。相当有趣的是,在纯Pd表面,MSR反应却基本上仅产生CO。为了深入理解Zn添加导致选择性的这一差异,有必要弄清MSR在PdZn合金上的反应机理。传统的观点认为1:1PdZn合金是这一体系的活性相。然而,近来有人认为1：1PdZn可能对MSR不具有活性,掺入0.03-0.06ML Zn的Pd(111)可能最具活性。这一推测使得我们在机理研究之前,首要任务是研究Zn对Pd表面活性的影响并评估低Zn浓度下的Zn/Pd(111)体系是否对MSR具有催化活性。
水是MSR过程的主角之一,彻底弄清楚水在PdZn合金表面的行为是全面认识MSR反应的前提。过去的理论研究曾报道,水在PdZn(111)体相合金表面的吸附能仅为23kJ/mol.如此小的吸附能预示着水在PdZn(111)表面的解离非常困难或PdZn(111)表面不是水解离的活性相。近来的实验研究指出1：1PdZn单层合金不能活化水而1：1多层合金可有效的活化。这一实验结论看起来与上述理论结果相矛盾。我们不禁会问,在PdZn合金上水能解离这一结论对吗?如果是对的,为什么多层和单层合金表现出如此大的差异?如果不对,水到底是在什么地方活化的?
带着这些疑问,在本论文中我们主要运用密度泛函理论(DFT)结合蒙特卡罗(MC)技术研究Zn对Pd(111)表面吸附和反应的影响,评估低Zn浓度的Pd(111)表面对MSR的活性并最终揭示MSR过程的微观机理。
论文的主要内容简要地介绍如下。
首先我们考察了CO在PdZn表面合金上的吸附,对Zn的掺入如何影响Pd表面的性质作了系统的研究。结果表明,位于表层的Zn对CO吸附的影响远小于在次表层的Zn。这一现象在CO位于穴位吸附时尤为明显。引起这一现象的原因源于Zn的引入导致合金表面出现两种作用相反的效应：有利于CO吸附的应变效应和不利于其吸附的电子效应。当Zn原子掺入表层时,应变效应基本上与电子效应相互抵消；当Zn原子位于次表层时,应变效应很弱,不能有效地抵消电子效应。
为进一步弄清Zn对Pd(111)表面化学性质的影响,我们系统地研究了甲醇在系列Pd-Zn表面合金模型上的解离。结果表明,吸附能在不同底物的变化规律可以归结为Zn在不同位置的分布。即表层Zn有利于增强依靠O与底物作用的物种,如CH3O等。随着表层Zn浓度的增加,这类物种的吸附能增大；对于那些主要通过C-Pd作用在表面吸附的物种,如CH2O、CHO等,其吸附能随次表层Zn的增加而减小。添加Zn减小了CH3OH/CHO的O-H/C-H键断裂的活化能,增加了CH3O和CH2O的脱氢能垒。与过去的DFT结果比较,第三层Zn对表面的吸附和反应影响甚微。
Jeroro等在TDP实验中观察到甲醛在沉积有0.03-0.06ML Zn浓度Pd(111)表面有两个脱附峰,其中一个峰中心位于210K,另一个位于360K。根据Redhead公式,后者对应的吸附能约为1.0eV。我们首先采用了MC模拟,结果表明,当沉积少量Zn时,Pd(111)表面形成含3-5个原子的表面团簇。随着沉积量的增加,这种小团簇数量急剧减少。基于MC的结果,我们构建了系列表面团簇模型并考察了作为“机理指示剂”的甲醛在其上的吸附和化学行为。结果表明,360K脱附峰可能来源于CH2O吸附在Pd和(或)Zn形成的表面团簇。由于CH2O在Zn团簇上脱氢困难,预示着该结构可能会对MSR具有一定的选择性。另一方面,计算得到CH2O+O反应的活化能低于CH2O脱氢,因此,如果沉积有～0.05ML Zn的Pd(111)表确对MSR具有活性,那么表面Zn团簇将最有可能是MSR的活性相。但我们的计算和分析还表明,在这种团簇上不仅CH3O脱氢形成CH2O难于1：1合金,而且其热力学稳定性也很差,因此,这种结构即便在实际催化体系中存在,其对MSR的贡献也是很小的。
对水的吸附和解离研究表明,不论多层还是单层PdZn合金均可以活化水。在平整的PdZn(111)表面,水形成六聚体时有利于解离；在(221)阶梯表面,水可以形成一维水链并易于在Zn暴露的阶梯处解离。我们的结果与文献的观点矛盾,值得进一步研究。此外,我们还发现在OH-H2O/PdZn(111)体系中,传统意义上共价键与氢键的区别变得模糊,这一重要发现仍有待于进一步探讨。
基于上述研究和相关的实验,我们采用1:1PdZn合金模型模拟Pd/ZnO催化剂并据此系统地研究了MSR反应机理。结果显示,CH3OH先逐步脱氢得到CH2O,随后CH2O可以和表面OH或O反应生成H2COOH或H2COO物种。这些产物再经逐步脱氢产生CO2。整个过程的决速步骤是CH3O的C-H断裂。OH的参与在热力学上对C-H和O-H断裂均有利,但在动力学上共存的OH只有利于O-H断裂而对C-H键断裂不仅没有促进作用反而抑制其发生。这些结果清楚地给出了在MSR过程的微观图像,提供了MSR过程详细的热力学和动力学参数,对解释实验现象、优化MSR反应条件和设计催化剂具有一定的参考价值。
总之,本论文阐述了Zn对Pd(111)表面化学的影响；提出低Zn浓度的Zn/Pd(111)体系对催化MSR反应并不重要；水在单层表面合金上的分解比多层合金更有利；并最终给出MSR反应在PdZn(111)表面的完整机理。
With fossil fuels becoming rare everyday, renewable energy attracts more and more attention. As one of the most promising substitutions, hydrogen energy has many merits such as high-efficiency, condensed-density and zero-emission etc. Methanol is an ideal energy carrier which can produce hydrogen in situ for on-board fuel cells. One proposed method is the methanol steam reforming (MSR, CH3OH+H2O→CO2+H2).
Iwasa et al. discovered that Pd/ZnO catalyst displays good stability and exhibits high activity and selectivity towards MSR reaction. Quite interesting, on pure Pd metal, MSR produces exclusively CO. To gain insight into understanding the selectivity difference with Zn modification, it is necessary to make clear the reaction mechanism of MSR on PdZn alloy. Traditional point of view believed that1:1Pd-Zn alloy is the active components. However, recent study proposed that the1:1PdZn alloy might have no activity toward MSR, whereas Pd(111) surface deposited with0.03-0.06ML Zn may be most active. This speculation makes us before MSR reaction mechanism exploration, primary task is to investigate the effect of Zn on the activity of Pd(111) surface and evaluate the activity of Pd(111) surface with low Zn deposition towards MSR.
As a participator among the MSR process, a thorough understanding of the behavior of water on PdZn alloy is a prerequisite for obtaining comprehensive knowledge of MSR. Previous theoretical study reported an adsorption energy of water to be only23kJ/mol on the (111) surface of PdZn bulk alloy. Such small adsorption energy implies that water dissociation is difficult on the PdZn(111) or the PdZn(111) is not the active sites for water activation. Recent experiments demonstrate that while water keeps intact on1:1PdZn monolayer alloy, dissociation of water takes place on multilayer of1:1PdZn alloy actively. This experimental conclusion seems to contradict the abovementioned theoretical predictions. We cannot help but asking:is the conclusion that water dissociation occurs on PdZn multilayer correct? If yes, why the multilayer and monolayer PdZn display such striking different behavior toward H2O activation? If not, where can H2O be activated?
With these questions in mind, in this dissertation we mainly use density functional theory (DFT) combined with Monte-Carlo (MC) technique to investigate the effect of Zn on the adsorption and reaction of Pd(111), to evaluate the activity on Pd(111) surface with low Zn deposition towards MSR and finally to reveal the microcosmic mechanism of the MSR process.
The primary investigation contents are briefly introduced as follows.
Firstly we present a systematic theoretical study of the change of surface reactivity induced by incorporation of Zn by examining the CO adsorption on PdZn surface alloy. The results show that Zn atoms in the topmost layer have smaller effect on CO adsorption than the Zn in the second layer, especially for hollow sites. The reason for this phenomenon originates from the strain effect and ligand effect that have different influences on CO adsorption. When Zn atoms are doped on the topmost layer of Pd(111), the strain effect that favors the bonding of CO to the surface alloy offsets almost completely the ligand effect which is unfavorable for CO adsorption. At variance, when Zn atoms are deposited on the subsurface, the strain effect is much weak and cannot standoffs the ligand effect which, in this case, dominates the CO adsorption.
To further understand the modification of Zn on the reactivity of Pd(111), we carried out a systematic study of methanol dehydrogenation on a series of Pd-Zn surface alloys using DFT. We find that the variation of binding energy on different substrates can be well rationalized with distribution of Zn:the top-layer Zn enhances the interaction of species like CH3O that binds to the substrate via the oxygen atom. For such species the binding energy increases with the increase of the surface Zn content. For those adsorbates that adsorb on the substrate mainly through the C-Pd interaction, the binding energy decreases with the increase of subsurface Zn concentration. Addition of Zn reduces the activation energy of O-H/C-H bond breaking of CH3OH/CHO whereas it raises the energy barriers of dehydrogenation of CH3O and CH2O. Compared with previous DFT results, we suggest that Zn atoms beyond the third layer have essentially no influence on the adsorption and reaction at the surface.
Jeroro et al. observed in the TPD experiment two desorption peaks of CH2O on Pd(111) surface on which low Zn is deposited. One peak centers at210K which is derived from CH2O adsorbed on Pd(111) or normal PdZn alloy surface, and the other at360K. The latter peak corresponds to a binding energy of1.0eV estimated with Redhead formula. To gain the knowledge of surface structure, we performed MC simulation. The results demonstrated that at very low zinc coverage, small surface ensembles of3to5atoms exist preferentially on the surface. Based on these findings, we constructed a series of surface cluster models to mimic the adsorption and reaction of CH2O,"an indicator of MSR mechanism". The results reveal that the360K desorption peak is originated from the formaldehyde adsorbed on the small surface clusters with Pd and/or Zn content. Investigations of CH2O dehydrogenation to CHO and formation of H2COO from CH2O and O show that the supported Zn clusters (very likely as well as clusters dominated with Zn) are most likely the speculated active phases if the Pd(111) surface deposited with0.03to0.06ML Zn is really active for MSR reaction. However, on the surface Zn clusters dehydrogenation of CH3O to CH2O is harder than on1:1alloy surface. Further, the stability of such surface clusters is much lower. Hence, surface Zn clusters, even though they exist in realistic catalysis system, they will not contribute significantly to MSR reaction
Investigations of water adsorption and dissociation in various aggregation forms on multi-and monolayer surface alloy of both flat and stepped surfaces reveal that both the PdZn multi-and mono-layer can activate H2O. On multi-flat PdZn(111) surface, aggregation favors H2O dissociation. In most cases, monolayer surface alloy is more active for water dissociation than the multilayer. On stepped PdZn(221) surfaces, H2O is favorably dissociated on exposed Zn step. Contrary to the point of view of the Austria research groups that the PdZn monolayer cannot activate H2O, our first-principles results clearly demonstrate that as long as the multilayer surfaces are able to dissociate water, water dissociate can take place on the monolayer surface without question. This discrepancy needs further studies from both experimental and theoretical sides. Furthermore, we find that the traditional distinction between covalent and hydrogen bonds is faint in OH-H2O overlayers on PdZn substrate which we have highlighted.
Based on the above theoretical studies and the pertinent experiments, we employed the1:1PdZn alloy model to mimic Pd/ZnO catalyst and explored systematically the MSR mechanism. Calculations show that the MSR reaction proceeds from dehydrogenation of CH3OH to CH2O via CH3O, subsequently CH2O facilely reacts with OH or O to yield H2COOH or H2COO species. The yielded products experience stepwise dehydrogenation to produce CO2. The rate-determining step is the dehydrogenation of CH3O. The presence of OH always makes the C-H and O-H bond breaking more exothermic or less endothermic. However, kinetically, the coadsorbed OH reduces the O-H scission barrier, but does not facilitate or even inhibits the C-H rupture. Our results present a vivid microscopic picture of the MSR reaction. They are deemed to shed light on experimental observations, provide detailed thermodynamic and kinetic parameters for further microkinetic simulation of MSR process, and are informative for optimizing the MSR reaction condition and for designing new MSR catalysts of high quality.
To recap, this dissertation elucidates the modification of Zn on the chemistry of Pd(111). The Pd(111) surface modified with low Zn concentration is demonstrated to be unimportant for MSR reaction. We show that monolayer surface alloy is more active for water dissociation than the multilayer alloy surface. Finally we furnished a complete energy profile of the MSR process on PdZn(111) surface.
引文
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