铂活性位空间结构调控氧还原机理的理论研究★

doi:10.6023/A23050221

摘要/Abstract

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.

关键词: 铂催化剂, 氧还原, 多晶面活性位, 空间结构, 密度泛函理论

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.

Key words: Pt-based catalysts, oxygen reduction reaction, active site on polycrystalline surface, spatial structure, density functional theory

引用此文

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.

Jinjing Liu, Na Yang, Li Li, Zidong Wei. Theoretical Study on the Regulation of Oxygen Reduction Mechanism by Modulating the Spatial Structure of Active Sites on Platinum^★[J]. Acta Chimica Sinica, 2023, 81(11): 1478-1485.

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图/表 6

图1. (a) Pt多低指数晶面模型结构与活性位点分类示意图; 施加应力前后(+3%, 0和–3%)(b)*OOH和*OH自由能间的线性关系图; (c)各类活性位与单一低指数晶面(111)、(100)、(110)上*OOH和*OH自由能分布

Figure 1. (a) Schematic diagram of Pt polycrystalline model and the classification of active sites; (b) the relationship between the ?G*OOH and ?G*OH, and (c) the distribution of ?G*OOH and ?G*OH on the Pt active sites of polycrystalline model with and without strain (+3%, 0 and –3%), compared to the single active site on the pure Pt(111), (100) and (110)

图2. 施加应力(+3%, 0, –3%)前后各活性位的(a) d带中心分布图; d带中心与(b)?G*OOH和(c)?G*OH的关系图; CUS[per site]与(d) ?G*OOH和(e) ?G*OH的关系图

Figure 2. (a) The d-band center (εd); the relationship between the εd and (b) ?G*OOH and (c) ?G*OH; the relationship between the CUS[per site] and (d) ?G*OOH and (e) ?G*OH of the active sites with and without strain (+3%, 0 and –3%)

活性位空间结构	活性位晶面结构	site	CUS[本征]			CUS[交错晶面]	CUS[per site]	∆G_*OOH/eV
平面	Pt(111)	—	3	—	3	3.74	0.80
“平点”	Pt(100)	1	4	—	4	3.77	0.51
	Pt(111)	3	3	—	3	3.95	0.90
	Pt(110)	6	5	—	5	3.53	0.48
“凸点”	Pt(111)-(100)	2	5	4 (100)	3 (111)	4	3.68	0.64
“凸点”	Pt(111)-(110)	4	5	3 (111)	5 (110)	4.33	3.60	0.60
“凹点”	Pt(111)-(110)	8	3	5 (110)	3 (111)	3.67	3.73	0.61
“凹点”	Pt(111)-(100)	9	2	3 (111)	4 (100)	3	3.98	0.97

表1. 活性位结构类型与对应的CUS、*OOH和*OH的自由能

Table 1. The spatial structure of active sites and corresponding CUS, ?G*OOH and ?G*OH

图3. 单活性位催化ORR(4e–)联合机理的吉布斯自由能能变图: (a)类纯晶面“平点”活性位; (b)交错晶面“凸点”和“凹点”活性位; (c)施加 +3%应力前后的site 8和(d)施加–3%应力前后的site 3

Figure 3. The free energy diagram of ORR(4e–) associative mechanism on single active sites: (a) plane active sites, (b) convex and concave active sites, (c) site 8 with and without +3% strain and (d) site 3 with and without –3% strain

图4. 双活性位催化ORR(4e–)解离机理的吉布斯自由能能变图: (a)同类双活性位和(b)异类双活性位

Figure 4. The free energy diagram of ORR(4e–) dissociative mechanism on dual active sites: (a) homogeneous dual active sites and (b) heterogeneous dual active sites

活性位结构类型	site	η_{双活性位-per site}/V	η_单活性位/V	∆η^a/V
活性位结构类型	site	η_{双活性位-per site}/V	“平点”	“凸点”	“凹点”
“平点-凸点”	12	0.54	0.72	0.59	—	–0.05
	23	0.48	0.64	0.59	—	–0.11
	34	0.51	0.64	0.63	—	–0.12
	46	0.71	0.75	0.63	—	0.08
“平点-凹点”	68	0.49	0.75	—	0.62	–0.13
“平点-凹点”	91	0.27	0.72	—	0.46	–0.19

表2. 异类双活性位结构类型与对应的理论过电位η

Table 2. The spatial structure of heterogeneous dual active sites and corresponding theoretical overpotential η

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