The enhanced role of surface amination on the catalytic performance of polyacrylonitrile supported palladium nanoparticles in hydrogen generation from formic acid

Hydrogen production by formic acid (FA) has attracted widespread attention in the field of catalysis and energy chemistry. Here, we develop a highly efficient catalyst for FA dehydrogenation by surface amination of polyacrylonitrile (PAN) supported palladium nanoparticles (Pd NPs). The support of PAN derived from a soap-free emulsion polymerization was ammoniated by simply treating it with ethylenediamine (EDA) solution under heating. Compared with the parent PAN material, the aminated PAN (EDA-PAN) is a more suitable support to achieve high dispersion of Pd NPs with ultra-small particle size (around 1.2 nm), and to fabricate more active and stable supported Pd-based catalyst for FA dehydrogenation. The turnover frequency (TOF) of the Pd/EDA-PAN catalyst could reach to 3989 h −1 at 333 K without using any additional bases or additives. More significantly, the aminated catalyst could even work well at ambient temperature with a TOF of 688 h −1 at 303 K.