On the monolayer dispersion behavior of Co<sub>3</sub>O<sub>4</sub> on HZSM-5 support: designing applicable catalysts for selective catalytic reduction of nitrogen oxides by ammonia

doi:10.1007/s11705-023-2332-x

Front. Chem. Sci. Eng.

2023, Vol. 17

Issue (11) : 1741-1754 https://doi.org/10.1007/s11705-023-2332-x

RESEARCH ARTICLE

On the monolayer dispersion behavior of Co₃O₄ on HZSM-5 support: designing applicable catalysts for selective catalytic reduction of nitrogen oxides by ammonia

Yufeng Yang¹, Lihong Zhang¹, Tao Song¹, Yixing Huang¹, Xianglan Xu¹, Junwei Xu¹, Xiuzhong Fang¹, Qing Wang², Haiming Liu², Xiang Wang¹(

)

¹. Key Laboratory of Jiangxi Province for Environment and Energy Catalysis, School of Chemistry and Chemical Engineering, Nanchang University, Nanchang 330031, China
². Shanghai Tech University, School of Physical Science & Technology, Shanghai 201210, China

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Abstract

Based on monolayer dispersion theory, Co₃O₄/ZSM-5 catalysts with different loadings have been prepared for selective catalytic reduction of nitrogen oxides by ammonia. Co₃O₄ can spontaneously disperse on HZSM-5 support with a monolayer dispersion threshold of 0.061 mmol 100 m^–2, equaling to a weight percentage around 4.5%. It has been revealed that the quantities of surface active oxygen (O₂^–) and acid sites are crucial for the reaction, which can adsorb and activate NO_x and NH₃ reactants effectively. Below the monolayer dispersion threshold, Co₃O₄ is finely dispersed as sub-monolayers or monolayers and in an amorphous state, which is favorable to generate the two kinds of active sites, hence promoting the performance of ammonia selective catalytic reduction of nitrogen oxide. However, the formation of crystalline Co₃O₄ above the capacity is harmful to the reaction performance. 4% Co₃O₄/ZSM-5, the catalyst close to the monolayer dispersion capacity, possesses the most abundant active O₂^– species and acidic sites, thereby demonstrating the best reaction performance in all the samples. It is proposed the optimal Co₃O₄/ZSM-5 catalyst can be prepared by loading the capacity amount of Co₃O₄ onto HZSM-5 support.

Keywords Co₃O₄/ZSM-5 NO_x-SCR by NH₃ monolayer dispersion threshold effect surface acid sites surface active O₂^– anions

Corresponding Author(s): Xiang Wang

About author:

Peng Lei and Charity Ngina Mwangi contributed equally to this work.

Online First Date: 26 September 2023 Issue Date: 25 October 2023

Cite this article:

Yufeng Yang,Lihong Zhang,Tao Song, et al. On the monolayer dispersion behavior of Co₃O₄ on HZSM-5 support: designing applicable catalysts for selective catalytic reduction of nitrogen oxides by ammonia[J]. Front. Chem. Sci. Eng., 2023, 17(11): 1741-1754.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-023-2332-x
https://academic.hep.com.cn/fcse/EN/Y2023/V17/I11/1741

Fig.1 (a) XRD patterns of Co₃O₄/ZSM-5 catalysts; (b) extrapolated Co₃O₄ monolayer dispersion threshold on HZSM-5 zeolite.

Fig.2 XPS spectra of Co₃O₄/ZSM-5 catalysts. (a) Si 2p, (b) Al 2p (c) Co 2p, and (d) Co₃O₄ dispersion threshold on HZSM-5 obtained by the XPS extrapolation method.

Fig.3 The ¹H MAS NMR spectra of the catalysts.

Fig.4 (a) NO_x conversion over Co₃O₄/ZSM-5 catalysts, (b) N₂ and N₂O concentrations over Co₃O₄/ZSM-5 catalysts, (c) NO_x conversion rates (R_w and R_s) at 400 °C, and (d) stability test of 4% Co₃O₄/ZSM-5 with H₂O or/and SO₂ at 450 °C.

Fig.5 NO oxidation on Co₃O₄/ZSM-5 catalysts (reaction condition: [NO] = 500 ppm, [O₂] = 5 vol %, and weight hourly space velocity (WHSV) = 30000 mL·h^–1·g^–1).

Fig.6 NH₃ oxidation on (A) HZSM-5, (B) 4% Co₃O₄/ ZSM-5 (dotted line for NH₃ conversion) (reaction condition: [NH₃] = 500 ppm, [O₂] = 5 vol %, and WHSV = 30000 mL·h^–1·g^–1).

Tab.1 Quantified surface acidic sites of the catalysts determined by pyridine-IR experiments

Fig.7 Pyridine-IR spectra of different catalysts. (A) Pyridine adsorption at 50 °C, and (B) pyridine adsorption on 4% Co₃O₄/ZSM-5 at different temperature.

Fig.8 (A) H₂-TPR investigation of Co₃O₄/ZSM-5, and (B) O₂-TPD profiles of Co₃O₄/ZSM-5.

Tab.2 Quantified H₂-TPR and O₂-TPD results of Co₃O₄/ZSM-5

Fig.9 (a) EPR spectra of Co₃O₄/ZSM-5, (b) XPS O 1s spectra of Co₃O₄/ZSM-5, and (c) NO_x conversion at 400 °C versus surface O₂^–/O^2– ratio.

Tab.3 Surface oxygen properties of Co₃O₄/ZSM-5 measured by XPS

Fig.10 In situ DRIFT spectra of 4% Co₃O₄/ ZSM-5 catalyst in a 50 mL·min^–1 500 ppm NO + 500 ppm NH₃ + 5% O₂/Ar flow. (a) At 200 °C; (b) at 200–500 °C.

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