铂活性位空间结构调控氧还原机理的理论研究★
收稿日期: 2023-05-10
网络出版日期: 2023-08-28
基金资助
国家重点研发计划(2021YFA1501000); 国家自然科学基金(52021004)
Theoretical Study on the Regulation of Oxygen Reduction Mechanism by Modulating the Spatial Structure of Active Sites on Platinum★
Received date: 2023-05-10
Online published: 2023-08-28
Supported by
National Key Research and Development Program of China(2021YFA1501000); National Natural Science Foundation of China(52021004)
氧还原反应(ORR)的两个主要中间物种(*OH和*OOH)吸附强度不同且又存在线性比例关系, 导致对*OH和*OOH吸附强度调节的顾此失彼, 即使在最好的Pt催化剂上, ORR理论过电位约有0.45 V, *OH脱附为决速步(PDS). 本工作构建了具有三维空间结构的多低指数晶面Pt(100)-(110)-(111)模型, 多晶面交错形成的凹凸结构上, *OH和*OOH的吸附不再有线性比例关系, 达到同步优化*OH和*OOH吸附强度, 进而实现降低固有过电位的目的. 密度泛函理论计算结果表明, Pt(111)-(100)晶面交错的“凹点”因配位不饱和度最小, 对中间物种的调节最强, 吸附最弱; 同时还可平衡*OOH与*OH吸附强度, 使*O的质子化成为联合机理的PDS; 晶面交错形成的“平点-凹点”双活性位, 可催化解离机理的进行, 过电位可降低至0.27 V. 该策略有望推广到其它具有类似线性比例关系的反应中, 突破顾此失彼的症结, 实现催化活性根本性提高.
刘金晶 , 杨娜 , 李莉 , 魏子栋 . 铂活性位空间结构调控氧还原机理的理论研究★[J]. 化学学报, 2023 , 81(11) : 1478 -1485 . DOI: 10.6023/A23050221
Improving the cathodic oxygen reduction reaction (ORR) activity faces significant challenges due to the linear scaling relationship and disparate adsorption strengths of the intermediate species, *OH and *OOH. This causes the ORR cannot proceed under nearly thermodynamic equilibrium potential, leading to low reaction kinetics compared to the anodic hydrogen oxidation reaction. Even with the use of optimal catalysts like Pt, the theoretical overpotential remains at around 0.45 V, because of the excessively strong *OH adsorption and weak *OOH adsorption, with *OH desorption serving as the potential determining step (PDS). In this study, we aim to enhance the intrinsic catalytic activity of ORR by constructing a three-dimensional spatial geometric structure utilizing a Pt crystalline model with multi-low index surface consisting of (100)-(110)-(111). The density functional theory calculations are employed to investigate the impact of a concave and convex arrangement formed by interlacing polycrystalline surfaces on the adsorption of *OH and *OOH. The results indicate that the investigated spatial configuration can break the linear scaling relationship between *OH and *OOH adsorption and allow for independent optimization of their adsorption strengths, thereby reducing the originally theoretical overpotential. The adsorption of intermediates reveals that the coordination unsaturation of active sites can be utilized as an indicator of the effect of the spatial geometric structure on species adsorption. The adsorption strength of the active site spatial structure follows the order of “concave”<“convex”≤“flat”, with the concave sites of Pt(111)-(100) exhibiting the most optimal adsorption strength for both *OH and *OOH. The 4e– associative mechanism on single sites further reveals that the concave active sites located at Pt(111)-(100) play a significant role in independently regulating the adsorption of intermediate species and show higher catalytic activity than Pt model with single-low index surface. This is due to the minimal coordination unsaturation, which allows for a balance of *OOH and *OH adsorption strengths and then regulates the protonation of *O as the PDS. On the other hand, the 4e– dissociative mechanism demonstrates that dual active sites can further enhance intrinsic catalytic activity compared to single active sites. Specifically, the “flat-concave” dual active sites at Pt(111)-(100) are shown to significantly reduce the theoretical overpotential to 0.27 V. This polycrystalline faceted catalyst with a concave-convex spatial structure is highly promising for use in other reactions that require the selective modulation of multispecies adsorption and the enhancement of intrinsic catalytic activity, particularly those that exhibit a linear scaling relationship.
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