Syngas, consisting of equimolar CO and H2, is an important feedstock for large-scale production of a wide range of commodity chemicals including aldehyde, methanol, ammonia, and other oxygenated chemicals. Dry reforming of methane (DRM), proceeding by reacting greenhouse gases, CO2 and CH4, at high temperatures in the presence of a metal catalyst, is considered one of the most environmentally friendly routes for syngas production. Nevertheless, nonprecious metal-based catalysts, which can operate at relatively low temperatures for high product yields and selectivities, are required to drive the DRM process for industrial applications effectively. Here, we developed NiCo@C nanocomposites from a corresponding NiCo-based bimetallic metal–organic framework (MOF) to serve as high-performance catalysts for the DRM process, achieving high turnover frequencies (TOF) at low temperatures (>5.7 s–1 at 600 °C) and high product selectivities (H2/CO = 0.9 at 700 °C). The incorporation of Co in Ni catalysts improves the operation stability and light-off stability. The present development for MOF-derived nanocomposites opens a new horizon for design of DRM catalysts.

Spherical porous nanoclusters composed of NiO and CeO2 nanoparticles were successfully developed by a refined gas-phase controlled synthesis method, which were shown to be useful for syngas production via a high-performance catalysis of dry reforming of methane (DRM) coupled with partial oxidation of methane (POM). The synthetic method combines the principles of aerosol-phase evaporation-induced aggregation of polyethylene glycol (PEG; as soft template) followed by thermal decomposition of the self-assembled precursor crystallites for the creation of mesopores in the hybrid nanostructure directly in gas phase. Specific surface area, pore volume, and metal surface area in the Ni–Ce–O hybrid nanostructure increased by using the PEG. The results show a remarkably high turnover frequency of methane (0.93 s–1 at 600 °C) by using the developed Ni–Ce–O porous nanostructure as catalyst, where the H2/CO ratio was tunable for attaining a high syngas selectivity. Both a high light-off stability and 100 h operation stability were achieved through a remarkable reduction of coke formation on the Ni–Ce–O hybrid nanostructure. The work demonstrates a facile aerosol route for fabricating hybrid nanoporous clusters as useful catalysts for methane-based combined reactions.

We develop a new Ni–CeO x hybrid nanoparticle as a high-performance catalyst for dry reforming of methane with carbon dioxide (DRM) using a facile gas-phase synthetic approach. The crystallites of Ni and CeO2 were homogeneously self-assembled as a hybrid nanostructure, creating a large amount of Ni–Ce–O interface for a strong metal–support interfacial interaction. Chemical composition and oxidation state of the hybrid nanostructure were tunable directly in the aerosol state. The results show that the starting temperature of catalysis by Ni-based catalysts reduced by ∼150 °C through the hybridization with CeO2 followed by a direct H2 reduction in the aerosol state. In comparison to Ni-only nanoparticle, the Ni–CeO x hybrid nanoparticle showed stable and high conversion for CH4 and CO2 with a remarkably turnover frequency at low temperature (0.1 s–1 at 450 °C). The amount of coke formation greatly reduced by 18×, whereas the H2/CO ratio was constant at ∼0.8 by a 1.5× of the increase of CO2/CH4 ratio. The work demonstrated a facile route for controlled synthesis of Ni–CeO x hybrid nanoparticles with a very high catalytic activity and stability of DRM. The findings of this study can shed light on the mechanism of Ni–Ce–O synergistic catalysis, which can be especially useful for methane-based energy applications.

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