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Glucose‐ and Cellulose‐Derived Ni/C‐SO 3 H Catalysts for Liquid Phase Phenol Hydrodeoxygenation
Author(s) -
Kasakov Stanislav,
Zhao Chen,
Baráth Eszter,
Chase Zizwe A.,
Fulton John L.,
Camaioni Donald M.,
Vjunov Aleksei,
Shi Hui,
Lercher Johannes A.
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201405242
Subject(s) - hydrodeoxygenation , catalysis , phenol , cyclohexanol , chemistry , inorganic chemistry , cyclohexane , cellulose , hexadecane , nuclear chemistry , organic chemistry , selectivity
Sulfonated carbons were explored as functionalized supports for Ni nanoparticles to hydrodeoxygenate (HDO) phenol. Both hexadecane and water were used as solvents. The dual‐functional Ni catalysts supported on sulfonated carbon (Ni/C‐SO 3 H) showed high rates for phenol hydrodeoxygenation in liquid hexadecane, but not in water. Glucose and cellulose were precursors to the carbon supports. Changes in the carbons resulting from sulfonation of the carbons resulted in variations of carbon sheet structures, morphologies and the surface concentrations of acid sites. While the C‐SO 3 H supports were active for cyclohexanol dehydration in hexadecane and water, Ni/C‐SO 3 H only catalysed the reduction of phenol to cyclohexanol in water. The state of 3–5 nm grafted Ni particles was analysed by in situ X‐ray absorption spectroscopy. The results show that the metallic Ni was rapidly formed in situ without detectable leaching to the aqueous phase, suggesting that just the acid functions on Ni/C‐SO 3 H are inhibited in the presence of water. Using in situ IR spectroscopy, it was shown that even in hexadecane, phenol HDO is limited by the dehydration step. Thus, phenol HDO catalysis was further improved by physically admixing C‐SO 3 H with the Ni/C‐SO 3 H catalyst to balance the two catalytic functions. The minimum addition of 7 wt % C‐SO 3 H to the most active of the Ni/C‐SO 3 H catalysts enabled nearly quantitative conversion of phenol and the highest selectivity (90 %) towards cyclohexane in 6 h, at temperatures as low as 473 K, suggesting that the proximity to Ni limits the acid properties of the support.