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Hydrogenation of lignin-derived phenol to KA oil (the mixture of cyclohexanone (K) and cyclohexanol (A)) is attractive yet challenging in the sustainable upgrading of biomass derivatives under mild conditions. Traditional supported metal catalysts have been widely studied but the active components on supports often exhibit low recyclability due to their instability under experimental conditions. Here we show fabricating ultrasmall Pt/NiO in the pores of chromium terephthalate MIL-101 as catalysts for hydrogenation of phenol. Impressively, Pt/NiO@MIL-101 achieves catalytic phenol hydrogenation to KA oils of tunable K/A ratios and good reusability under room temperature and atmospheric hydrogen pressure, superior to contrast Pt@MIL-101 and Pt/NiO samples. Such excellent performance mainly originates from the effective adsorption and activation of phenol by coordinatively unsaturated Cr sites and H2 activation on ultrasmall Pt/NiO as well as its effective spillover to the adsorbed phenol over Cr sites for hydrogenation reaction. Substantially, such catalyst also displays the excellent performances for hydrogenation of phenol’s derivatives under mild conditions.
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