Synthesis of tetrahedrally coordinated CoO for higher alcohol synthesis directly from syngas

doi:10.1007/s11705-024-2448-7

Front. Chem. Sci. Eng.

2024, Vol. 18

Issue (8) : 92 https://doi.org/10.1007/s11705-024-2448-7

Synthesis of tetrahedrally coordinated CoO for higher alcohol synthesis directly from syngas

Zhuoshi Li^1,², Han Yang¹, Xiaofeng Pei¹, Jiahui Li¹, Jing Lv^1,³, Shouying Huang^1,³, Yue Wang^1,^2,³(

), Xinbin Ma^1,³

¹. Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
². Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou 350207, China
³. Haihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, China

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Abstract

Higher alcohol synthesis directly from syngas is highly desirable as one of the efficient non-petroleum energy conversion routes. Co⁰–CoO catalysts showed great potential for this reaction, but the alcohol selectivity still needs to be improved and the crystal structure effect of CoO on catalytic behaviors lacks investigation. Here, a series of tetrahedrally coordinated CoO polymorphs were prepared by a thermal decomposition method, which consisted of wurtzite CoO and zinc blende CoO with varied contents. After diluting with SiO₂, the catalyst showed excellent performance for higher alcohol synthesis with ROH selectivity of 45.8% and higher alcohol distribution of 84.1 wt % under the CO conversion of 38.0%. With increasing the content of wurtzite CoO, the Co⁰/Co²⁺ ratio gradually increased in the spent catalysts, while the proportion of highly active hexagonal close packed cobalt in Co⁰ decreased, leading to first decreased then increased CO conversion. Moreover, the higher content of zinc blende CoO in fresh catalyst facilitated the retention of more Co²⁺ sites in spent catalysts, promoting the ROH selectivity but slightly decreasing the distribution of higher alcohols. The catalyst with 40% wurtzite CoO obtained the optimal performance with a space time yield toward higher alcohols of 7.9 mmol·g_cat^–1·h^–1.

Keywords higher alcohol synthesis CO hydrogenation wurtzite CoO zinc blende CoO hexagonal-closest-packed Co

Corresponding Author(s): Yue Wang

Just Accepted Date: 03 April 2024 Issue Date: 12 July 2024

Cite this article:

Zhuoshi Li,Han Yang,Xiaofeng Pei, et al. Synthesis of tetrahedrally coordinated CoO for higher alcohol synthesis directly from syngas[J]. Front. Chem. Sci. Eng., 2024, 18(8): 92.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-024-2448-7
https://academic.hep.com.cn/fcse/EN/Y2024/V18/I8/92

Fig.1 XRD patterns and the corresponding semiquantitative analysis of the as-prepared xW-CoO polymorphs.

Fig.2 (a–c) TEM images and particle size statistical histograms of the as-prepared xW-CoO polymorphs: (a) 0.4W-CoO, (b) 0.75W-CoO, and (c) 1.0W-CoO; (d–f) corresponding HRTEM images of (a–c).

Fig.3 XRD patterns of the (a) fresh xW-CoO/SiO₂ and (b) spent xW-CoO/SiO₂ catalysts. (c) Slow-scanning XRD of (b) in the range of 2θ = 43°–49° and the corresponding semiquantitative results.

Fig.4 Raman spectra of the (a) xW-CoO nanocrystals, (b) fresh xW-CoO/SiO₂, and (c) spent xW-CoO/SiO₂ catalysts.

Fig.5 (a) Co 2p XPS spectra of the spent xW-CoO/SiO₂ catalysts; (b) H₂-TPR profiles of the fresh xW-CoO/SiO₂ catalysts.

Tab.1 Catalytic performance of the xW-CoO/SiO₂ catalysts^a)

Fig.6 Structure-performance relationship of the xW-CoO/SiO₂ catalysts. (a) The CO conversion, Co⁰ content in total Co species, and hcp-Co content in metallic cobalt of different xW-CoO/SiO₂ catalysts; (b) ROH selectivity, HA distribution in total alcohols, and Co²⁺ content in total Co species. Reaction conditions: P = 3 MPa, T = 260 °C, H₂/CO = 2, and GHSV = 3600 mL·g_cat^–1·h^–1.

Fig.7 (a) High-angle annular dark-field scanning transmission electron microscopy (HADDF-STEM) image, (b–d) the corresponding EDS mapping images, and (e–f) HRTEM images of the spent 0.4W-CoO/SiO₂ catalyst.

Fig.8 CO-TPD-MS profiles of the spent xW-CoO/SiO₂ catalysts.

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