弹性应变对C、H、O在过渡金属氧化物表面吸附的影响

doi:10.15541/jim20240085

摘要/Abstract

摘要：

目前铂(Pt)基贵金属催化剂(PGMs)是应用最广泛的商业催化剂, 但存在成本高、储量低、易引发小分子中毒的问题, 过渡金属氧化物(TMOs)因在氧化环境中具有较好的稳定性和出色的催化性能而被视为PGMs的潜在替代品。本研究通过密度泛函理论(DFT)计算, 全面分析了弹性应变对TMOs表面上碳(C)、氢(H)和氧(O)吸附能的影响。系统探究了这些影响在四方结构(PtO₂、PdO₂)和六方结构(ZnO、CdO)中的作用, 以及它们与各自过渡金属的关系。结果显示, 在金属氧化物表面上, 最有利的吸附位点主要位于氧原子顶部或金属原子顶部, 而过渡金属则更倾向于面心立方(FCC)和六方密排(HCP)的空位。此外, 在弹性应变的影响下, 虽然TMOs和过渡金属对H和O的吸附能存在很大差异, 但弹性应变对TMOs上C、H和O吸附能的影响与过渡金属类似: 在压缩应变下吸附能增加、吸附减弱, 而在拉伸应变下吸附能减小、吸附增强。这种现象可以用基于吸附发生在金属原子顶部时的d带模型或吸附发生在O原子顶部时的p带模型来合理解释。因此, 调控弹性应变也可用于改变TMOs的催化特性。

关键词: 密度泛函理论, 吸附能, 弹性应变工程, 过渡金属氧化物, 催化剂

Abstract:

Platinum (Pt)-based noble metal catalysts (PGMs) are the most widely used commercial catalysts, but they have the problems of high cost, low reserves, and susceptibility to small-molecule toxicity. Transition metal oxides (TMOs) are regarded as potential substitutes for PGMs because of their stability in oxidizing environments and excellent catalytic performance. In this study, comprehensive investigation into the influence of elastic strains on the adsorption energies of carbon (C), hydrogen (H) and oxygen (O) on TMOs was conducted. Based on density functional theory (DFT) calculations, these effects in both tetragonal structures (PtO₂, PdO₂) and hexagonal structures (ZnO, CdO), along with their respective transition metals were systematically explored. It was identified that the optimal adsorption sites on metal oxides pinpointed the top of oxygen or the top of metal atom, while face-centered cubic (FCC) and hexagonal close-packed (HCP) holes were preferred for the transition metals. Furthermore, under the influence of elastic strains, the results demonstrated significant disparities in the adsorption energies of H and O between oxides and transition metals. Despite these differences, the effect of elastic strains on the adsorption energies of C, H and O on TMOs mirrored those on transition metals: adsorption energies increased under compressive strains, indicating weaker adsorption, and decreased under tension strains, indicating stronger adsorption. This behavior was rationalized based on the d-band model for adsorption atop a metallic atom or the p-band model for adsorption atop an oxygen atom. Consequently, elastic strains present a promising avenue for tailoring the catalytic properties of TMOs.

Key words: density functional theory, adsorption energy, elastic strain engineering, transition metal oxide, catalyst

中图分类号:

TQ174

谢天, 宋二红. 弹性应变对C、H、O在过渡金属氧化物表面吸附的影响[J]. 无机材料学报, 2024, 39(11): 1292-1300.

XIE Tian, SONG Erhong. Effect of Elastic Strains on Adsorption Energies of C, H and O on Transition Metal Oxides[J]. Journal of Inorganic Materials, 2024, 39(11): 1292-1300.

图/表 11

Fig. 1 Lateral and top views of (2×2×4) slab models (a) (0001) surface of hexagonal close-packed Zn; (b) (111) surface of face-centered cubic Pt; (c) (0001) surface of hexagonal ZnO; (d) (110) surface of tetragonal PtO2; Surfaces are separated by 15 Å of vacuum; T, B, H, and F stand for top, bridge, HCP hollow, and FCC hollow adsorption sites in (a, b); TO, TM, HO, and B stand for top of O, top of metal, hollow, and metal-oxygen bridge adsorption sites in (c, d) Colorful figures are available on website

Table 1 Adsorption energies and preferred adsorption sites for H, O, and C on TM and TMO

	Zn	Cd	Pd	Pt	ZnO	CdO	PdO₂	PtO₂
$E_{\text{ads}}^{\text{H}}/\text{eV}$	0.63	0.81	-0.57	-0.49	-1.94	-0.69	-2.13	-1.05
Adsorption site (H)	HCP	FCC	FCC	FCC	O top	O top	O top	O top
$E_{\text{ads}}^{\text{O}}/\text{eV}$	-2.41	-2.24	-2.11	-2.16	-0.25	1.17	-0.43	-0.72
Adsorption site (O)	HCP	FCC	FCC	FCC	O top	O top	M top	M top
$E_{\text{ads}}^{\text{C}}/\text{eV}$	-5.04	-4.70	-7.97	-8.39	-8.32	-4.62	-9.86	-5.43
Adsorption site (C)	FCC	FCC	HCP	FCC	O top	O top	M top	M top

Fig. 2 Variation of the adsorption energy under biaxial strain with respect to the unstrained state $E_{\text{ads}}^{\text{X}}(\varepsilon )-E_{\text{ads}}^{\text{X}}(0)$ for different absorbates as a function of the biaxial strain $\varepsilon $ Hexagonal Zn and Cd as well as ZnO and CdO, adsorbed with (a) H, (b) O, and (c) C; Cubic Pd and Pt as well as tetragonal PdO2 and PtO2, adsorbed with (d) H, (e) O and (f) C

Fig. 3 Adsorption energies of strained slabs as a function of the Fermi energy in the strained slab with the corresponding adsorbate (a) H, (b) O and (c) C adsorption on TM; (d) H, (e) O and (f) C adsorption on TMO Empty symbol: adsorption energy without strain; Solid symbol on the left of empty symbol: adsorption energy under biaxial tensile strains; Solid symbol on the right of empty symbol: adsorption energy under biaxial compressive strains

Fig. 4 PDOS onto d orbital of the Pt atom nearest to the C or O adsorbate and PDOS onto p orbital of the O atom nearest to the H adsorbate on the (111) PtO2 surface (a) Unstrained, clean slab and unstrained slab with different adsorbates; (b) Clean slab subjected to different biaxial strains; Slabs with (c) H, (d) O, and (e) C adsorbed and subjected to different biaxial strains; (f) Positions of the d-band center of Pt atom close to the C or O adsorbate and of the p-band center of O atom nearest to the H adsorbate on the (111) PtO2 surfaces subjected to different strains; Energy values are referenced to the Fermi level of the slab; Colorful figures are available on website

Fig. 5 PDOS onto p orbital of the O atom nearest to the H adsorbate on the (110) ZnO surface (a) Unstrained, clean slab and unstrained slab with different adsorbates; (b) Clean slab subjected to different biaxial strains; Slabs with (c) H, (d) O, and (e) C adsorbed and subjected to different biaxial strains; (f) Positions of the p-band of O atom nearest to the adsorbate on the (110) ZnO surfaces subjected to different strains; Energy values are referenced to the Fermi level of the slab; Colorful figures are available on website

Fig. S1 Schematic diagram of the most stable adsorption site (a, b) C adsorbed on Zn surface (a) FCC site and (b) HCP site; (c, d) C adsorbed on Pt surface (c) FCC site and (d) HCP site; (e) The most stable adsorption site for C atom on the ZnO surface; (f, g) C adsorbed on PtO2 surface (f) metal top site and (g) oxygen top site Colorful figures are available on website

Fig. S2 Effect of biaxial elastic strains $\varepsilon $ on adsorption energies of H, O and C on TM and TMO (a) H on TM; (b) O on TM; (c) C on TM; (d) H on TMO; (e) O on TMO; (f) C on TMO

Table S1 Adsorption energy (eV) for H, O, and C on TM

Adsorbate	Zn			Cd			Pd			Pt
Adsorbate	H	O	C	H	O	C	H	O	C	H	O	C
Top metal	0.88	-0.23	-4.33	1.13	-0.19	-2.88	-0.18	-0.77	-6.92	-0.11	-0.48	-6.36
Bridge	0.71	-1.55	-4.57	0.84	-1.69	-3.04	-0.41	-1.65	-7.13	-0.35	-1.76	-7.22
FCC	0.68	-2.26	-5.04	0.81	-2.24	-3.92	-0.57	-2.11	-7.97	-0.49	-2.16	-8.39
HCP	0.63	-2.41	-4.79	0.83	-2.21	-3.85	-0.48	-1.98	-7.63	-0.44	-2.14	-8.13

Table S2 Adsorption energy (eV) and preferred adsorption sites for H, O, and C on TMO

Adsorbate	ZnO			CdO			PdO₂			PtO₂
Adsorbate	H	O	C	H	O	C	H	O	C	H	O	C
M top	1.37	1.91	-6.16	1.68	3.14	-1.12	-0.77	-0.43	-9.86	1.12	-0.72	-5.43
O top	-1.94	-0.25	-8.32	-0.69	1.17	-4.61	-2.13	0.99	-6.45	-1.05	1.03	-2.17
M-O Bridge	-0.13	-0.15	-7.16	1.63	2.17	-3.85	-1.02	0.36	-6.52	0.98	-0.32	-2.22
Hollow	-0.37	-0.22	-8.22	-0.64	1.51	-4.26	-1.35	0.03	-6.88	0.86	-0.66	-2.85

Table S3 Bader charges for selected atoms in ZnO, CdO, PdO2, and PtO2

	ZnO	CdO	PdO₂	PtO₂		ZnO	CdO	PdO₂	PtO₂
Adsorbed O	0.02	-0.41	-0.36	-0.47	Adsorbed O	0.43	-0.07	0.49	0.56
Charge O	-0.47	-0.98	-0.57	-0.71	Charge O	-1.08	-1.07	-0.76	-0.76
Charge M	1.32	1.23	1.68	1.98	Charge M	1.26	1.15	1.62	1.81
Surface O average	-1.03	-1.04	-0.72	-0.83	Surface O average	-1.15	-1.10	-0.85	-0.92
Surface M average	1.26	1.22	1.66	1.93	Surface M average	1.24	1.13	1.50	1.61
$E_{ads}^{O}/eV$	-0.25	1.17	-0.43	-0.72	$E_{ads}^{H}/eV$	-1.94	-0.69	-2.13	-1.05

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