Facile synthesis of ultrafine cobalt oxides embedded into N-doped carbon with superior activity in hydrogenation of 4-nitrophenol

Xiuling Zhang; Na Wang; Longlong Geng; Junna Fu; Hui Hu; Dashuai Zhang; Baoyong Zhu; Jesse Carozza; Haixiang Han

doi:10.1016/j.jcis.2017.11.005

Facile synthesis of ultrafine cobalt oxides embedded into N-doped carbon with superior activity in hydrogenation of 4-nitrophenol

J Colloid Interface Sci. 2018 Feb 15:512:844-852. doi: 10.1016/j.jcis.2017.11.005. Epub 2017 Nov 7.

Authors

Xiuling Zhang¹, Na Wang², Longlong Geng³, Junna Fu², Hui Hu⁴, Dashuai Zhang⁴, Baoyong Zhu⁴, Jesse Carozza⁵, Haixiang Han⁵

Affiliations

¹ Key Laboratory of Coordination Chemistry and Functional Materials in Universities of Shandong, College of Chemistry and Chemical Engineering, De Zhou University, De Zhou 253023, PR China; College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266000, PR China. Electronic address: xlzhang99@126.com.
² College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266000, PR China.
³ Key Laboratory of Coordination Chemistry and Functional Materials in Universities of Shandong, College of Chemistry and Chemical Engineering, De Zhou University, De Zhou 253023, PR China. Electronic address: llgeng@126.com.
⁴ Key Laboratory of Coordination Chemistry and Functional Materials in Universities of Shandong, College of Chemistry and Chemical Engineering, De Zhou University, De Zhou 253023, PR China.
⁵ Department of Chemistry, University at Albany, State University of New York, Albany 12222, USA.

PMID: 29126073
DOI: 10.1016/j.jcis.2017.11.005

Abstract

Design and synthesis of low-cost catalysts with high activity and stability for hydrogenation reactions is an important research area of applied catalysis. In this work, we present a kind of ultrafine cobalt oxides encapsulated by N-doped carbon (donated as CoO_x/CN) as efficient catalysts for hydrogenation of 4-nitrophenol (4-NP) process. The CoO_x/CN was fabricated through a pyrolysis strategy using an N-containing metal-organic framework (Co-MOF) as precursor followed by a fine thermal-treatment. With an optimized pyrolysis temperature of 500 °C, the CoO_x species present as ultrafine particles highly dispersed in the obtained catalyst (CoO_x/CN-500). CoO_x/CN-500 exhibits excellent activity and stability in hydrogenation of 4-NP at ambient conditions. The activity is much higher than that of not only bulk cobalt oxides, but also carbon supported CoO_x catalysts. It could be used for more than 8 times without obvious fading in activity. In addition, the concrete role of Co-MOF precursor and pyrolysis condition in the catalyst design was investigated in detail. The interaction between organic ligands and Co ions and the confinement of the crystalline structure of Co-MOF could restrain the aggregation of Co ions during pyrolysis and lead to high dispersion of ultrafine CoO_x species. Meanwhile, the N-containing ligands could be transformed into doped N species (pyridinic and pyrrolic N), endowing the CoO_x species with high electron density and promoting the formation of active sites for the hydrogenation reaction.

Keywords: Cobalt oxides; Hydrogenation reaction; Metal-organic frameworks; N-doped carbon.