Effect of metal dispersion and support structure of Ni/silicalite-1 catalysts on non-thermal plasma (NTP) activated CO₂ hydrogenation

Non-thermal plasma (NTP) activated heterogeneous catalysis is a promising alternative to thermal catalysis for enabling many challenging reactions (e.g. catalytic CO₂ hydrogenation) under mild conditions. However, the mechanistic insight into the interaction between highly energetic electrons and vibrationally-exited reactive species with metal catalyst is still lacking. Here, catalytically active Ni nanoparticles supported on silicalite-1 zeolites with different configurations regarding the location of Ni active sites and support pore structures were comparably investigated using catalytic CO₂ hydrogenation under the thermal and NTP conditions. Experimental results revealed that the performance of the NTP-catalysis depends on the configuration of the catalysts significantly. Specifically, catalysts with Ni active sites sit on the outer surface of zeolite crystals (i.e. microporous Ni/S1 and Ni/M-S1@Shell with steam-assisted recrystallised micro-meso-porous structure) showed relatively good catalytic performance at a low applied voltage of 6.0 kV. Conversely, the encapsulated catalyst with hierarchical meso-micro-porous structure (i.e. Ni/D-S1) which has relatively small (i.e. average Ni particle sizes of 2.8±0.7 nm) and dispersed Ni nanoparticles (i.e. Ni dispersion of ca. 2.5 %) demonstrated comparatively the best catalytic performance (i.e. CO₂ conversion of ca. 75 %) at 7.5 kV. Additionally, under the NTP conditions studied, Ni on carbon-templated mesoporous silicalite-1 (Ni/M-S1) showed the worst selectivity to CH₄, which was attributed to the poor accessibility of Ni active sites encapsulated in the enclosed mesopores. This study demonstrated the crucial role of catalyst design in NTP activated catalysis.