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Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction
Published on: April 10, 2018
Evolution Pathway from Iron Precursors to Fe-N4 Single-Atom Catalysts via High-Temperature Cyanide Coordination
Dongxu Cao1, Weishen Song1, Meixi Zhang1
1New Cornerstone Science Laboratory, State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and National & Local Joint Engineering Research Center of Preparation Technology of Nanomaterials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
None:
The rational synthesis of atomically dispersed iron-nitrogen-carbon (Fe-N-C) catalysts is hindered by the opacity of the high-temperature pyrolysis, in which the specific chemical drivers of active site formation remain elusive. Here, we employ a spatially separated chemical vapor pyrolysis strategy to decouple this process and probe the role of vapor-phase nitrogen-containing species in the evolution from iron oxide aggregates to isolated Fe-N4 sites. In this model system, HCN is found to be more effective than NH3 in promoting the disintegration of FeOx aggregates through the transient formation of Fe─C≡N intermediates. We further identify a synergistic process in which HCN facilitates FeOx aggregate dispersion, while Fe species reciprocally catalyze the dissociation of HCN, thereby accelerating the construction of nitrogen-rich support that stabilizes the dispersed Fe atoms. Spectroscopic analysis and ab initio molecular dynamics (AIMD) simulations collectively support this ligand-mediated atomization pathway and pinpoint the temperature onset of Fe-N4 formation at 800 °C. This method effectively deconvolutes the Fe-N4 formation from supremely complex pyrolysis processes, illuminating pathways for the controllable design of M-N-C catalysts.
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