Comprehensive understanding of sulfide oxidation on α-Ag2WO4 (110) surface: A DFT study on ROS storm-driven catalytic mechanism

doi:10.1016/S1872-2067(26)65115-7

Abstract

Abstract:

Understanding how metal oxide surfaces generate and manage reactive oxygen species (ROS) is fundamental to catalytic oxidation; however, the precise nature of active sites and reaction mechanisms remains poorly understood at the molecular level. Herein, using density functional theory calculations, we identify a novel reaction mechanism for the complete activation pathways of O₂, H₂O, and H₂O₂ to generate ROS—¹O₂, ·O₂^-, ·OH, and ·OOH—on the α-Ag₂WO₄ (110) surface. We demonstrate that undercoordinated surface silver cations act as active sites, significantly enhancing adsorption energetics and reducing activation energy barriers. Subsequently, dimethyl sulfide oxidation to sulfoxide and sulfone serves as a benchmark reaction to characterize the free energy profiles of the underlying molecular mechanism, advancing fundamental concepts in the chemistry of the α-Ag₂WO₄ (110) surface. Notably, this surface exhibits exceptional catalytic performance for H₂O₂ activation, achieving the formation of reactive intermediates ¹O₂ and ·OOH via low activation energy barriers. These consecutive stages define the most favorable pathways, where mid-gap states induce the necessary structural and electronic characteristics to stabilize paired- and unpaired-electron intermediates in the first and second steps, respectively. Collectively, these insights provide a theoretical foundation for the adsorption and activation processes governing the ROS regulation mechanism at highly reactive multifunctional surface sites, representing a significant advancement in the field of catalysis.

Key words: ROS generation, Sulfide oxidation, Surface catalysis, DFT study, α-Ag₂WO₄

Felipe Lipsky, Miguel A. San-Miguel, Vicent S. Safont, Mo´nica Oliva, Juan Andr´es. Comprehensive understanding of sulfide oxidation on α-Ag₂WO₄ (110) surface: A DFT study on ROS storm-driven catalytic mechanism[J]. Chinese Journal of Catalysis, 2026, 89: 292-309.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65115-7

https://www.cjcatal.com/EN/Y2026/V89/I10/292

Figures/Tables 7

Fig. 1. (a) Slab model representing the AWO (110) surface. The stoichiometric layer units for layer-resolved DOS projection (1?4) are highlighted. The 23 ? vacuum layer is omitted for clarity. (b) DOS projection; the Fermi level is set to 0 eV. States below 0.25 1/eV are excluded to eliminate spurious states arising from numerical integration artifacts and enhance clarity of relevant features. Bulk structure is retrieved in layers 2 and 3, while layers 1 and 4 show surface effects.

Fig. 2. Adsorption geometries of O2 in its triplet ground state (T1) (a), non-adiabatic Franck-Condon singlet state (S1-FC) (b), and adiabatic singlet state (S1-Adia) (c) on the α-Ag2WO4 (110) surface. Surface Ag-O clusters involved in the adsorption are highlighted. Oxygen atoms for the O2 molecule are depicted in light blue. Side views display spin densities with isosurfaces at 10% of the maximum value; colors distinguish spin-majority and spin-minority channels. (d) Schematic energy diagram along the reaction coordinate, showing the relative energies of T1, S1-FC, and S1-Adia, and indicating the nonadiabatic excitation followed by vibronic relaxation pathways.

Fig. 3. Minimum-energy pathways on α-Ag2WO4(110) for OH formation from H2O (a) and 1O2 formation from bidentate H2O2 (b). The reaction coordinate in (a) corresponds to the distance between the dissociating H atom and the surface O anion. Relative energies are referenced to the clean slab and gas-phase molecules. Adsorbate atoms are colored blue (O) and yellow (H); H-bonds are black. Spin-density isosurfaces (10% of maximum) show an absence of polarization (heterolytic pathway) in (a), contrasting with the distinct spin evolution observed in (b) (homolytic pathway). Spin majority and minority channels are depicted in red and green.

Fig. 4. (a) Gibbs energy profile for the stepwise oxidation of DMS to DMSO and DMSO2 on α-Ag2WO4(110). Energies are referenced to the final activation step in Section 3.2.3 (0 eV). The primary pathway proceeds via an additional H2O2 adsorption and decomposition, while the alternative route (denoted with primes, ‘) involves a second 1O2 molecule for the DMSO → DMSO2 step. (b) Optimized geometries and total magnetic moments (μB) for all intermediates. Atom colors: S (orange), C (brown), O (light blue), H (yellow)

Table 1 Wigner-corrected Eyring rate estimates at T = 323.15 K using calculated ?G?. Steps named after Fig. 4. Imaginary-mode frequencies ν? were used to compute the Wigner tunneling factor.

Step	∆G^‡ (eV)	ν^‡ (cm^-1)	Wigner κ	τ = ln 2/k (s)
6→ 8	0.01	42.9007	1.0015 4.7090 × 10¹²	1.47 × 10^-13
4→ 6	0.17	804.2088	1.5342 2.3058 × 10¹⁰	3.01 × 10^-11
1→ 2	0.52	213.8600	1.0378 5.4266 × 10⁴	1.28 × 10^-5
8→ 10	0.86	385.8300	1.1230 2.9256 × 10^-1	2.37

Table 2 Correlation of electronic descriptors with ROS activation barriers on the α-Ag2WO4 (110) Surface.

Active site system	ϵ_d - E_F (eV)	Work function Φ (eV)	O 2p charge (e)	∆G^† (eV)
H₂O_2(ads)	2.66	6.643	+0.1	0.07
H₂O_(ads)	2.73	5.845	0.0	0.12
O2(ads) (Triplet)	3.01	5.908	0.0	0.86

Table 3 Correlation of electronic descriptors for the sequential DMS oxidation on α-Ag2WO4 (110). IS: initial state; TS: transition state.

Reaction step	State	ϵ_d - E_F (eV)^a	Φ (eV)	Bader q (e)	∆G^† (eV)
DMS → DMSO	IS	3.06	5.751	0.0 (S)	—
	TS	3.45	6.055	-1.20 (O₂)	0.52
DMSO → DMSO₂	IS	3.66	5.641	+1.30 (S)	—
	TS	2.76	5.000	—	0.86

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Comprehensive understanding of sulfide oxidation on α-Ag₂WO₄ (110) surface: A DFT study on ROS storm-driven catalytic mechanism

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