Highly efficient hydrogenation of NO to NH3 via a Fe2O3/TiO2 catalyst

doi:10.1016/S1872-2067(24)60251-2

Abstract

Abstract:

Nitrogen oxides (NO_x) present in flue gas are economically renewable N1 resources. Unlike traditional selective catalytic reduction processes that convert NO into N₂, redirecting NO towards the synthesis of value-added NH₃ offers significant practical benefits. In this study, a Ti-based metal-organic framework (Ti-MOF), specifically MIL-125, was utilized as a support for Fe, which was subsequently calcined at 400 °C to produce a Fe₂O₃/TiO₂-MOF catalyst. The resulting catalyst demonstrated exceptional performance, achieving 99% NO conversion and 95% NH₃ selectivity under optimal conditions of 450 °C, 0.1 MPa, and a gas hourly space velocity of 38000 mL g^-1 h⁻¹. Additionally, the catalyst exhibited excellent stability and resistance to water and sulfur. The high efficiency of Fe₂O₃/TiO₂-MOF is attributed to the abundance of Fe²⁺ sites at the reaction temperature, which enhances NO adsorption and activation. Furthermore, density functional theory calculations suggest that NO undergoes hydrogenation at the N-terminus on the Fe₂O₃/TiO₂-MOF surface, leading directly to NH₃ synthesis rather than dissociation followed by hydrogenation. This catalyst presents a novel approach for converting NO_x into high-value chemical products.

Key words: Nitrogen oxides, Synthetic ammonia, NO hydrogenation, Selective catalytic reduction, Denitration

Yanqin Li, Wenlong Wang, Junqi Tian, Dan Cui, Jun Yuan, Bin Fang, Nianliang Yin, Zelong Li, Feng Yu. Highly efficient hydrogenation of NO to NH₃ via a Fe₂O₃/TiO₂ catalyst[J]. Chinese Journal of Catalysis, 2025, 71: 330-339.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60251-2

https://www.cjcatal.com/EN/Y2025/V71/I4/330

Figures/Tables 5

Fig. 1. Catalytic performance of the catalyst. (a) NO conversion. (b) NH3 selectivity of the TiO2-HC, TiO2-MOF, Fe2O3, Fe2O3/TiO2-HC, and Fe2O3/TiO2-MOF catalysts. Stability test (c) and resistance to H2O and SO2 (d) of the Fe2O3/TiO2-MOF catalysts. Reaction conditions: [NO] = 350 ppm, [H2] = 2000 ppm, balance N2, total flow rate: 100 mL min?1, GHSV: 38000 mL g-1 h?1, catalyst: 0.2 g.

Fig. 2. Structural characterization of the catalysts. (a) XRD patterns of the Ti-MOF (MIL-125), TiO2-HC, TiO2-MOF, Fe2O3/TiO2-HC, and Fe2O3/TiO2-MOF catalysts. (b,c) Raman spectra of catalysts at 532 and 325 nm laser. XPS spectra of the Fe 2p (d), O 1s (e), Ti 2p (f). (g) EPR spectra of the TiO2-HC, TiO2-MOF, Fe2O3/TiO2-HC, and Fe2O3/TiO2-MOF catalysts. (h) H2-TPR profiles of the TiO2-HC, TiO2-MOF, Fe2O3, Fe2O3/TiO2-HC, and Fe2O3/TiO2-MOF catalysts. (i) Schematic description of the Fe2O3/TiO2 catalyst model.

Fig. 3. NO desorption, NH3 desorption, and characterization of surface species. NO-TPD (a) and NH3-TPD (b) curves of the TiO2-HC, TiO2-MOF, Fe2O3, Fe2O3/TiO2-HC, and Fe2O3/TiO2-MOF catalysts after treatment with H2 at 450 °C. In situ DRIFTS spectra of the Fe2O3/TiO2-MOF catalyst: (c) adsorption spectra of NO on the catalyst at different temperatures; (d) Co-adsorption spectra of NO-H2 gas at different temperatures.

Fig. 4. DFT calculations. (a,b) Partial density of states (PDOS) of NO and NH3 adsorbed at the surface of Fe2O3/TiO2. (c,d) Corresponding charge differential density. The pink area represents the accumulation of electrons; the blue area represents the loss of electrons. (e) Energy potential and molecular configuration changes during the (I) *NO → *N + *O dissociation, (II) *NO + H → *NOH hydrogenation, and (II) *HNO → *NO + *H processes. The initial state (IS), transition state (TS), and final state (FS) are shown. The units of the values in the images are in Angstrom (?).

Fig. 5. Reaction path calculation. Possible pathway of NO hydrogenation to NH3 using the Fe2O3/TiO2 catalyst.

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Highly efficient hydrogenation of NO to NH₃ via a Fe₂O₃/TiO₂ catalyst

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