密度泛函理论研究无水环境下铂基催化剂上氧还原反应活性位点和反应机制

doi:10.1016/S1872-2067(22)64125-1

摘要/Abstract

摘要：

2050‒2060年实现碳净零排放已经成为世界上很多国家的战略使命. 为实现该目标, 氢燃料电池将在汽车燃料方面发挥重要作用. 虽然客运燃料电池电动汽车已经成功推出, 但其广泛应用仍是一个挑战, 主要是因为质子交换膜燃料电池的铂阴极氧还原反应动力学过于缓慢. 理论上, 提高氢燃料电池的运行温度有助于改善氧还原反应动力学, 例如低温质子交换膜燃料电池的工作温度在80 °C, 如果反应活性位点和反应机制不变, 将操作温度提升到120 °C就可以使反应速率提高一个数量级. 但是在实际应用过程中, 目前最先进的高温质子交换膜燃料电池的性能仍然低于低温质子交换膜燃料电池的性能. 为了进一步提高高温质子交换膜燃料电池的性能, 研究人员在优化质子交换膜、电解质、催化剂结构、纳米颗粒的稳定性等方面开展了大量的研究工作并取得了显著进展, 但对活性位点和反应机制仍缺乏了解. 虽然已知高温质子交换膜燃料电池中的铂催化剂在温度高于100 °C的无水条件下的活性位点和氧还原机制可能与低温质子交换膜燃料电池的不同, 但以往研究并没有从原子尺度上获得相关的认识.

本文结合平整的Pt(111)表面上以及含有(110)和(100)型台阶的Pt(332)和Pt(322)台阶表面上的氧还原反应, 采用密度泛函理论计算研究了无水条件下铂基催化剂的氧还原反应的活性位点和催化机理. 结合反应自由能和表面相图, 发现在典型的氧还原反应电位下, Pt(111), Pt(332)和Pt(322)表面上分别集聚0.25, 0.2和0.4 ML的氧原子. 与有水环境下Pt(111)平台面的氧还原反应不同, 由于无水条件下平台面上O^*的聚集, 使得氧还原中间体的吸附减弱, 过电势远大于实验值. 此外氧的聚集会增加O₂的解离势垒, 这些都表明平台面在无水环境下不是氧还原反应的活性位. 虽然台阶边缘位置在有水环境下不是氧还原反应的活性位, 但是理论计算表明, 它们是无水环境下的活性位点. 这是因为台阶边缘的存在能稳定O₂的吸附, 促进O₂的解离势垒. 独特O聚集构型的(110)型台阶边缘尤其如此: 与0.25 ML O集聚的Pt(111)表面相比, O₂的吸附能增强了0.36 eV, O₂的解离势垒降低了0.32 eV, 反应过电势为0.38 V. 综上, 本文研究为设计具有更高性能的高温质子交换膜燃料电池的氧还原催化剂提供了理论指导.

关键词: 氧还原反应, 活性位, 无水环境, 高温质子交换膜燃料电池, 密度泛函理论

Abstract:

Identifying active sites and catalytic mechanism of the oxygen reduction reaction under anhydrous conditions are crucial for the development of next generation proton exchange membrane fuel cells (PEMFCs) operated at a temperature > 100 °C. Here, by employing density functional theory calculations, we studied ORR on flat and stepped Pt(111) surfaces with both (110) and (100) type of steps. We found that, in contrast to ORR under hydrous conditions, (111) terrace sites are not active for ORR under anhydrous conditions, because of weakened binding of ORR intermediates induced by O* accumulation on the surface. On the other hand, step edges, which are generally not active for ORR under hydrous conditions, are predicted to be the active sites for ORR under anhydrous conditions. Among them, (110) type step edge with a unique configuration of accumulated O stabilizes O₂ adsorption and facilitates O₂ dissociation, which lead an overpotential < 0.4 V. To improve ORR catalysts in high-temperature PEMFCs, it is desirable to maximize (110) step edge sites that present between two (111) facets of nanoparticles.

Key words: Oxygen reduction, Active site, Anhydrous condition, High-temperature PEMFCs, Density functional theory

刘广东, 邓辉球, 曾振华. 密度泛函理论研究无水环境下铂基催化剂上氧还原反应活性位点和反应机制[J]. 催化学报, 2022, 43(12): 3126-3133.

Guangdong Liu, Huiqiu Deng, Jeffrey Greeley, Zhenhua Zeng. Density functional theory study of active sites and reaction mechanism of ORR on Pt surfaces under anhydrous conditions[J]. Chinese Journal of Catalysis, 2022, 43(12): 3126-3133.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(22)64125-1

https://www.cjcatal.com/CN/Y2022/V43/I12/3126

图/表 6

Fig. 1. Reaction free energy of the associative mechanism and the surface phase diagram on Pt(111) surface. Free energy diagram of ORR without (a) and with (c) O* accumulation on Pt(111) under anhydrous conditions. As a comparison, the reaction free energy on clean Pt(111) under hydrous condition is also given. The red and blue solid lines represent reaction free energy at the potential that all reaction steps are down-hill and at the equilibrium potential (U = 1.23 V), respectively. (b) Surface phase diagram for O adsorption on Pt(111) surface at 126.85 °C.

Fig. 2. Reaction free energy diagram of ORR on Pt(111) with dissociative mechanism under anhydrous conditions. Reaction free energy without (a) and with (b) O* accumulation on the surface.

Fig. 3. Reaction free energy diagram of ORR with associative mechanism and surface phase diagram on stepped Pt(111) surface under anhydrous conditions. Reaction free energy on clean Pt(332) and Pt(322) (a). Surface phase diagram for O adsorption on Pt(332) (b) and Pt(322) (c).

Fig. 4. Reaction free energy diagram of ORR with associative mechanism on O* accumulated stepped Pt(111) surface. Reaction free energy on Pt(332) with 0.2 ML O* accumulation (a) and Pt(322) with 0.4 ML O* accumulation (b).

Fig. 5. Dissociative mechanism on Pt(332) with 0.2 ML O* accumulation (a), Pt(322) with 0.3 ML O accumulation (b) and Pt(322) with 0.4 ML O* accumulation (c) under anhydrous conditions.

Fig. 6. Transition states and dissociation barrier for O2 dissociation on flat and stepped Pt(111) surfaces. Transition states on Pt(111) (a), Pt(332) (c) and Pt(322) (e) without O* accumulation, and Pt(111) with 0.25 ML O* accumulation (b), Pt(332) with 0.2 ML O* accumulation (d) and Pt(322) with 0.4 ML O* accumulation (f). Ea is O2 dissociation barrier. An orange dashed outline indicates a Pt(111)-(2 × 2)-fcc-O structure.

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