Pseudopyrolysis of Metal-Organic Frameworks: A Synchronous Nucleation Mechanism to Synthesize Ultrafine Metal Compound Nanoparticles

Metal-Organic frameworks (MOFs) are increasingly being investigated for the synthesis of carbon-supported metal-based ultrafine nanoparticles (UNPs). However, the collapse of the carbon framework and aggregation of metal particles in the pyrolysis process have severely hindered their stability and applications. Here, we report the synchronous nucleation pseudopyrolysis of MOFs to confine Fe/FeOx UNPs in intact porous carbon nanorods (IPCNs), revealed by in situ transmission electron microscopy experiments and ex situ structure analysis. The pseudopyrolysis mechanism enables strong physical and chemical confinement effects between UNPs and carbon by moderate thermal kinetics and abundant oxygen defects. Further, this strong confinement is greatly beneficial for subsequent chemical transformations to obtain different Fe-based UNPs and excellent electrochemical performance. As a proof of concept, the as-prepared FeSe UNPs in IPCNs show superior lithium storage performance with an ultrahigh and stable capacity of 815.1 mAh g-1 at 0.1 A g -1 and 379.7 mAh g-1 at 5 A g-1 for 1000 cycles.

Automated summary

In this study, a synchronous nucleation pseudopyrolysis method was used to confine Fe/FeOx ultrafine nanoparticles (UNPs) in intact porous carbon nanorods (IPCNs). The strong physical and chemical confinement effects between UNPs and carbon were achieved through moderate thermal kinetics and abundant oxygen defects. This strong confinement greatly benefited subsequent chemical transformations and resulted in different Fe-based UNPs with excellent electrochemical performance. As a proof of concept, FeSe UNPs in IPCNs exhibited superior lithium storage performance with an ultrahigh and stable capacity of 815.1 mAh g-1 at 0.1 A g -1 and 379.7 mAh g-1 at 5 A g-1 for 1000 cycles.