Nickel Nanoparticles Encapsulated in SSZ-13 Cage for Highly Efficient CO₂ Hydrogenation

Abstract

CO2 catalytic hydrogenation to energy-rich chemical feedstocks using renewable hydrogen provides an attractive avenue for the climate-change issues and global energy demands. However, the rational design of catalysts with high activity, selectivity, and stability toward CO2 hydrogenation remains exceptionally challenging. Here, we report Ni/SSZ-13 catalyst that captures the design concept of metal nanoparticle encapsulation in a cage of porous materials. The results indicate that nickel species mainly exist in the form of Ni metal on the SSZ-13 support and serve as the active phase for CO2 hydrogenation. The stronger interaction between metallic nickel and the SSZ-13 support is responsible for the stability of nickel nanoparticles. 15%Ni/SSZ-13 catalyst exhibits 72% CO2 conversion and 96% CH4 selectivity at 450 °C. The relatively higher CO selectivity of Ni/SSZ-13 catalyst at the higher temperatures is associated with the reverse water–gas shift reaction due to its endothermic nature. There is no obvious catalyst deactivation during the long-term hydrogenation experiments. The encapsulation effect of nickel nanoparticles in the well-ordered SSZ-13 cage is responsible for the high antisintering ability and thermal stability of Ni/SSZ-13 catalyst. Quantum chemistry calculation was also conducted to reveal the microcosmic reaction mechanism of CO2 hydrogenation. The nickel–zeolite interface is found to be the active center of Ni/SSZ-13 catalyst. CO2 hydrogenation over Ni/SSZ-13 catalyst is mainly controlled by the direct C–O bond scission pathway. This study marks a step ahead toward CO2 hydrogenation to value-added fuels and reveals the encapsulation effects of metallic nanoparticles that will spark inspiration for other industrial applications.

Study on the tolerance of low-temperature CO methanation with single pulse experiments

“…However, the obtained value fits to dynamic measurements investigating carbon hydrogenation [50] and CO methanation with SSITKA experiments [51], obtaining 71 kJ mol -1 and 64.4 kJ mol -1 , respectively. These findings are supported by the fact that the carbon mechanism (C−O bond scission pathway) has a lower activation barrier (𝐸 A < 95 kJ/mol) [52,53]. Moreover, dynamic DRIFTS investigations at 200 and 300 °C support this proposed mechanism and agree with the observations of the present study [54].…”

Advances and Perspectives of Photopromoted CO2 Hydrogenation for Methane Production: Catalyst Development and Mechanism Investigations

“…Yang et al loaded Ni on a porous crystalline chabazite SSZ-13 by the impregnation method to obtain the Ni/SSZ-13 catalyst., which had excellent catalytic performance and stability. 115 This work provides a new idea for improving the stability and antisintering ability of catalysts.…”

Inverse Oxide/Metal Catalysts for CO2 Hydrogenation to Methanol

“…While the RWGS reaction mainly involves the use of Cu-, Pt-, and Rh-based catalysts, the methanation reaction (eq ), also referred to as the Sabatier reaction, has been mainly studied using supported Ni, Ru, Rh, and Pd catalysts. − Although the methanation reaction is thermodynamically favorable (Δ G 298K = −130.8 kJ/mol), the reduction of fully oxidized carbon to methane involves four-electron pairs, making the reaction kinetically limited . Stoichiometrically, this reaction also consumes the most hydrogen, imposing a significant expense on the process.…”