NO hydrogenation to NH<sub>3</sub> over FeCu/TiO<sub>2</sub> catalyst with improved activity

doi:10.1007/s11705-023-2364-2

Front. Chem. Sci. Eng.

2023, Vol. 17

Issue (12) : 1973-1985 https://doi.org/10.1007/s11705-023-2364-2

RESEARCH ARTICLE

NO hydrogenation to NH₃ over FeCu/TiO₂ catalyst with improved activity

Dan Cui¹, Yanqin Li¹, Keke Pan¹, Jinbao Liu¹, Qiang Wang¹, Minmin Liu¹, Peng Cao¹, Jianming Dan¹, Bin Dai¹, Feng Yu^1,²(

)

¹. Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, School of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832003, China
². Carbon Neutralization and Environmental Catalytic Technology Laboratory, Bingtuan Industrial Technology Research Institute, Shihezi University, Shihezi 832003, China

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Abstract

Ammonia is crucial in industry and agriculture, but its production is hindered by environmental concerns and energy-intensive processes. Hence, developing an efficient and environmentally friendly catalyst is imperative. In this study, we employed a straightforward and efficient impregnation technique to create various Cu-doped catalysts. Notably, the optimized 10Fe-8Cu/TiO₂ catalyst exhibited exceptional catalytic performance in converting NO to NH₃, achieving an NO conversion rate exceeding 80% and an NH₃ selectivity exceeding 98% at atmospheric pressure and 350 °C. We employed in situ diffuse reflectance Fourier transform infrared spectroscopy and conducted density functional theory calculations to investigate the intermediates and subsequent adsorption. Our findings unequivocally demonstrate that Cu doping enhances the rate-limiting hydrogenation step and lowers the energy barrier for NH₃ desorption, thereby resulting in improved NO conversion and enhanced selectivity toward ammonia. This study presents a pioneering approach toward energy-efficient ammonia synthesis and recycling of nitrogen sources.

Keywords NO hydrogenation synthetic ammonia 10Fe-xCu/TiO₂ high selectivity

Corresponding Author(s): Feng Yu

Just Accepted Date: 13 September 2023 Online First Date: 19 October 2023 Issue Date: 30 November 2023

Cite this article:

Dan Cui,Yanqin Li,Keke Pan, et al. NO hydrogenation to NH₃ over FeCu/TiO₂ catalyst with improved activity[J]. Front. Chem. Sci. Eng., 2023, 17(12): 1973-1985.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-023-2364-2
https://academic.hep.com.cn/fcse/EN/Y2023/V17/I12/1973

Fig.1 (a) XRD spectra, (b) EPR spectra, (c) N₂ adsorption-desorption isotherm, and (d) Barrett-Joyner-Halenda pore size distribution curve spectra for the catalysts.

Tab.1 BET specific surface area, pore size and pore volume of the catalysts

Fig.2 TEM and HRTEM images of (a) 10Fe/TiO₂, (b) 10Fe-1Cu/TiO₂, (c) 10Fe-3Cu/TiO₂, (d) 10Fe-5Cu/TiO₂, (e) 10Fe-8Cu/TiO₂, and (f) 10Fe-10Cu/TiO₂ catalysts, and (g) the corresponding element mapping images (Cu, Fe, O, and Ti) of 10Fe-8Cu/TiO₂.

Tab.2 Surface atomic species on the surface of the catalysts

Fig.3 XPS spectra of (a) Fe 2p, (b) Cu 2p, (c) O1s, and (d) Ti 2p for the catalysts.

Fig.4 (a) H₂-TPR and (b) NO-TPD curves of the catalysts.

Fig.5 (a) NO conversion, (b) NH₃ selectivity, (c) NH₃ concentration for the catalysts; (d) the stability test of 10Fe-8Cu/TiO₂ catalyst at 350 °C (Inset: antipoisoning performance of the 10Fe-8Cu/TiO₂ catalyst at 350 °C (5 vol % H₂O, 100 ppm SO₂). Reaction conditions: [NO] = 350 ppm, [H₂] = 2000 ppm, balance N₂, total flow rate: 100 mL·min^–1, GHSV = 38000 h ^–1, catalyst: 0.2 g).

Fig.6 In situ DRIFTS of 10Fe-8Cu/TiO₂ catalyst: (a) adsorption spectra of NO on the catalyst at different temperatures; (b) Co-adsorption spectra of NO + H₂ at different temperatures.

Fig.7 PDOS of NO adsorbed on (a) 10Fe/TiO₂ and (b) 10Fe-8Cu/TiO₂ surfaces; (c, d) the corresponding charge differential density (The pink area represents the accumulation of electrons, and the blue area represents a loss of electrons).

Fig.8 PDOS of NH₃ adsorbed on (a) 10Fe/TiO₂ and (b) 10Fe-8Cu/TiO₂ surfaces; (c, d) the corresponding charge differential density (The pink area represents the accumulation of electrons, and the blue area represents a loss of electrons).

Fig.9 Energy potential and molecular configuration changes of (a) the *NO → *N + *O dissociation process, (b) the *NO + H → *NOH hydrogenation process and (c) the *HNO → *NO + *H dissociation process on the surface of 10Fe/TiO₂ (black) and 10Fe-8Cu/TiO₂ (red) catalysts (The IS, TS and FS are shown in the figure. The numbers in the figure are in units of Angstroms).

Fig.10 Schematic showing the pathway of NO formation on the surface of 10Fe/TiO₂ (black) and 10Fe-8Cu/TiO₂ (red).

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