Periodic Density Functional Theory calculations reveal the potential application of 10 imidazole based N-heterocyclic carbenes (NHCs) to behave as “molecular corks” for hydrogen storage on single atom alloys, comprised of Pd/Cu(111) or Pt/Cu(111). Calculations show that functionalizing the NHC with different electron withdrawing/donating functional groups results in different binding energies of the NHC with the alloy surfaces. The results are compared to DFT calculations of carbon monoxide bound to these alloys. The Huynh electronic parameter (HEP) is calculated for several simple imidazole NHCs to gauge σ-donor ability, while Se-NMR and P-NMR calculations of selenourea derivatives and carbene-phosphinidene adducts, respectively, have been utilized to gauge π-acidity of the NHCs. It is demonstrated that consideration of both σ and π donating/accepting ability must be considered when predicting the surface-adsorbate binding energy. It was found that electron withdrawing groups tend to weaken the NHC-surface interaction while electron donating substituents tend to strengthen the interaction.
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Understanding bonding of N-heterocyclic carbenes on Pd/Cu(111) single atom alloys via non-local density functional theory to store hydrogen via the molecular corking effect
N-heterocyclic carbenes(NHCs) have garnered the attention of material scientists and chemists for their tunable electronic properties. NHCs anchored to surfaces have attractive features and may provide new applications that traditional self-assembled monolayers (SAMs) have yet to be employed. In-fact, NHCs have been utilized to functionalize surfaces to tune reactivity and/or selectivity. However, the underlying mechanisms to control the surface-adsorbate interaction is still in its infancy, especially for SAAs. Herein we utilize periodic non-local density functional theory (DFT) calculations to better understand how changing the NHC backbone influences the bonding between the surface and the adsorbate with the end goal to utilize a relatively new mechanism to store hydrogen.
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- Award ID(s):
- 2142874
- NSF-PAR ID:
- 10497198
- Publisher / Repository:
- sciMeetings
- Date Published:
- Journal Name:
- ACS Spring 2024
- Format(s):
- Medium: X
- Location:
- New Orleans
- Sponsoring Org:
- National Science Foundation
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Periodic Density Functional Theory calculations reveal the potential application of 10 imidazole based N-heterocyclic carbenes to behave as “molecular corks” for hydrogen storage on single atom alloys, comprised of Pd/Cu(111) or Pt/Cu(111). Calculations show that functionalizing the NHC with different electron withdrawing/donating functional groups results in different binding energies of the NHC with the alloy surfaces. The results are compared to DFT calculations of carbon monoxide bound to these alloys. The Huynh electronic parameter (is calculated for several simple imidazole NHCs to gauge σ-donor ability, while Se-NMR of and P-NMR calculations of selenourea derivatives and carbene-phosphinidene adducts, respectively, have been utilized to gauge π-acidity of the NHCs. It is demonstrated that consideration of both σ and π donating/accepting ability must be considered when predicting the surface-adsorbate binding energy. It was found that electron withdrawing groups tend to weaken the NHC-surface interaction while electron withdrawing substituents tend to strengthen the interaction.more » « less
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