Effect of Elastic Strains on Adsorption Energies of C, H and O on Transition Metal Oxides

doi:10.15541/jim20240085

Abstract

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

CLC Number:

TQ174

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.

Figures/Tables 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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