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

Abstract 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 LaO x phase. The resulting Pt/LaO x /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 La 2 O 3 . The interfacial amorphous LaO x 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 LaO x enhanced the dissociation of water, thus enabling the water‐gas shift reaction under mild conditions.