Carbon Nanofiber Growth Rates on NiCu Catalysts: Quantitative Coupling of Macroscopic and Nanoscale In Situ Studies.

Since recently, gas-cell transmission electron microscopy allows for direct, nanoscale imaging of catalysts during reaction. However, often systems are too perturbed by the imaging conditions to be relevant for real-life catalyzed conversions. We followed carbon nanofiber growth from NiCu-catalyzed methane decomposition under working conditions (550 °C, 1 bar of 5% H, 45% CH, and 50% Ar), directly comparing the time-resolved overall carbon growth rates in a reactor (measured gravimetrically) and nanometer-scale carbon growth observations (by electron microscopy). Good quantitative agreement in time-dependent growth rates allowed for validation of the electron microscopy measurements and detailed insight into the contribution of individual catalyst nanoparticles in these inherently heterogeneous catalysts to the overall carbon growth. The smallest particles did not contribute significantly to carbon growth, while larger particles (8-16 nm) exhibited high carbon growth rates but deactivated quickly. Even larger particles grew carbon slowly without significant deactivation. This methodology paves the way to understanding macroscopic rates of catalyzed reactions based on nanoscale in situ observations.