Melem (2,6,10-triamino-s-heptazine) is the building block of melon, a carbon nitride (CN) polymer that is proven to produce H2from water under visible illumination. With the aim of bringing additional insight into the electronic structure of CN materials, we performed a spectroscopic characterization of gas-phase melem and of a melem-based self-assembled 2D H-bonded layer on Au(111) by means of ultraviolet and X-ray photoemission spectroscopy (UPS, XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. In parallel, we performed density functional theory (DFT) simulations of the same systems to unravel the molecular charge density redistribution caused by the in-plane H-bonds. Comparing the experimental results with the spectroscopic DFT simulations, we can correlate the induced charge accumulation on the Naminoatoms to the red-shift of the corresponding N 1s binding energy (BE) and of the Namino1s → LUMO+n transitions. Moreover, when introducing a supporting Au(111) surface in the computational simulations, we observe a molecule-substrate interaction that almost exclusively involves the out-of-plane molecular orbitals, leaving those engaged in the in-plane H-bonded network rather unperturbed.

Ugolotti, A., Lanzilotto, V., Grazioli, C., Schio, L., Zamalloa-Serrano, J., Stredansky, M., et al. (2023). In-Plane Hydrogen Bonds and Out-of-Plane Dipolar Interactions in Self-Assembled Melem Networks. JOURNAL OF PHYSICAL CHEMISTRY. C, 127(23), 11307-11316 [10.1021/acs.jpcc.3c01990].

In-Plane Hydrogen Bonds and Out-of-Plane Dipolar Interactions in Self-Assembled Melem Networks

Ugolotti, Aldo
Primo
;
Ferraro, Lorenzo;Di Valentin, Cristiana
Ultimo
2023

Abstract

Melem (2,6,10-triamino-s-heptazine) is the building block of melon, a carbon nitride (CN) polymer that is proven to produce H2from water under visible illumination. With the aim of bringing additional insight into the electronic structure of CN materials, we performed a spectroscopic characterization of gas-phase melem and of a melem-based self-assembled 2D H-bonded layer on Au(111) by means of ultraviolet and X-ray photoemission spectroscopy (UPS, XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. In parallel, we performed density functional theory (DFT) simulations of the same systems to unravel the molecular charge density redistribution caused by the in-plane H-bonds. Comparing the experimental results with the spectroscopic DFT simulations, we can correlate the induced charge accumulation on the Naminoatoms to the red-shift of the corresponding N 1s binding energy (BE) and of the Namino1s → LUMO+n transitions. Moreover, when introducing a supporting Au(111) surface in the computational simulations, we observe a molecule-substrate interaction that almost exclusively involves the out-of-plane molecular orbitals, leaving those engaged in the in-plane H-bonded network rather unperturbed.
Articolo in rivista - Articolo scientifico
melem; H-bond; XPS; DFT, NEXAFS; covalent-network
English
6-giu-2023
2023
127
23
11307
11316
reserved
Ugolotti, A., Lanzilotto, V., Grazioli, C., Schio, L., Zamalloa-Serrano, J., Stredansky, M., et al. (2023). In-Plane Hydrogen Bonds and Out-of-Plane Dipolar Interactions in Self-Assembled Melem Networks. JOURNAL OF PHYSICAL CHEMISTRY. C, 127(23), 11307-11316 [10.1021/acs.jpcc.3c01990].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/419958
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