Improved Low-Temperature Hydrogen Production from Aqueous Methanol Based on Synergism between Cationic Pt and Interfacial Basic LaOx

Aqueous phase reforming of methanol (APRM) is simple, inexpensive and provides a high hydrogen gravimetric density of 18.8 wt. %, and so is superior to traditional gas-phase reactions performed at relatively high temperatures. In the present work, the interface between Pt nanoparticles and a TiN support was modified using a highly dispersed amorphous LaOx phase. The resulting Pt/LaOx/TiO(N) exhibited enhanced activity and long-term stability during the APRM reaction under base-free conditions compared with Pt catalysts supported on unmodified TiN or crystalline La2O3. The interfacial amorphous LaOx phase promoted the deposition of small Pt nanoparticles having a narrow size distribution, and also generated electron-deficient Pt. An assessment of kinetic isotope data and theoretical investigations demonstrated that the cationic Pt nanoparticles facilitated the cleavage of O-H and C-H bonds in methanol while the amorphous LaOx enhanced the dissociation of water, thus enabling the water-gas shift reaction under mild conditions.