燃料电池电催化剂催化机理与可控制备
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摘要
燃料电池因具有高效能和环境友好等优点而成为最有发展前途的一种电池。但当前所使用的电极催化剂以Pt为主，价格昂贵，要真正实现燃料电池的商业化，设计和寻找有效的低Pt和非Pt催化剂势在必行。本文主要结合当前的研究现状，从揭示电极反应的机理入手，针对当前研究存在的不足，做了以下四方面的工作：1）利用DFT方法研究了不同介质中甲醇在Pd(111)面的催化反应机理；2）探究了H在Pd(111)面的吸附、迁移和渗透行为及H的亚层吸收对于催化剂本身性质的影响；3）解析了氧还原反应在MPt^双金属催化剂表面的反应机理；4）利用连续有机金属法制备了不同形貌的双金属PtRu催化剂。旨在于为催化剂的设计和合成提供一定的理论基础和实验指导，为推动燃料电池事业的发展贡献一点微薄之力。
首先，针对当前甲醇氧化反应机理模拟主要限于理想真空体系的问题，建立了不同介质中甲醇分子在Pd/溶液界面的吸附和反应理论模型，利用DFT方法研究了Pd对甲醇分子的催化活性。结果表明：中性介质中，Pd对甲醇分子不具有催化活性，甲醇分子的OH与水分子形成稳定的界面六边形氢键体系，甲醇分子的吸附能因氢键的生成而增大28.20kJ mol-1。酸性介质中，由于H质子的引入，界面层内发生质子转移，形成水合H离子和局域强氢键；同时，六边形氢键体系由于Cl-的引入而遭到破坏，体系能量降低，但甲醇分子内部键长保持不变，Pd对甲醇氧化也不具有催化活性。碱性介质中，规则六边形氢键体系因甲醇活化而破坏，但会有新的紧缩六边形氢键体系生成；甲醇分子以伸长O-H键或甲氧基的形式存在，体系能量明显降低，Pd对甲醇表现出较好的催化活性。
其次，针对阳极氧化反应中H在催化剂表面的吸附、跃迁和渗透行为，及其对催化剂性质的影响缺少系统理论解析的现状，利用DFT方法研究了不同覆盖度下H在Pd(111)表面吸附、亚层吸收和体相渗透等行为的热力学和动力学性质。结果表明：H覆盖度为0.25ML时，H原子优先形成表面三重空位FCC和HCP的吸附，并且可在表面top位及亚层OSS和TSS位稳定存在，但不能稳定吸附于bridge位。当H覆盖度低于1.00ML时，Pd(111)最外层Pd原子的皱褶效应较小，超过1.00ML时，皱褶效应明显增大，并在1.50ML时达到最大值0.087。PDOS研究表明Pd-H间的作用会使Pd(111)表面最外层Pd原子的d能带分裂，随着氢覆盖度的增加，Pd(111)最外层原子的d电子态密度火山峰值增大，而d带中心则降低，并导致相应的H-Pd作用减弱。H在Pd(111)面的亚层吸收会使Pd(111)的催化性能略微下降。
再次，从低Pt催化剂设计和氧还原反应机理解析的角度出发，研究了元素周期表中以三个近Pt元素Ir、Pd和Au为基底金属，表面Pt单层覆盖的MPt^双金属的催化氧还原反应机理。利用DFT方法计算了ORR过程中O2的吸附与解离，以及两个中间物种O和OH在IrPt^、PdPt^和AuPt^(111)面的吸附情况，并与单金属Pt(111)面作了比较。发现O和OH的结合能都随着d带中心的增大而增大，IrPt^、PdPt^和AuPt^按照基底金属在元素周期表中的排布，对ORR催化过程中O2解离反应的活化能和中间产物O原子的吸附能的影响符合BEP关系，IrPt^、PdPt^和AuPt^对ORR的催化活性呈现出其在元素周期表中的火山关系。表面应力效应、电荷转移和PDOS对于d带中心影响的研究表明：表面压力导致d带中心远离费米能级，而表面张力则导致d带中心移向费米能级。对于IrPt^而言，电子自表层Pt流向基底金属Ir，表层Pt原子的d电子减少，使d电子平均密度降低，进而导致d带中心远离Fermi能级；而PdPt^和AuPt^则发生Pd、Au电子流向表层Pt的现象，使Pt的d带中心移向Fermi能级。表面应力效应跟电子配位效应同时影响d带中心的性质，但是表面应力效应起主要作用。Ir基底使表面单层Pt的d带展宽；Pd基底对表层Pt的d带宽度影响较小；Au基底则使表层Pt的d带略微收缩。PdPt^(111)可被认是潜在的ORR低Pt催化剂。
最后，利用分步有机金属法制备了双金属Ru@Pt核壳纳米粒子和改性的T-PtRu (tuned-PtRu)纳米粒子。WAXS、TEM和HRTEM的表征及ICP-MS和EDS的分析证明：在温和反应条件下，分步有机金属法成功制备了高分散、窄尺寸粒径分布的核壳结构Ru@Pt纳米粒子，Ru@Pt/PPP的粒径尺寸在1.80nm左右，较共还原法制备的纳米粒子粒径尺寸小0.2nm左右。结合HRTEM和理论模型分析可知，Ru:Pt用量比为1:1时，壳层Pt原子不能形成有效单层覆盖，粒子表面为Ru(0001)晶面；Ru:Pt用量比为1:2时，刚好实现单层覆盖，晶型较好，呈现明显的截断八面体结构，粒子表面多为Ru(0001)，粒子边缘原子排布间距略微减小，原子层间距介于Ru(0001)和Pt(111)面之间；Ru:Pt用量比为1:4时，晶粒表面会有明显的Pt(111)特征。通过连续还原Pt2(dba)3和Ru(COD)(COT)的方法，不能有效制备Pt@Ru/PPP催化剂，但可制备高分散、窄尺寸粒径分布的改性T-PtRu/PPP纳米粒子。
Fuel cells (FCs) are regarded as ideal candidates for stationary and mobile powergeneration due to their high energy conversion efficiency and environmental benefits.However, the high cost and low Pt utilization of electrocatalyst have been recentlyrecognized as the most important issues to be addressed before commercialization. Thusresearches on the effective low-Pt and non-Pt catalysts have attracted more and moreattention. In the present study, we did the following work:1) DFT study on themechanism of methanol reaction catalyzed by Pd(111);2) the behavior of H adsorption,migration and penetration on Pd(111) and the effect of absorbed H on the property ofcatalyst;3) the mechanism of oxygen reduction reaction (ORR) on monolayer platinumover substrate metal (MPt^);4) synthesis of shape-controlled bimetallic PtRunanoparticles with organometallic method.
Firstly, a model reflecting the effect of different solution on methanol reactivity onPd(111) has been proposed. The DFT calculation based on the established model hasreached the following conclusions. Pd(111) does not show any activity toward methanoloxidation either in neutral or acid solution. In neutral solution, with the substitution ofone methanol molecule for one water molecule, puckered hexagonal network ofhydrogen bonds has few changes compared with the pure water system. The adsorptionenergy of methanol is28.20kJ mol-1more than that in vacuum. Such a decrease in theadsorption energy is attributed to the contribution of one hydrogen bond betweenmethanol and neighboring water molecules. In acid solution, methanol is stillmolecularly adsorbed on Pd(111) with a slight relaxation of O-C and O-H bonds. Theslight change in methanol structure suggests that methanol in acid solution is notactivated. Different from those in neutral and in acid solution, the reactivity of methanolcatalyzed by Pd(111) in alkaline solution can be categorized into three cases. Theactivation of methanol in every case is indisputable, which is symbolized by elongatedhydroxyl or methoxy formation.
Secondly, the interaction of hydrogen atoms with Pd(111) surface is studied withdensity functional theory (DFT) method. Various coverages ranging from0.25to2.00monolayer (ML) are considered. Particular attention is paid to the thermodynamics andkinetics of the adsorption or absorption processes and to the structural and electronicproperties. The results show that the threefold hollow sites, face centered cubic (FCC) and hexaganol close packed (HCP) are most energetically favorable. The diffusionprocessed in the same layer is more preferential than the penetration processed in twodifferent layers. For the coverages more than1.00ML, it is predicted that the additionalhydrogen easily penetrates into subsurface. PDOS research shows that the interaction ofhydrogen atoms with Pd leads to a splitting of d electron density of the outmost Pd(111)and to a gradual decrease of d band center of surface Pd atoms with coveragesincreasing. The Pd(111) occupied by hydrogen atoms shows a little bit less activity thanthe clean Pd(111).
Thirdly, DFT is used to calculate the energetics of oxygen reduction reaction (ORR)on MPt^catalysts over substrates including Ir, Pd and Au. The binding energy of bothatomic oxygen and hydroxyl radical is found to correlate well with the d band center ofsurface Pt^. The binding energy of both atomic oxygen and hydroxyl radical increasesas the d band center increases. The relationship between energy barrier of molecularoxygen dissociation and binding energy of oxygen atom on various MPt^bimetalliccatalysts meets the BEP rules. The effect of surface strain, charge transfer and PDOS onthe d band center are well studied, and it can be found that both the surface strain effectand electronic effect will affect the d band center of surface Pt^in bimetallic MPt^catalyst，while the strain effect plays the most important role for the d band center ofPt(111) over various bimetallic MPt^catalysts. Surface compressive strain whichcorresponds to expansive Pt-Pt bond and electrons delation of Pt^drives the d bandcenter of Pt^over Ir substrate downward away from the Fermi level. Surface tensionand surplus electrons of Pt^over Au substrate makes the d band center of Pt^movetowards to the Fermi level. However, Pd substrate makes the d band center of surfacemonolayer Pt of MPt^comparable with the monometallic Pt, bringing similar catalyticactivity to ORR. Their catalytic activities show the volcano relationship as theirpositions in the periodic table, and it can be deemed that the MPt^over Pd substrate willbe the most potential candidate for ORR catalysts.
Finally, Ru@Pt core-shell nanoparticles and surfacre tuned T-PtRu bimetalliccatalysts are prepared through the two-step orgnometallic approach. The wide-angleX-ray scattering (WAXS), transmission electron microscope (TEM) and high resolutiontransmission electron microscope (HRTEM) are used to characterize the nanoparticles.It is found that in mild conditions, high dispersed Ru@Pt nanoparticles with a narrowsize distribution are synthesized successfully with two-step orgnometallic approach. Theaverage size diameters are around1.80nm which is about0.20nm smaller than the PtRu nanoparticles synthesized with one-step orgnometallic method. The analysisthrough inductively coupled plasma mass spectrometry (ICP-MS) and energy dispersivespectrum (EDS) further prove our results. HRTEM and the theoretical model analysisshow that the Pt atoms are insufficient to form one monolayer coverage over Ru(0001).Truncated octahedron can be observed obviously through HRTEM when the Ru:Pt ratiois1:2, and the nanoparticles own the character of HCP Ru. Meanwhile, the boundaryatoms among which the distances become smaller show the character of Pt(111). SomePt(111) islands can be determined when the Ru:Pt ratio is1:4. However, it can be foundthat Pt@Ru/PPP nanoparticles can not be synthesized through the two-steporgnometallic method with the precursor of Pt2(dba)3and Ru(COD)(COT), but the CALselective hydrogenation catalyzed by the nanoparticle shows that the surface tunedT-PtRu/PPP nanoparticles have been prepared.
首先，针对当前甲醇氧化反应机理模拟主要限于理想真空体系的问题，建立了不同介质中甲醇分子在Pd/溶液界面的吸附和反应理论模型，利用DFT方法研究了Pd对甲醇分子的催化活性。结果表明：中性介质中，Pd对甲醇分子不具有催化活性，甲醇分子的OH与水分子形成稳定的界面六边形氢键体系，甲醇分子的吸附能因氢键的生成而增大28.20kJ mol-1。酸性介质中，由于H质子的引入，界面层内发生质子转移，形成水合H离子和局域强氢键；同时，六边形氢键体系由于Cl-的引入而遭到破坏，体系能量降低，但甲醇分子内部键长保持不变，Pd对甲醇氧化也不具有催化活性。碱性介质中，规则六边形氢键体系因甲醇活化而破坏，但会有新的紧缩六边形氢键体系生成；甲醇分子以伸长O-H键或甲氧基的形式存在，体系能量明显降低，Pd对甲醇表现出较好的催化活性。
其次，针对阳极氧化反应中H在催化剂表面的吸附、跃迁和渗透行为，及其对催化剂性质的影响缺少系统理论解析的现状，利用DFT方法研究了不同覆盖度下H在Pd(111)表面吸附、亚层吸收和体相渗透等行为的热力学和动力学性质。结果表明：H覆盖度为0.25ML时，H原子优先形成表面三重空位FCC和HCP的吸附，并且可在表面top位及亚层OSS和TSS位稳定存在，但不能稳定吸附于bridge位。当H覆盖度低于1.00ML时，Pd(111)最外层Pd原子的皱褶效应较小，超过1.00ML时，皱褶效应明显增大，并在1.50ML时达到最大值0.087。PDOS研究表明Pd-H间的作用会使Pd(111)表面最外层Pd原子的d能带分裂，随着氢覆盖度的增加，Pd(111)最外层原子的d电子态密度火山峰值增大，而d带中心则降低，并导致相应的H-Pd作用减弱。H在Pd(111)面的亚层吸收会使Pd(111)的催化性能略微下降。
再次，从低Pt催化剂设计和氧还原反应机理解析的角度出发，研究了元素周期表中以三个近Pt元素Ir、Pd和Au为基底金属，表面Pt单层覆盖的MPt^双金属的催化氧还原反应机理。利用DFT方法计算了ORR过程中O2的吸附与解离，以及两个中间物种O和OH在IrPt^、PdPt^和AuPt^(111)面的吸附情况，并与单金属Pt(111)面作了比较。发现O和OH的结合能都随着d带中心的增大而增大，IrPt^、PdPt^和AuPt^按照基底金属在元素周期表中的排布，对ORR催化过程中O2解离反应的活化能和中间产物O原子的吸附能的影响符合BEP关系，IrPt^、PdPt^和AuPt^对ORR的催化活性呈现出其在元素周期表中的火山关系。表面应力效应、电荷转移和PDOS对于d带中心影响的研究表明：表面压力导致d带中心远离费米能级，而表面张力则导致d带中心移向费米能级。对于IrPt^而言，电子自表层Pt流向基底金属Ir，表层Pt原子的d电子减少，使d电子平均密度降低，进而导致d带中心远离Fermi能级；而PdPt^和AuPt^则发生Pd、Au电子流向表层Pt的现象，使Pt的d带中心移向Fermi能级。表面应力效应跟电子配位效应同时影响d带中心的性质，但是表面应力效应起主要作用。Ir基底使表面单层Pt的d带展宽；Pd基底对表层Pt的d带宽度影响较小；Au基底则使表层Pt的d带略微收缩。PdPt^(111)可被认是潜在的ORR低Pt催化剂。
最后，利用分步有机金属法制备了双金属Ru@Pt核壳纳米粒子和改性的T-PtRu (tuned-PtRu)纳米粒子。WAXS、TEM和HRTEM的表征及ICP-MS和EDS的分析证明：在温和反应条件下，分步有机金属法成功制备了高分散、窄尺寸粒径分布的核壳结构Ru@Pt纳米粒子，Ru@Pt/PPP的粒径尺寸在1.80nm左右，较共还原法制备的纳米粒子粒径尺寸小0.2nm左右。结合HRTEM和理论模型分析可知，Ru:Pt用量比为1:1时，壳层Pt原子不能形成有效单层覆盖，粒子表面为Ru(0001)晶面；Ru:Pt用量比为1:2时，刚好实现单层覆盖，晶型较好，呈现明显的截断八面体结构，粒子表面多为Ru(0001)，粒子边缘原子排布间距略微减小，原子层间距介于Ru(0001)和Pt(111)面之间；Ru:Pt用量比为1:4时，晶粒表面会有明显的Pt(111)特征。通过连续还原Pt2(dba)3和Ru(COD)(COT)的方法，不能有效制备Pt@Ru/PPP催化剂，但可制备高分散、窄尺寸粒径分布的改性T-PtRu/PPP纳米粒子。
Fuel cells (FCs) are regarded as ideal candidates for stationary and mobile powergeneration due to their high energy conversion efficiency and environmental benefits.However, the high cost and low Pt utilization of electrocatalyst have been recentlyrecognized as the most important issues to be addressed before commercialization. Thusresearches on the effective low-Pt and non-Pt catalysts have attracted more and moreattention. In the present study, we did the following work:1) DFT study on themechanism of methanol reaction catalyzed by Pd(111);2) the behavior of H adsorption,migration and penetration on Pd(111) and the effect of absorbed H on the property ofcatalyst;3) the mechanism of oxygen reduction reaction (ORR) on monolayer platinumover substrate metal (MPt^);4) synthesis of shape-controlled bimetallic PtRunanoparticles with organometallic method.
Firstly, a model reflecting the effect of different solution on methanol reactivity onPd(111) has been proposed. The DFT calculation based on the established model hasreached the following conclusions. Pd(111) does not show any activity toward methanoloxidation either in neutral or acid solution. In neutral solution, with the substitution ofone methanol molecule for one water molecule, puckered hexagonal network ofhydrogen bonds has few changes compared with the pure water system. The adsorptionenergy of methanol is28.20kJ mol-1more than that in vacuum. Such a decrease in theadsorption energy is attributed to the contribution of one hydrogen bond betweenmethanol and neighboring water molecules. In acid solution, methanol is stillmolecularly adsorbed on Pd(111) with a slight relaxation of O-C and O-H bonds. Theslight change in methanol structure suggests that methanol in acid solution is notactivated. Different from those in neutral and in acid solution, the reactivity of methanolcatalyzed by Pd(111) in alkaline solution can be categorized into three cases. Theactivation of methanol in every case is indisputable, which is symbolized by elongatedhydroxyl or methoxy formation.
Secondly, the interaction of hydrogen atoms with Pd(111) surface is studied withdensity functional theory (DFT) method. Various coverages ranging from0.25to2.00monolayer (ML) are considered. Particular attention is paid to the thermodynamics andkinetics of the adsorption or absorption processes and to the structural and electronicproperties. The results show that the threefold hollow sites, face centered cubic (FCC) and hexaganol close packed (HCP) are most energetically favorable. The diffusionprocessed in the same layer is more preferential than the penetration processed in twodifferent layers. For the coverages more than1.00ML, it is predicted that the additionalhydrogen easily penetrates into subsurface. PDOS research shows that the interaction ofhydrogen atoms with Pd leads to a splitting of d electron density of the outmost Pd(111)and to a gradual decrease of d band center of surface Pd atoms with coveragesincreasing. The Pd(111) occupied by hydrogen atoms shows a little bit less activity thanthe clean Pd(111).
Thirdly, DFT is used to calculate the energetics of oxygen reduction reaction (ORR)on MPt^catalysts over substrates including Ir, Pd and Au. The binding energy of bothatomic oxygen and hydroxyl radical is found to correlate well with the d band center ofsurface Pt^. The binding energy of both atomic oxygen and hydroxyl radical increasesas the d band center increases. The relationship between energy barrier of molecularoxygen dissociation and binding energy of oxygen atom on various MPt^bimetalliccatalysts meets the BEP rules. The effect of surface strain, charge transfer and PDOS onthe d band center are well studied, and it can be found that both the surface strain effectand electronic effect will affect the d band center of surface Pt^in bimetallic MPt^catalyst，while the strain effect plays the most important role for the d band center ofPt(111) over various bimetallic MPt^catalysts. Surface compressive strain whichcorresponds to expansive Pt-Pt bond and electrons delation of Pt^drives the d bandcenter of Pt^over Ir substrate downward away from the Fermi level. Surface tensionand surplus electrons of Pt^over Au substrate makes the d band center of Pt^movetowards to the Fermi level. However, Pd substrate makes the d band center of surfacemonolayer Pt of MPt^comparable with the monometallic Pt, bringing similar catalyticactivity to ORR. Their catalytic activities show the volcano relationship as theirpositions in the periodic table, and it can be deemed that the MPt^over Pd substrate willbe the most potential candidate for ORR catalysts.
Finally, Ru@Pt core-shell nanoparticles and surfacre tuned T-PtRu bimetalliccatalysts are prepared through the two-step orgnometallic approach. The wide-angleX-ray scattering (WAXS), transmission electron microscope (TEM) and high resolutiontransmission electron microscope (HRTEM) are used to characterize the nanoparticles.It is found that in mild conditions, high dispersed Ru@Pt nanoparticles with a narrowsize distribution are synthesized successfully with two-step orgnometallic approach. Theaverage size diameters are around1.80nm which is about0.20nm smaller than the PtRu nanoparticles synthesized with one-step orgnometallic method. The analysisthrough inductively coupled plasma mass spectrometry (ICP-MS) and energy dispersivespectrum (EDS) further prove our results. HRTEM and the theoretical model analysisshow that the Pt atoms are insufficient to form one monolayer coverage over Ru(0001).Truncated octahedron can be observed obviously through HRTEM when the Ru:Pt ratiois1:2, and the nanoparticles own the character of HCP Ru. Meanwhile, the boundaryatoms among which the distances become smaller show the character of Pt(111). SomePt(111) islands can be determined when the Ru:Pt ratio is1:4. However, it can be foundthat Pt@Ru/PPP nanoparticles can not be synthesized through the two-steporgnometallic method with the precursor of Pt2(dba)3and Ru(COD)(COT), but the CALselective hydrogenation catalyzed by the nanoparticle shows that the surface tunedT-PtRu/PPP nanoparticles have been prepared.
引文
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