31 P Solid‐State NMR‐Enabled Development of a Pt/Aluminum Tripolyphosphate Catalyst for Selective C─O Bond Hydrogenolysis of Phenols

ABSTRACT Understanding the active structure of phosphate‐based supports is essential for designing catalysts for selective C─O bond hydrogenolysis. Herein, 31 P solid‐state NMR analysis revealed that the support in our previously reported Pt/Al(PO 3 ) 3 catalyst was actually an aluminum condensed phosphate mixture (ACPM), rather than a single aluminum metaphosphate (AMP) phase, consisting of aluminum metaphosphate (AMP), aluminum cyclohexaphosphate (ACP), and aluminum tripolyphosphate (ATPP), with the ATPP phase located on the catalyst surface. Guided by these findings, a Pt/ATPP catalyst was developed, showing high selectivity for the hydrogenolysis of 4‐heptylphenol to heptylbenzene. Mechanistic studies suggested that the Lewis acid sites on ATPP contribute to the enhanced selectivity by facilitating C─O bond activation, a key step in phenol hydrogenolysis.