The cooperative effect of Co and CoO in Co/CoO enabled efficient catalytic hydrogenation and demethoxylation of guaiacol to cyclohexanol

• Published in: Sustainable energy & fuels Vol. 8; no. 1; pp. 2153 - 2166
• Main Authors: Singh, Bhupendra Pratap, More, Ganesh Sunil, Bal, Rajaram, Srivastava, Rajendra
• Format: Journal Article
• Language: English
• Published: London Royal Society of Chemistry 14.05.2024
• Subjects: Ammonia; Catalysts; Catalytic activity; Catalytic converters; Chemical synthesis; Cobalt oxides; Cyclohexanol; Fine chemicals; Fossil fuels; Guaiacol; Heavy metals; Hydrogenation; Lignin; Nanoparticles; Noble metals; Petrochemicals; Pharmaceutical industry; Phenols
• ISSN: 2398-4902; 2398-4902
• DOI: 10.1039/d4se00183d

The selective catalytic transformations of lignin-derived phenolics into cyclohexanol provide an alternative renewable solution to fine-chemical industries over the fossil-fuel-dependent routes. Herein, low-cost, non-noble metal-based Co/CoO catalysts with oxygen vacancies were prepared by a simple reduction of Co 3 O 4 at 300 °C for 20 minutes. The catalyst was utilized for the hydrogenation and demethoxylation of guaiacol, a lignin model compound, into cyclohexanol, an industrially important compound. Under relatively milder reaction conditions of 170 °C, 2 MPa H 2 pressure and 2 h, 94% conversion of guaiacol with 80% cyclohexanol selectivity was obtained. The catalytic activity of Co/CoO towards hydrogenation and demethoxylation of guaiacol relied on the Co and CoO ratio, which in turn was varied through alteration in the reduction conditions of Co 3 O 4 . Metallic Co nanoparticles growth and its influence on the electronic environment of CoO in Co/CoO catalysts was confirmed using XPS, H 2 -TPD, NH 3 -TPD, and H 2 -TPR techniques. Several phenolics were successfully converted to corresponding cyclohexanols with the developed catalyst. The catalyst was efficiently recycled with no appreciable loss in the activity. The spent catalyst showed similar chemical environments to that of the fresh catalyst. The present work provides useful insights into the simple synthesis of an economical heterogeneous catalyst that can encourage researchers to produce other valuable chemicals and fuels from non-fossil resources under milder conditions required by the petrochemical, fine chemical, and pharmaceutical industries. Guaiacol, a key building block of lignin, which is the intricate glue that holds biomass, was transformed into cyclohexanol, an industrial chemical used as a solvent, nylon precursor, and plasticizer over a Co/CoO catalyst.