Theoretical Study on the Regulation of Oxygen Reduction Mechanism by Modulating the Spatial Structure of Active Sites on Platinum★

doi:10.6023/A23050221

Abstract

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

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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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Fig. & Tab. 6

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)

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

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

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

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

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

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铂活性位空间结构调控氧还原机理的理论研究^★