钇稳定二氧化锆的抗硫中毒机制研究
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摘要
固体氧化物燃料电池(SOFCs)因具有燃料适应性广、能量转换效率高、零污染、全固态和模块化组装等优点已成为一种很有发展前景的能量转换装置，可用于发电、交通、航空和其他许多领域，被称为21世纪的绿色能源之一。然而燃料中含有的各种各样的含硫污染物，例如H2S等，能够在阳极表面发生反应使阳极产生硫中毒，从而使电池性能丧失，这是燃料电池存在的问题之一。如SOFCs的Ni-YSZ阳极表面常因出现硫中毒现象而失去活性，从而引起人们的关注。本文基于密度泛函理论（DFT）的第一性原理方法，采用VASP计算程序包，结合缀加平面波赝势法、过渡态搜索方法及第一性原理热力学方法，研究了YSZ（111）表面及其富氧表面YSZ+O（111）的抗硫中毒机制。主要进行了以下三方面的工作：
1. H2S在YSZ（111）表面上的吸附
利用基于DFT的第一性原理方法计算了H2S、SH和S原子在YSZ（111）表面上的吸附以及H2S的解离机制。结果表明，H2S和SH被弱束缚在YSZ表面上，而S原子与YSZ表面则有很强的相互作用，被束缚在表面氧原子上与之相结合形成oxido-sulfate（SO2-）物种。过渡态搜索方法分析H2S在YSZ（111）表面的解离表明H2S第一步解离生成SH+H是很容易的，而共吸附的H将阻碍SH的进一步解离。反之，从SH脱氢的反向势垒发现吸附S原子的氢化却是很容易的。由此可知， YSZ（111）表面的硫中毒将受到共吸附的氢的阻碍。
2. H2S在YSZ+O（111）表面上的吸附
在富氧的YSZ+O（111）表面上，H2S和SH均存在着分子吸附和解离吸附两种方式，H2S在YSZ+O（111）表面很容易解离，解离势垒仅有0.5eV，解离的S原子在表面上存在着SO分子和次硫酸根（SO22）两种稳定的吸附种类，这将阻碍燃料氧化的活性位使YSZ+O产生硫中毒。此外利用第一原理热力学方法研究硫中毒的YSZ+O（111）表面再生或去硫化过程得出，可以通过加入O2和H2O等氧化剂的方法，氧化进而除去吸附在表面的硫原子。
3. SO2在YSZ（111）表面的吸附和氧化
首先利用基于密度泛函理论的第一性原理方法研究了SO2与YSZ（111）表面以及富氧的YSZ+O（111）表面的相互作用，研究结果表明：在YSZ（111）表面上，SO2除了分子形式的物理吸附外，还与表面氧离子束缚形成SO32-物种；而在YSZ+O（111）面上，除了上述吸附外，还生成SO3分子和SO42-物种；所有形成的SOx物种（其中x=24）都很强地束缚在YSZ表面上，使表面中毒。最后利用第一原理热力学方法研究了外界环境，例如温度或SO2分压对SO2YSZ/YSZ+O体系的影响。结果表明，在相同的外界条件下，YSZ+O表面比YSZ表面更易于硫中毒。
本文通过研究YSZ（111）表面的硫中毒过程以及再生机制，以期为进一步探究SOFCs工作条件下YSZ表面的抗硫中毒方法提供一定的理论参考。通过SO2和YSZ表面的相互作用分析，我们可以更深入地理解SOFCs阳极材料YSZ部分产生硫中毒的微观机制。
Due to their many advantages in terms of high efficiency, fuel adaptability, all-solid state, modularassembly and low pollution, the solid oxide ruel cells (SOFCs) as a prospective power generation systemhave attracted much attention．SOFCs have been proven useful in industrial, residential, and transportapplications in the past and present, and continue to be developed and improved upon to meet growingenergy demands. However, the YSZ-based anode (Ni/YSZ) for SOFCs is highly susceptible to deactivation(poisoning) by contaminants commonly encountered in readily available fuels, especially sulfur-containingcompounds, which is one of major problems of SOFCs. Using the first-principles method based on densityfunctional theory (DFT) and the Vienna Ab-initio Simulation Package (VASP) package with the projectoraugmented wave (PAW) potential and the Perdewe Burkee Ernzerhof (PBE) functional, in combinationwith the ab initio atomistic thermodynamics method, we study the mechanism for the sulfur tolerant of theYSZ exposure to H2S.
1. The adsorption of H2S on YSZ (111) surface
The adsorption and dissociation of H2S on the yttria-stabilized zirconia (YSZ)(111) surface arestudied using the first-principles methods. It is found that H2S and SH species are bound weakly on theYSZ (111) surface, while the S atom is strongly bound and stably anchored on the O atop of the YSZsurface with the formation of the SO2-fragment. The nudged elastic band (NEB) calculations show that theformation of SH+H from the first dissociation of H2S is very easy, while the presence of a co-adsorbed Hwould inhibit the further dissociation of SH. In contrast, the hydrogenation of the adsorbed sulfur is rathereasy. It is concluded that H could inhibit the formation of sulfur, thus the sulfur poisoning of the YSZsurface would be prevented by co-adsorbed hydrogen.
2. The adsorption of H2S on YSZ+O (111) surface
The strudies from the first-principles method based on DFT show that there exist both molecularadsorption and dissociative adsorption modes for the H2S and SH adsorbed on the YSZ+O (111) surface.For S adsorption, there exist two types of stable species, namely, the SO and the hyposulfite (SO22), whichwill block the active sites for fuel oxidation and result in the poisoning of the YSZ+O surface. The dissociation of H2S is very easy with low energy barriers (~0.5eV), and the dissociative S atoms may resultin the poisoning of the YSZ+O surface. In addition, using the ab initio atomistic thermodynamics method,the surface regeneration or de-sulfurization process of a sulfur-poisoned (i.e. sulfur covered) YSZ+O (111)surface is studied. It is concluded that by introducing oxidizing reagents (e.g. O2and H2O), the adsorbedatomic sulfur can be oxidized to SO2and removed from the YSZ+O surface
3. Adsorption and oxidation of SO2on the YSZ surface
The interaction of SO2with the YSZ (111) and the YSZ+O (111) surfaces is investigated using thefirst-principles method based on DFT. It is found that SO2is adsorbed either as a molecule or a SO2
3species with new S–O bonds to a surface oxygen on the YSZ (111) surface. In addition, there exist otherspecies, e.g., SO3and SO24on the very active YSZ+O (111) surface. All the formed SOxspecies (with x=24) are strongly bound to the surfaces and are of a poisoning nature for the YSZ surfaces. Using the abinitio atomistic thermodynamics method, we present a detailed analysis on the stability of theSO2YSZ/YSZ+O system as a function of the ambient conditions, such as temperature and SO2partialpressure. For example, at the same ambient conditions, the YSZ+O surface is more susceptible to sulfurpoisoning than the YSZ surface
The results from analyzing the sulfurization process of the YSZ (111) upon exposure to H2S and theregeneration mechanism of the sulfur-poisoned surface would be helpful for understanding and furtherexploring sulfur tolerance properties of the YSZ surface under SOFCs operating conditions and searchingfor sulfur tolerant anodes. Through detecting the oxidized species and analyzing of their mutualtransformation in the ambient conditions for SO2adsorption on the YSZ (111) surface, we reach betterunderstanding on the sulfur poisoning mechanism of the YSZ anode of SOFCs.
1. H2S在YSZ（111）表面上的吸附
利用基于DFT的第一性原理方法计算了H2S、SH和S原子在YSZ（111）表面上的吸附以及H2S的解离机制。结果表明，H2S和SH被弱束缚在YSZ表面上，而S原子与YSZ表面则有很强的相互作用，被束缚在表面氧原子上与之相结合形成oxido-sulfate（SO2-）物种。过渡态搜索方法分析H2S在YSZ（111）表面的解离表明H2S第一步解离生成SH+H是很容易的，而共吸附的H将阻碍SH的进一步解离。反之，从SH脱氢的反向势垒发现吸附S原子的氢化却是很容易的。由此可知， YSZ（111）表面的硫中毒将受到共吸附的氢的阻碍。
2. H2S在YSZ+O（111）表面上的吸附
在富氧的YSZ+O（111）表面上，H2S和SH均存在着分子吸附和解离吸附两种方式，H2S在YSZ+O（111）表面很容易解离，解离势垒仅有0.5eV，解离的S原子在表面上存在着SO分子和次硫酸根（SO22）两种稳定的吸附种类，这将阻碍燃料氧化的活性位使YSZ+O产生硫中毒。此外利用第一原理热力学方法研究硫中毒的YSZ+O（111）表面再生或去硫化过程得出，可以通过加入O2和H2O等氧化剂的方法，氧化进而除去吸附在表面的硫原子。
3. SO2在YSZ（111）表面的吸附和氧化
首先利用基于密度泛函理论的第一性原理方法研究了SO2与YSZ（111）表面以及富氧的YSZ+O（111）表面的相互作用，研究结果表明：在YSZ（111）表面上，SO2除了分子形式的物理吸附外，还与表面氧离子束缚形成SO32-物种；而在YSZ+O（111）面上，除了上述吸附外，还生成SO3分子和SO42-物种；所有形成的SOx物种（其中x=24）都很强地束缚在YSZ表面上，使表面中毒。最后利用第一原理热力学方法研究了外界环境，例如温度或SO2分压对SO2YSZ/YSZ+O体系的影响。结果表明，在相同的外界条件下，YSZ+O表面比YSZ表面更易于硫中毒。
本文通过研究YSZ（111）表面的硫中毒过程以及再生机制，以期为进一步探究SOFCs工作条件下YSZ表面的抗硫中毒方法提供一定的理论参考。通过SO2和YSZ表面的相互作用分析，我们可以更深入地理解SOFCs阳极材料YSZ部分产生硫中毒的微观机制。
Due to their many advantages in terms of high efficiency, fuel adaptability, all-solid state, modularassembly and low pollution, the solid oxide ruel cells (SOFCs) as a prospective power generation systemhave attracted much attention．SOFCs have been proven useful in industrial, residential, and transportapplications in the past and present, and continue to be developed and improved upon to meet growingenergy demands. However, the YSZ-based anode (Ni/YSZ) for SOFCs is highly susceptible to deactivation(poisoning) by contaminants commonly encountered in readily available fuels, especially sulfur-containingcompounds, which is one of major problems of SOFCs. Using the first-principles method based on densityfunctional theory (DFT) and the Vienna Ab-initio Simulation Package (VASP) package with the projectoraugmented wave (PAW) potential and the Perdewe Burkee Ernzerhof (PBE) functional, in combinationwith the ab initio atomistic thermodynamics method, we study the mechanism for the sulfur tolerant of theYSZ exposure to H2S.
1. The adsorption of H2S on YSZ (111) surface
The adsorption and dissociation of H2S on the yttria-stabilized zirconia (YSZ)(111) surface arestudied using the first-principles methods. It is found that H2S and SH species are bound weakly on theYSZ (111) surface, while the S atom is strongly bound and stably anchored on the O atop of the YSZsurface with the formation of the SO2-fragment. The nudged elastic band (NEB) calculations show that theformation of SH+H from the first dissociation of H2S is very easy, while the presence of a co-adsorbed Hwould inhibit the further dissociation of SH. In contrast, the hydrogenation of the adsorbed sulfur is rathereasy. It is concluded that H could inhibit the formation of sulfur, thus the sulfur poisoning of the YSZsurface would be prevented by co-adsorbed hydrogen.
2. The adsorption of H2S on YSZ+O (111) surface
The strudies from the first-principles method based on DFT show that there exist both molecularadsorption and dissociative adsorption modes for the H2S and SH adsorbed on the YSZ+O (111) surface.For S adsorption, there exist two types of stable species, namely, the SO and the hyposulfite (SO22), whichwill block the active sites for fuel oxidation and result in the poisoning of the YSZ+O surface. The dissociation of H2S is very easy with low energy barriers (~0.5eV), and the dissociative S atoms may resultin the poisoning of the YSZ+O surface. In addition, using the ab initio atomistic thermodynamics method,the surface regeneration or de-sulfurization process of a sulfur-poisoned (i.e. sulfur covered) YSZ+O (111)surface is studied. It is concluded that by introducing oxidizing reagents (e.g. O2and H2O), the adsorbedatomic sulfur can be oxidized to SO2and removed from the YSZ+O surface
3. Adsorption and oxidation of SO2on the YSZ surface
The interaction of SO2with the YSZ (111) and the YSZ+O (111) surfaces is investigated using thefirst-principles method based on DFT. It is found that SO2is adsorbed either as a molecule or a SO2
3species with new S–O bonds to a surface oxygen on the YSZ (111) surface. In addition, there exist otherspecies, e.g., SO3and SO24on the very active YSZ+O (111) surface. All the formed SOxspecies (with x=24) are strongly bound to the surfaces and are of a poisoning nature for the YSZ surfaces. Using the abinitio atomistic thermodynamics method, we present a detailed analysis on the stability of theSO2YSZ/YSZ+O system as a function of the ambient conditions, such as temperature and SO2partialpressure. For example, at the same ambient conditions, the YSZ+O surface is more susceptible to sulfurpoisoning than the YSZ surface
The results from analyzing the sulfurization process of the YSZ (111) upon exposure to H2S and theregeneration mechanism of the sulfur-poisoned surface would be helpful for understanding and furtherexploring sulfur tolerance properties of the YSZ surface under SOFCs operating conditions and searchingfor sulfur tolerant anodes. Through detecting the oxidized species and analyzing of their mutualtransformation in the ambient conditions for SO2adsorption on the YSZ (111) surface, we reach betterunderstanding on the sulfur poisoning mechanism of the YSZ anode of SOFCs.
引文
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