ABSTRACT
Noble metal catalysts exhibit high catalytic activity in lean CH4 combustion at low temperatures. However, the high surface energy of noble metal nanoparticles makes them susceptible to deactivation due to migratory-aggregation during the catalytic process. Herein, a core-shell structure with a Pd/CeO2 core and a SiO2 shell (denoted as Pd/CeO2@SiO2) was designed and prepared to enhance the thermal stability for catalytic lean CH4 combustion. A series of characterization methods demonstrated the successful encapsulation of SiO2 and the modified thermal stability. The results of activity tests indicated that Pd/CeO2@SiO2 exhibited the optimal catalytic performance. After seven runs, Pd/CeO2@SiO2 achieved 90% conversion of CH4 at 385 °C compared to Pd/CeO2 at 440 °C. The remarkable catalytic performance was attributed to the synergistic effect of strengthened metal-support interactions and the core-shell structure. On the one hand, the migration and aggregation of Pd nanoparticles were limited due to the protection of the SiO2 shell layer. On the other hand, the SiO2 shell layer further enhanced the interactions between the Pd nanoparticles and CeO2, thus promoting the formation of PdxCe1-xO2-δ solid solutions and active oxygen species, which were beneficial for the improvement of the stability and redox capacity of the catalyst.
ABSTRACT
Preferential oxidation of carbon monoxide (CO-PROX) plays a vital role in H2 purification in the upstream systems of proton exchange membrane fuel cells (PEMFCs) for its high efficiency, low cost and practicability. The key to the application of CO-PROX is the design and preparation of catalysts, and the supported metal catalysts have been the mainstay after decades of development. The metal-support interaction (MSI), which acts as a bridge between the design of supported catalysts and atomic-level theoretical research, has triggered increasing attention. There is a growing body of literature that recognizes the importance of the MSI in heterogeneous catalysis. In this review, the impacts of the MSI including strong metal-support interactions and electronic metal-support interactions on the essential characteristics of supported single atom, nanocluster and nanoparticle catalysts, and therefore, on catalytic behaviors were discussed, respectively, primarily focusing on electron transfer, chemical bonding and the encapsulation of active sites induced by the MSI. We also presented an overview of how the MSI can be utilized to rationally design catalysts to meet target requirements such as high activity, selectivity or stability via appropriate selection and modification of support and active species. The perspectives of the future development for comprehensive understanding of the MSI were also proposed.
ABSTRACT
Nanoreactors with a delimited void space and a large number of mesoporous structures have attracted great attention as potential heterogeneous catalysts. In this work, a cobalt and nitrogen co-doped binary carbon@silica@carbon hydrophobic nanoreactor was synthesized by an in situ synthesis method. Cobalt porphyrin was used as an active component to construct Co-Nx sites, and the purpose of the double carbon layer coating was to enhance the hydrophobicity of the surface of the nanoreactor. The optimal nanoreactor could achieve 96.9% ethylbenzene conversion and 99.1% acetophenone selectivity and showed outstanding universality to many other aromatic alkanes. The superior performance was mainly due to the presence of double carbon layers and the high content of Co-Nx sites. The double hydrophobic carbon layer coating could not only promote the adsorption of organic molecules, but also implant Co-Nx active sites on both the inner and outer surfaces of the nanoreactor. This work proposed a meaningful strategy to obtain a highly efficient nanoreactor for C-H bond oxidation.
