密度泛函理论计算在电催化反应以及电催化剂设计中的应用
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摘要
发展低贵金属含量、高催化活性和高稳定性的氧还原反应(ORR)催化剂是质子交换膜燃料电池(PEMFC)成为规模化实用技术的关键。催化剂的合理设计依赖于对反应机理的深入认识。由于“电极/电解液”界面难以实现超低温与超高真空等条件,因而直接从实验上获得电化学条件下氧还原反应的分子水平信息非常困难。同时,单纯依赖实验技术的“合成—测试”这一传统催化剂筛选模式不仅效率低,而且成本高。建立在以密度泛函理论(DFT)为主的量子化学方法和高性能计算技术基础上的现代计算化学则为分子水平的电催化研究带来契机。基于此,本论文利用DFT计算对Pt电极表面的ORR机理进行了深入研究,在此基础上建立了基于DFT计算设计筛选ORR催化剂的判据,并对贵金属Pt、Pd与元素周期表中各种过渡金属形成的合金的热力学、化学及电子性质进行了详细计算,从而确定有应用前景的ORR催化剂。另外,鉴于CO2的化学转化在解决当前能源和环境问题方面的重要性,我们对CO2的化学与电化学还原过程进行了初步研究。本论文的主要内容和结果总结如下：
1.Pt(111)表面ORR机理的DFT计算研究
利用基于平面波的DFT几何结构优化、电子结构分析和最小能量路径计算等方法研究了氧气分子在Pt表面的吸附和解离、以及解离产物进一步质子化形成H20的过程,结果表明：
(1)ORR中形成了两种类型的分子态化学吸附中间体：质子化的端位(end-on)吸附物OOH*和非质子化的桥式(t-b-t)吸附物OO*。其中端位OOH*中间体为亚稳态,可以在几乎无需活化的情况下经过去质子化过程形成更稳定的桥式吸附态OO*或解离成原子吸附态。也就是说,O2分子的化学吸附过程经历了一个先质子化再去质子化的过程。
(2)在水合质子存在时,02分子的化学吸附是一个强放热过程,其释放的能力足以克服随后的解离过程所需的活化能垒。因此,02分子的解离过程无需外部能量输入。无论是在高覆盖度还是低覆盖度的表面,整个四电子ORR过程的决速步骤是吸附O原子质子化形成OH吸附物的过程。这修正了早期关于ORR决速步骤是OOH*的形成的认识,并解释了为什么氧原子吸附能可以作为ORR催化剂理论设计的依据。
2.基于DFT计算的ORR合金催化剂设计
提出以合金形成能、贵金属表面偏析能和氧原子吸附能作为描述符设计低贵金属含量、高活性和高稳定性ORR合金催化剂的思路。利用DFT计算对Pt.Pd与各种过渡金属形成的合金的热力学、表面化学和电子性质进行了系统研究,在此基础上预测Pt3V、Pt3Fe、Pt3Co、Pt3Ni、Pt3Cu、Pt3Zn、Pt3Mo和Pt3W等Pt基合金,以及Pd3V,Pd3Fe,Pd3Zn,Pd3Nb和Pd3Ta等Pd基合金具有好的ORR催化活性和稳定性。部分结果已有文献报道或经过本实验室的实验验证。
对引起合金ORR催化活性增强的原因进行了探讨,分析了各种合金中晶格收缩效应和配体效应对表面贵金属原子的电子性质的影响。结果表明,晶格收缩使得d-band中心(εd)下移,而配体效应即可以导致d-band中心下移,也可以导致d-band中心的上移。例如,晶格为面心立方且d电子数为10的过渡金属的配体效应会使Pt的εd上移,而晶格为六方晶系且d电子数为10的过渡金属的配体效应则使Pt的劬下移,d电子数小于10的过渡金属的配体效应在大多数情况下使Pt的εd下移。
3.CO2在Cu表面还原为碳氢化合物的DFT计算研究
通过DFT反应能计算和最小能量路径分析研究了气相中C02在Cu(111)和Cu(100)单晶表面的还原过程。结果表明在Cu(111)表面C02还原的可能反应路径为：C02(g)+H*→COOH*→(CO+OH)*、(CO+H)*→CHO*、CHO+H→CH2O*←(CH2+O)*、CH2*+2H*→CH4或2CH2*→C2H4,整个反应由CO2(g)+H*→COOH*→(CO+OH)*,(CO+H)*→CHO*和CH2O*→(CH2+O)术这几个反应步骤共同控制；Cu(100)表面的可能反应路径为：C02(g)→(CO+O)*,(CO+H)*→CHO*,CHO+H→CH2O*→(CH2+O)*,2CH2*→C2H4,整个反应由(CO+H)*→CHO*步骤控制。
计算了不同电极电势下C02电化学还原各步骤的反应能。结果表明在-0.50V(Vs RHE)以正的电势下Cu(111)和Cu(100)表面主要形成HCOO和CO吸附物。随着电势逐渐变负,C02加氢解离形成CO的反应越来越容易,CO成为主要产物。随电势进一步变负,CO的后续加氢反应逐渐变为强放热反应,因而形成碳氢化合物的趋势变强。与CO2的化学还原不同的是,电化学环境下CO质子化形成的CHO中间体倾向于解离形成CH,而在气相中,CHO中间体则倾向于进一步质子化形成CH20中间体。无论在气相中还是电化学环境下,Cu(100)表面更有利于C2H4产物的形成。这与实验的观察结果一致。
Developing catalysts for oxygen reduction reaction(ORR) with low noble metal contents、high catalytic activity and high stability is the key for large-scale application of proton exchange membrane fuel cell (PEMFC). Rational design of catalysts relies on in-depth understanding of ORR mechanism. Since the "electrode/electrolyte" interfaces are mostly inaccessible to low temperature and ultra-high vacuum conditions, it is difficult to experimentally obtain molecular information of ORR with surface-science techniques. At the same time, the traditional "synthesis-test" catalyst searching mode is a rather cost-ineffective process. However, modern computational chemistry based on density functional theory (DFT) and high-performance computing technology offers a novel opportunity for studying electrocatalysis at the molecular level. In this thesis, we have performed detailed DFT calculations studies on the ORR electrocatalysis, including the reaction mechanism and catalysts design. Considering the increasing importance of the chemical transformation of CO2 in the area of energy and environment, we also performed DFT calculations studies on the chemical and electrochemical reduction processes of CO2. The main contents and results are summarized as follows:
1. DFT Study of ORR Mechanism on Pt(111) Surface
The DFT geometric optimization, electronic structure and minimum energy paths calculations have been used to investigate the adsorption and dissociation of O2 molecule, and the protonation of the dissociated adsorbates. The results indicated the following:
(1) Two molecular chemisorbed intermediates are involved in ORR:the protonated end-on state of OOH* and the unprotonated t-b-t state of OO*. The end-on OOH* is metastable, which can transform to the more stable t-b-t molecular state or dissociates to atomic adsorbates in nearly nonactivated processes. That is, O2 may undergo a sequential protonation and de-protonation process in the earlier stage of reduction;
(2) In the presence of the hydrated proton, the chemisorption of O2 molecule is a strong exothermic process, releasing energy larger than the activation energy required for the subsequent dissociation. Therefore, O2 molecule could dissociate without external energy input. In the entire four-electron ORR, the protonation of adsorbed 0 atom to form OH is the slowest step, therefore the rate-determining-step(rds). Such a finding about the rds of ORR can well explain why catalysts that bind atomic oxygen more weakly have better ORR activity, which can not be well accounted for with the earlier view that the rds of ORR is the formation of OOH*.
2. Theoretical design of ORR catalysts based on DFT calculations
In the light of the above reaction mechanism study, we have proposed a multiple-descriptor strategy for rational design of efficient and durable ORR alloy catalysts with low precious metal content. We argued that good alloy catalysts for ORR should simultaneously have negative alloy formation energy, negative surface segregation energy of precious metals and lower oxygen binding strength than pure Pt. By performing detailed DFT calculations on the thermodynamics, surface chemistry and electronic properties of Pt-M and Pd-M alloys (M refers to the non-precious transition metals in periodic table), Pt-based alloys including Pt3V, Pt3Fe, Pt3Co, Pt3Ni, Pt3Cu, Pt3Zn, Pt3Mo, Pt3W and Pd-based alloys including Pd3V, Pd3Fe, Pd3Zn, Pd3Nb, and Pd3Ta were predicted to have improved catalytic activity and durability for ORR, among which some alloys have indeed been reported to have excellent ORR catalytic activity in the literature.
The origins for ORR activity enhancement in these alloys have been analyzed in terms of the lattice compression effect and the ligand effect of the alloying transition metals on the electronic property of surface atoms. The results indicated that the lattice compression leads to downshift of d-band center of surface atoms, while the ligand effect could lead to either downshift or upshift of d-band center depending on the lattice and electronic properties of the transition metals. For metals with face-centered cubic lattice and ten d electrons, the ligand effect causes upshift of d-band center of Pt, while the ligand effect of the transition metals with hexagonal lattice structure and ten d electrons would downshift the d-band center of Pt. For transition metals with less than ten d electrons, the ligand effect mostly results in downshift of the d-band center of Pt.
3. DFT Calculation Study on the Reduction of CO2 to Hydrocarbons on Cu Surfaces
CO2 reduction processes on Cu(111) and Cu(100) single crystal surfaces were studied with DFT calculations on the reaction energy and the minimum energy paths. The results indicated that the possible reaction paths for CO2 reduction on Cu(111) surface are CO2(g)+H*→COOH*→(CO+OH)*, (CO+H)*→CHO*, CHO+H→CH2O*→(CH2+O)*, CH2*+2H*→CH4 or 2CH2*→C2H4, while on Cu(100) surface are CO2(g)→(CO+O)*, (CO+H)*→CHO*, CHO+H→CH2O*→(CH2+O)*,2CH2*→C2H4. On Cu(111) surface, the reaction rate is controlled by steps of CH2O*→(CH2+O)*, CO2(g)+H*→COOH→(CO+OH)* and (CO+ H)*→CHO*, while on Cu(100) surface the rate reaction is controlled by step of (CO +H)*→CHO*.
The reaction energies for various steps in the electrochemical reduction of C02 were calculated under different electrode potentials. The results indicated that HCOO and CO are mainly formed when the potential is more positive than-0.50V (vs.RHE). The hydrogenated dissociation of C02 to form CO and the subsequent hydrogenation of CO become increasingly exothermic as the potential goes negative, so that hydrocarbons gradually becomes the favored products in the electrochemical reduction. Under electrochemical conditions, CHO intermediate prefers to dissociate to form CH, rather than to form CH2O intermediate via protonation as does in gas phase reduction. Agreeing with experimental results, our calculations indicated that is preferably formed on Cu(100) surface.
1.Pt(111)表面ORR机理的DFT计算研究
利用基于平面波的DFT几何结构优化、电子结构分析和最小能量路径计算等方法研究了氧气分子在Pt表面的吸附和解离、以及解离产物进一步质子化形成H20的过程,结果表明：
(1)ORR中形成了两种类型的分子态化学吸附中间体：质子化的端位(end-on)吸附物OOH*和非质子化的桥式(t-b-t)吸附物OO*。其中端位OOH*中间体为亚稳态,可以在几乎无需活化的情况下经过去质子化过程形成更稳定的桥式吸附态OO*或解离成原子吸附态。也就是说,O2分子的化学吸附过程经历了一个先质子化再去质子化的过程。
(2)在水合质子存在时,02分子的化学吸附是一个强放热过程,其释放的能力足以克服随后的解离过程所需的活化能垒。因此,02分子的解离过程无需外部能量输入。无论是在高覆盖度还是低覆盖度的表面,整个四电子ORR过程的决速步骤是吸附O原子质子化形成OH吸附物的过程。这修正了早期关于ORR决速步骤是OOH*的形成的认识,并解释了为什么氧原子吸附能可以作为ORR催化剂理论设计的依据。
2.基于DFT计算的ORR合金催化剂设计
提出以合金形成能、贵金属表面偏析能和氧原子吸附能作为描述符设计低贵金属含量、高活性和高稳定性ORR合金催化剂的思路。利用DFT计算对Pt.Pd与各种过渡金属形成的合金的热力学、表面化学和电子性质进行了系统研究,在此基础上预测Pt3V、Pt3Fe、Pt3Co、Pt3Ni、Pt3Cu、Pt3Zn、Pt3Mo和Pt3W等Pt基合金,以及Pd3V,Pd3Fe,Pd3Zn,Pd3Nb和Pd3Ta等Pd基合金具有好的ORR催化活性和稳定性。部分结果已有文献报道或经过本实验室的实验验证。
对引起合金ORR催化活性增强的原因进行了探讨,分析了各种合金中晶格收缩效应和配体效应对表面贵金属原子的电子性质的影响。结果表明,晶格收缩使得d-band中心(εd)下移,而配体效应即可以导致d-band中心下移,也可以导致d-band中心的上移。例如,晶格为面心立方且d电子数为10的过渡金属的配体效应会使Pt的εd上移,而晶格为六方晶系且d电子数为10的过渡金属的配体效应则使Pt的劬下移,d电子数小于10的过渡金属的配体效应在大多数情况下使Pt的εd下移。
3.CO2在Cu表面还原为碳氢化合物的DFT计算研究
通过DFT反应能计算和最小能量路径分析研究了气相中C02在Cu(111)和Cu(100)单晶表面的还原过程。结果表明在Cu(111)表面C02还原的可能反应路径为：C02(g)+H*→COOH*→(CO+OH)*、(CO+H)*→CHO*、CHO+H→CH2O*←(CH2+O)*、CH2*+2H*→CH4或2CH2*→C2H4,整个反应由CO2(g)+H*→COOH*→(CO+OH)*,(CO+H)*→CHO*和CH2O*→(CH2+O)术这几个反应步骤共同控制；Cu(100)表面的可能反应路径为：C02(g)→(CO+O)*,(CO+H)*→CHO*,CHO+H→CH2O*→(CH2+O)*,2CH2*→C2H4,整个反应由(CO+H)*→CHO*步骤控制。
计算了不同电极电势下C02电化学还原各步骤的反应能。结果表明在-0.50V(Vs RHE)以正的电势下Cu(111)和Cu(100)表面主要形成HCOO和CO吸附物。随着电势逐渐变负,C02加氢解离形成CO的反应越来越容易,CO成为主要产物。随电势进一步变负,CO的后续加氢反应逐渐变为强放热反应,因而形成碳氢化合物的趋势变强。与CO2的化学还原不同的是,电化学环境下CO质子化形成的CHO中间体倾向于解离形成CH,而在气相中,CHO中间体则倾向于进一步质子化形成CH20中间体。无论在气相中还是电化学环境下,Cu(100)表面更有利于C2H4产物的形成。这与实验的观察结果一致。
Developing catalysts for oxygen reduction reaction(ORR) with low noble metal contents、high catalytic activity and high stability is the key for large-scale application of proton exchange membrane fuel cell (PEMFC). Rational design of catalysts relies on in-depth understanding of ORR mechanism. Since the "electrode/electrolyte" interfaces are mostly inaccessible to low temperature and ultra-high vacuum conditions, it is difficult to experimentally obtain molecular information of ORR with surface-science techniques. At the same time, the traditional "synthesis-test" catalyst searching mode is a rather cost-ineffective process. However, modern computational chemistry based on density functional theory (DFT) and high-performance computing technology offers a novel opportunity for studying electrocatalysis at the molecular level. In this thesis, we have performed detailed DFT calculations studies on the ORR electrocatalysis, including the reaction mechanism and catalysts design. Considering the increasing importance of the chemical transformation of CO2 in the area of energy and environment, we also performed DFT calculations studies on the chemical and electrochemical reduction processes of CO2. The main contents and results are summarized as follows:
1. DFT Study of ORR Mechanism on Pt(111) Surface
The DFT geometric optimization, electronic structure and minimum energy paths calculations have been used to investigate the adsorption and dissociation of O2 molecule, and the protonation of the dissociated adsorbates. The results indicated the following:
(1) Two molecular chemisorbed intermediates are involved in ORR:the protonated end-on state of OOH* and the unprotonated t-b-t state of OO*. The end-on OOH* is metastable, which can transform to the more stable t-b-t molecular state or dissociates to atomic adsorbates in nearly nonactivated processes. That is, O2 may undergo a sequential protonation and de-protonation process in the earlier stage of reduction;
(2) In the presence of the hydrated proton, the chemisorption of O2 molecule is a strong exothermic process, releasing energy larger than the activation energy required for the subsequent dissociation. Therefore, O2 molecule could dissociate without external energy input. In the entire four-electron ORR, the protonation of adsorbed 0 atom to form OH is the slowest step, therefore the rate-determining-step(rds). Such a finding about the rds of ORR can well explain why catalysts that bind atomic oxygen more weakly have better ORR activity, which can not be well accounted for with the earlier view that the rds of ORR is the formation of OOH*.
2. Theoretical design of ORR catalysts based on DFT calculations
In the light of the above reaction mechanism study, we have proposed a multiple-descriptor strategy for rational design of efficient and durable ORR alloy catalysts with low precious metal content. We argued that good alloy catalysts for ORR should simultaneously have negative alloy formation energy, negative surface segregation energy of precious metals and lower oxygen binding strength than pure Pt. By performing detailed DFT calculations on the thermodynamics, surface chemistry and electronic properties of Pt-M and Pd-M alloys (M refers to the non-precious transition metals in periodic table), Pt-based alloys including Pt3V, Pt3Fe, Pt3Co, Pt3Ni, Pt3Cu, Pt3Zn, Pt3Mo, Pt3W and Pd-based alloys including Pd3V, Pd3Fe, Pd3Zn, Pd3Nb, and Pd3Ta were predicted to have improved catalytic activity and durability for ORR, among which some alloys have indeed been reported to have excellent ORR catalytic activity in the literature.
The origins for ORR activity enhancement in these alloys have been analyzed in terms of the lattice compression effect and the ligand effect of the alloying transition metals on the electronic property of surface atoms. The results indicated that the lattice compression leads to downshift of d-band center of surface atoms, while the ligand effect could lead to either downshift or upshift of d-band center depending on the lattice and electronic properties of the transition metals. For metals with face-centered cubic lattice and ten d electrons, the ligand effect causes upshift of d-band center of Pt, while the ligand effect of the transition metals with hexagonal lattice structure and ten d electrons would downshift the d-band center of Pt. For transition metals with less than ten d electrons, the ligand effect mostly results in downshift of the d-band center of Pt.
3. DFT Calculation Study on the Reduction of CO2 to Hydrocarbons on Cu Surfaces
CO2 reduction processes on Cu(111) and Cu(100) single crystal surfaces were studied with DFT calculations on the reaction energy and the minimum energy paths. The results indicated that the possible reaction paths for CO2 reduction on Cu(111) surface are CO2(g)+H*→COOH*→(CO+OH)*, (CO+H)*→CHO*, CHO+H→CH2O*→(CH2+O)*, CH2*+2H*→CH4 or 2CH2*→C2H4, while on Cu(100) surface are CO2(g)→(CO+O)*, (CO+H)*→CHO*, CHO+H→CH2O*→(CH2+O)*,2CH2*→C2H4. On Cu(111) surface, the reaction rate is controlled by steps of CH2O*→(CH2+O)*, CO2(g)+H*→COOH→(CO+OH)* and (CO+ H)*→CHO*, while on Cu(100) surface the rate reaction is controlled by step of (CO +H)*→CHO*.
The reaction energies for various steps in the electrochemical reduction of C02 were calculated under different electrode potentials. The results indicated that HCOO and CO are mainly formed when the potential is more positive than-0.50V (vs.RHE). The hydrogenated dissociation of C02 to form CO and the subsequent hydrogenation of CO become increasingly exothermic as the potential goes negative, so that hydrocarbons gradually becomes the favored products in the electrochemical reduction. Under electrochemical conditions, CHO intermediate prefers to dissociate to form CH, rather than to form CH2O intermediate via protonation as does in gas phase reduction. Agreeing with experimental results, our calculations indicated that is preferably formed on Cu(100) surface.
引文
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