Asymmetric oxygen vacancies in La2FeMO6 double perovskite for boosting oxygen activation and H2S selective oxidation

doi:10.1016/S1872-2067(24)60051-3

Abstract

Abstract:

Tuning oxygen vacancy (V_O) in metal oxides catalysts that efficiently activates O₂ molecule to promote oxidation reactions remains challenging. Herein, transition metal (M = Mn, Co, and Mo) doping was used to moderate the coordination environment of V_O in La₂FeMO₆ and promote activity for selective oxidation of hydrogen sulfide (H₂S). Various techniques reveal that the introduction of Mn and Co forms the homogeneous double perovskite phase, which results in the formation of asymmetric V_O. Although these asymmetric V_O are more difficult to form than symmetric Fe-V_O-Fe due to the shorter bond distance and stronger bond strength of Fe-O, they are more conducive to the dissociation of O₂ molecules. Among them, the formed rich Fe-V_O-Mn sites from the alternate substitution of Mn to Fe boosted the activation of O₂ molecules of Mn-substituted LaFeO₃. Therefore, enhanced catalytic activity and outstanding sulfur selectivity were achieved as a result of promoted oxygen mobility and reducibility. This work provides an attractive strategy for rational design of advanced oxidation catalysts.

Key words: Double perovskite, Asymmetric oxygen vacancy, O₂ activation, H₂S selective oxidation, Sulfur recovery

Zheng Wei, Guoxia Jiang, Yiwen Wang, Ganggang Li, Zhongshen Zhang, Jie Cheng, Fenglian Zhang, Zhengping Hao. Asymmetric oxygen vacancies in La₂FeMO₆ double perovskite for boosting oxygen activation and H₂S selective oxidation[J]. Chinese Journal of Catalysis, 2024, 62: 198-208.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60051-3

https://www.cjcatal.com/EN/Y2024/V62/I7/198

Figures/Tables 10

Fig. 1. XRD patterns (a) and Raman spectra (b) of LaFe, LaFeMn, LaFeCo and LaFeMo.

Fig. 2. HR-TEM and the corresponding IFFT images of LaFe, LaFeMn, LaFeCo and LaFeMo.

Fig. 3. La 3d (a), Fe 2p (b) and O 1s (c) XPS spectra of LaFe, LaFeMn, LaFeCo and LaFeMo.

Fig. 4. Fe K edge XANES spectra (a) and Fourier transformed (FT) k3-weighted EXAFS spectra (b) of LaFe, LaFeMn and LaFeCo.

Fig. 5. 57Fe M?ssbauer spectra fitting results of LaFe (a), LaFeMn (b), LaFeCo (c) and LaFeMo (d). The solid lines show the curve fits to the raw data.

Table 1 57Fe M?ssbauer spectra results of LaFe, LaFeMn, LaFeCo and LaFeMo.

Catalyst	IS (mm s^‒1)^a	QS (mm s^‒1)^b	H_in (kOe) ^c	P (%) ^d	Fe state
LaFe	(a) 0.18	0.99	—	4.5	small particle
LaFe	(b) 0.37	‒0.03	514.5	95.5	Fe³⁺ (Oh, Fe-O-Fe)
LaFeMn	(a) 0.35	0.52	—	100	Fe³⁺ (Oh, Fe-O-Mn) and small particle
LaFeCo	(a) 0.33	0.44	—	49.4	Fe³⁺ (Oh, Fe-O-Co) and small particle
	(b) 0.36	‒0.03	490.8	19.4	Fe³⁺ (Oh, Fe-O-Fe)
	(c) 0.77	‒0.88	249.6	31.2	Fe³⁺ (Oh, Fe-Co random)
LaFeMo	(a) 0.29	1.01	—	11.0	small particle
LaFeMo	(b) 0.37	‒0.03	502.1	89.0	Fe³⁺ (Oh, Fe-O-Fe)

Fig. 6. (a) O2 desorption profiles in O2-TPD. H2 consumption (b) and O2 desorption profiles (c) in H2-TPR of LaFe, LaFeMn, LaFeCo and LaFeMo.

Fig. 7. Adsorption (a) and dissociation state (b) of O2 molecule on constructed LaFeO3 (110) slabs with VO. (c) Dissociation state of O2 molecule on constructed La2FeMnO6 (110) slabs with VO.

Fig. 8. H2S conversion (a), sulfur selectivity (b) and sulfur yield (c) for H2S oxidation of LaFe, LaFeMn, LaFeCo and LaFeMo.

Fig. 9. Effects of GHSV (a), H2S/O2 (b) molar ratio and H2O content (c) on the catalytic performance of LaFeMn.

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Asymmetric oxygen vacancies in La₂FeMO₆ double perovskite for boosting oxygen activation and H₂S selective oxidation

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