TY - JOUR
T1 - Carbon Nanofiber Growth Rates on NiCu Catalysts
T2 - Quantitative Coupling of Macroscopic and Nanoscale In Situ Studies
AU - Welling, Tom A.J.
AU - Schoemaker, Suzan E.
AU - de Jong, Krijn P.
AU - de Jongh, Petra E.
N1 - Funding Information:
T.A.J.W. and S.E.S. were funded by the Advanced Research Center for Chemical Building Blocks, ARC CBBC, which is cofounded and co-financed by the Dutch Research Council (NWO) and The Netherlands Ministry of Economic Affairs and Climate Policy. The electron microscopy experiments were performed in the Electron Microscopy Center Utrecht, and the authors thank Hans Meeldijk and Chris Schneijdenberg for the technical support. The authors also acknowledge the European Research Council, EU FP7 ERC Advanced Grant No. 338846. They furthermore thank Dennie Wezendonk for technical support for the TGA experiments, and Bennie Reesink, Alexander van Bavel, and Jovana Zečević for fruitful discussions.
Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.
PY - 2023/8/17
Y1 - 2023/8/17
N2 - 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% H2, 45% CH4, 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.
AB - 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% H2, 45% CH4, 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.
UR - http://www.scopus.com/inward/record.url?scp=85167824664&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcc.3c02657
DO - 10.1021/acs.jpcc.3c02657
M3 - Article
AN - SCOPUS:85167824664
SN - 1932-7447
VL - 127
SP - 15766
EP - 15774
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 32
ER -