Study on Synergistic Modulation of LaMnO3 Electronic Structure and CO Selective Catalytic Reduction Reaction Mechanism via Sr/Fe

doi:10.6023/A25060224

Abstract

This study investigates the reaction mechanisms and anti-poisoning performance associated with Sr/Fe doping in LaMnO₃ perovskite catalysts for CO selective catalytic reduction using density functional theory. The results demonstrate that both Fe single doping and Sr-Fe co-doping significantly enhance the adsorption capacity of CO and NO molecules on the catalyst surface, while Sr single doping inhibits NO adsorption. Fe doping transforms the surface Fe sites into centers of CO oxidative activity, whereas the Mn sites predominantly facilitate NO adsorption. On the surface of LaSrMnFeO₃, CO preferentially reacts with lattice oxygen to produce CO₂, generating oxygen vacancies. Subsequently, NO adsorption leads to the formation of an N₂O₂* intermediate that fills these vacancies, with an activation energy barrier of 0.69 eV, resulting in the formation of an N₂O* intermediate. This gas-phase N₂O* then adsorbs at the Lewis acid sites on the catalyst surface, where its dissociation produces N₂* and surface-adsorbed oxygen. Ultimately, CO and the surface-adsorbed oxygen overcome an activation energy barrier of 0.21 eV, facilitating an oxidation reaction that drives the equilibrium of the N₂O*→N₂*+O* reaction to the right, thereby significantly reducing the accumulation of N₂O* by-products. These findings indicate that the core reaction mechanism for CO-selective catalytic reduction (CO-SCR) on the surface of the LaSrMnFeO₃ catalyst follows the Mars-van Krevelen mechanism, transitioning from a bimodal mechanism to the Mars-van Krevelen mechanism. Notably, the reaction energy barrier for the key rate-controlling step (N₂O*→N₂*+O*) is significantly reduced to 1.64 eV, compared to 1.14 eV for the undoped bimodal reaction mechanism of LaMnO₃. Additionally, the adsorption performance of H₂O and SO₂ on the surface of the LaMnO₃ doping system was investigated. Our findings reveal that Fe single doping effectively enhances the catalyst’s sulfur resistance but exacerbates the irreversible adsorption of H₂O molecules, leading to catalyst poisoning and inactivation. In contrast, the synergistic effect of Sr-Fe co-doping provides excellent resistance to both water and sulfur, thereby offering a theoretical foundation for the design of efficient anti-poisoning perovskite catalysts.

Key words: density functional theory, LaMnO₃, oxygen vacancy, CO-selective catalytic reduction (CO-SCR), Mars-van Krevelen, water and sulfur resistance

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Zhihao Yao, Wei Zhang, Zhaoyi Zhou, Dancong Li, Kaikai Zhang, Tao Liu, Wenkai Hu, Shouan Cheng, Mingxuan Hu, Yujia Liu. Study on Synergistic Modulation of LaMnO₃ Electronic Structure and CO Selective Catalytic Reduction Reaction Mechanism via Sr/Fe[J]. Acta Chimica Sinica, 2026, 84(1): 30-42.

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Fig. & Tab. 17

Figure 1. Schematic diagram of LaMnO3 doping architecture model

Figure 2. Adsorption configuration of CO on the surface of LaMnO3 doped system

	d_C-O/nm	d_C-metal/nm	E_ads/eV
LaMnO₃-CO-Mn₀₁	0.114	0.211	–0.35
LaSrMnO₃-CO-Mn₀₁	0.114	0.207	–0.44
LaMnFeO₃-CO-Mn₁	0.114	0.202	–0.43
LaMnFeO₃-CO-Mn₂	0.114	0.202	–0.43
LaMnFeO₃-CO-Mn₃	0.114	0.212	–0.30
LaMnFeO₃-CO-Fe	0.116	0.175	–0.85
LaSrMnFeO₃-CO-Mn₁	0.114	0.202	–0.49
LaSrMnFeO₃-CO-Mn₂	0.114	0.202	–0.41
LaSrMnFeO₃-CO-Mn₃	0.114	0.208	–0.31
LaSrMnFeO₃-CO-Fe	0.116	0.174	–0.63

Table 1. Adsorption energy and bond length of CO on the surface of LaMnO3 doped system

	Q(Sr)/e	Q(Fe)/e	Q(C)/e	Q(O)/e	Q(Mn/Fe)/e	ΔQ_CO/e
LaMnO₃-CO	—	—	–0.292	0.246	–1.659	–0.046
LaSrMnO₃-CO	–1.659	—	–0.061	0.022	–1.710	–0.039
LaMnFeO₃-CO	—	–1.364	–0.120	0.238	–1.544	0.118
LaSrMnFeO₃-CO	–1.660	–1.436	–0.126	0.236	–1.608	0.110

Table 2. Bader charge for optimal CO adsorption configuration of LaMnO3 doping system

Figure 3. Differential charge density of the most stable adsorption configuration of CO on the surface of LaMnO3 doped system (a) LaMnO3; (b) LaMnFeO3; (c) LaSrMnO3; (d) LaSrMnFeO3.

Figure 4. Local charge density map of the most stable adsorption configuration of CO on the surface of LaMnO3 doped system (a)LaMnO3; (b) LaSrMnO3; (c) LaMnFeO3; (d) LaSrMnFeO3.

Figure 5. PDOS of CO on the optimal adsorption configuration of LaMnO3 doped system (a) LaMnO3; (b) LaSrMnO3; (c) LaMnFeO3; (d) LaSrMnFeO3.

Figure 6. Adsorption configuration of NO on the surface of LaMnO3 doped system (a) LaMnO3, (b) LaSrMnO3, (c) LaMnFeO3, (d) LaSrMnFeO3.

	d_N-O/nm	d_N-metal/nm	E_ads/eV
LaMnO₃-NO-Mn₀₁	0.118	0.165	–1.88
LaSrMnO₃-NO-Mn₀₁	0.117	0.163	–1.76
LaMnFeO₃-NO-Mn₁	0.117	0.164	–1.93
LaMnFeO₃-NO-Mn₂	0.117	0.165	–1.93
LaMnFeO₃-NO-Mn₃	0.117	0.164	–1.83
LaMnFeO₃-NO-Fe	0.117	0.172	–1.85
LaSrMnFeO₃-NO-Mn₁	0.117	0.164	–1.79
LaSrMnFeO₃-NO-Mn₂	0.117	0.164	–1.78
LaSrMnFeO₃-NO-Mn₃	0.117	0.163	–1.74
LaSrMnFeO₃-NO-Fe	0.116	0.163	–1.54

Table 3. Adsorption energy and bond length of NO on the surface of LaMnO3 doped system

Figure 7. Differential charge density of the most stable adsorption configuration of NO on the surface of LaMnO3 doped system (a) LaMnO3; (b) LaSrMnO3; (c) LaMnFeO3; (d) LaSrMnFeO3.

Figure 8. Local charge density map of the most stable adsorption configuration of NO on the surface of LaMnO3 doped system (a) LaMnO3; (b) LaSrMnO3; (c) LaMnFeO3; (d) LaSrMnFeO3.

	Q(Sr)/e	Q(Fe)/e	Q(N)/e	Q(O)/e	Q(Mn)/e	ΔQ_NO/e
LaMnO₃-NO	—	—	0.112	0.135	–1.636	0.245
LaSrMnO₃-NO	–1.664	—	0.106	0.126	–1.634	0.226
LaMnFeO₃-NO	—	–1.601	0.110	0.146	–1.641	0.256
LaSrMnFeO₃-NO	–1.658	–1.591	0.148	0.101	–1.698	0.249

Table 4. Bader charge for optimal NO adsorption configuration of LaMnO3 doping system

Figure 9. PDOS of NO on the optimal adsorption configuration of LaMnO3 doped system (a) LaMnO3; (b) LaSrMnO3; (c) LaMnFeO3; (d) LaSrMnFeO3.

Figure 10. Reaction activation energy barrier diagram related to CO oxidation process (a) NO*+CO*→N*+CO2*; (b) NO*→N*+O*; (c) CO*+O*→CO2; (d) CO*+OL→CO2+OV.

Figure 11. Activation energy barrier and optimization structure of reaction step of N2 generation on LaSrMnFeO3 catalyst

Figure 12. Adsorption energy and adsorption configuration of SO2 and H2O on the surface of LaMnO3 doped system (a) LaMnO3; (b) LaSrMnO3; (c) LaMnFeO3; (d) LaSrMnFeO3.

Figure 13. Path diagram of the main CO-SCR reaction surface of LaSrMnFeO3 catalyst

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Sr/Fe协同调控LaMnO₃电子结构及CO选择性催化还原反应机理研究

Study on Synergistic Modulation of LaMnO₃ Electronic Structure and CO Selective Catalytic Reduction Reaction Mechanism via Sr/Fe

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Sr/Fe协同调控LaMnO3电子结构及CO选择性催化还原反应机理研究