Abstract
Carbonaceous species, including subsurface carbidic carbon and surface carbon, play crucial roles in heterogeneous catalysis. Many reports suggested the importance of subsurface carbon in the selective hydrogenation of alkynes over Pd-based catalysts. However, the role of surface carbon has been largely overlooked. We demonstrate that subsurface carbon in Pd is not responsible for the selectivity in acetylene hydrogenation. In contrast, the structure of surface carbonaceous species plays a decisive role in hydrogenation selectivity. Electron microscopy and spectroscopy evidence, along with theoretical modelling, reveal that partial graphitization of surface carbonaceous species results in unique spatial confinement of surface reaction intermediates, thus altering the reaction energy landscape in favour of ethylene desorption as opposed to over-hydrogenation. This mechanism for selectivity control is analogous to enzyme catalysis, where the active centers selectively attract reactants and release products. Similar mechanism may be present in CO/CO2 hydrogenation and alkane dehydrogenation reactions.
Original language | English |
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Journal | Angewandte Chemie - International Edition |
DOIs | |
State | Accepted/In press - 2024 |
Funding
We thank Dr. Spivey for the access to IR instrument. K.D. acknowledges LIFT2 grant from Louisiana State University (LSU). The electron microscopy (HAADF\u2010STEM and EELS) portion of this research was supported by the Center for Nanophase Materials Sciences (CNMS), which is a US Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory. XRD/XPS/Raman studies were performed at the Shared Instrumentation Facility at LSU. DFT studies used high performance computing resources provided by LSU (hpc.lsu.edu).
Keywords
- acetylene
- carbon deposition
- confinement effect
- palladium carbide
- selective hydrogenation