Phosphorus-modification of Pt/Al2O3 catalysts improves dispersion and cycloalkane dehydrogenation activity

In this study, we demonstrate that phosphorus-modification of Pt/Al2O3 leads to sinter-stable catalysts with improved activity in the dehydrogenation of perhydro benzyltoluene, an attractive liquid organic hydrogen carrier. TEM images show that platinum nanoparticles are stabilized to a size below 1 nm by the P-modification procedure, while unmodified counterparts show considerable sintering after reduction at 600 °C. The modification procedure starts by a simple impregnation of Pt/Al2O3 with H3PO3, followed by a high temperature treatment above 550 °C. It is crucial to adjust the right P:Pt ratio to reach stabilization of all platinum nanoparticles and thereby high catalytic surface areas. In our dehydrogenation studies, a catalyst with the optimal molar P:Pt ratio of 1.8 shows a 18 % higher activity compared to the unmodified sample. Even after treating the catalyst at temperatures up to 900 °C, this activity boost remains. XPS and XRD measurements prove that Pt stays in its reduced elemental state, also after P-modification, which is essential for a good dehydrogenation activity. The phosphorus species act as an anchor for the Pt particles on the Al2O3 surface, reducing their mobility and preserving small nanoparticles.