School of Earth, Environmental, and Marine Sciences Faculty Publications and Presentations
Document Type
Article
Publication Date
2025
Abstract
The selectivity of acetylene hydrogenation by the Rh single-atom catalyst (SAC) supported on HY zeolite was investigated using density functional theory (DFT) and a 5/83T quantum mechanics/molecular mechanics (QM/MM) embedded cluster model. The calculated activation barrier (ΔG‡) for the oxidative addition of dihydrogen to the Rh metal center (15.9 kcal/mol) is lower in energy than that for the σ-bond metathesis of dihydrogen to the Rh—C bond (22.7 kcal/mol) and the Rh—O bond (28.4 kcal/mol). The activation barriers of the oxidative addition of subsequent dihydrogen molecules are significantly higher than that of the oxidative addition of the first dihydrogen molecule. These findings align with the experimentally observed activity and selectivity of the atomically dispersed Rh catalyst supported on HY zeolite. Natural bond orbital (NBO), molecular orbital (MO) and fuzzy bond order analyses were used to examine the interaction between the Rh metal center and acetylene versus ethylene ligands. The occupancies of the Rh lone pairs, π-bonding and π*-antibonding orbitals of acetylene and ethylene are consistent with the expected stronger interaction between the Rh metal center and acetylene compared to ethylene on the HY zeolite support.
Recommended Citation
Yordanlı, Melisa Su, Roberto Escobar, Jessica Meza, Deniz Akgül, Yuxin Zhao, Alper Uzun, Fatma Ahu Akin, Viktorya Aviyente, Abdurrahman Cagri Atesin, and Tűlay Aygan Ateşin. n.d. “DFT Study of the Mechanism of Selective Hydrogenation of Acetylene by Rhodium Single-Atom Catalyst Supported on HY Zeolite.” ChemPhysChem, e202400867. https://doi.org/10.1002/cphc.202400867
Publication Title
ChemPhysChem
DOI
10.1002/cphc.202400867
Comments
This is the peer reviewed version of the following article https://doi.org/10.1002/cphc.202400867. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.