Mode-selective Raman imaging of metal-organic frameworks reveals surface heterogeneities of single HKUST-1 crystals

Fuente: arXiv
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Main Authors: Ferreira, Matheus Esteves, Del Grande, Mariana, Oliveira, Felipe Lopes, Ferreira, Rodrigo Neumann Barros, da Silva, Ademir Ferreira, Carvalho, Pamela Costa, Lima, Geisa, Jorio, Ado, Steiner, Mathias
Format: Preprint
Published: 2024
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author Ferreira, Matheus Esteves
Del Grande, Mariana
Oliveira, Felipe Lopes
Ferreira, Rodrigo Neumann Barros
da Silva, Ademir Ferreira
Carvalho, Pamela Costa
Lima, Geisa
Jorio, Ado
Steiner, Mathias
author_facet Ferreira, Matheus Esteves
Del Grande, Mariana
Oliveira, Felipe Lopes
Ferreira, Rodrigo Neumann Barros
da Silva, Ademir Ferreira
Carvalho, Pamela Costa
Lima, Geisa
Jorio, Ado
Steiner, Mathias
contents Metal organic frameworks (MOFs) are nanoporous materials with high surface-to-volume ratio that have potential applications as gas sorbents. Sample quality is, however, often compromised and it is unclear how defects and surface contaminants affect the spectral properties of single MOF crystals. Raman micro-spectroscopy is a powerful tool for characterizing MOFs, yet spatial spectral heterogeneity distributions of single MOF crystals have not been reported so far. In this work, we use Raman micro-spectroscopy to characterize spatially isolated, single crystals of the MOF species HKUST-1. In a first step, we validate HKUST-1's Raman spectrum based on DFT simulations and we identify a previously unreported vibrational feature. In a second step, we acquire diffraction-limited, mode-selective Raman images of a single HKUST-1 crystals that reveal how the spectral variations are distributed across the crystal surface. In a third step, we statistically analyze the measured spectral peak positions and line widths for quantifying the variability occurring within the same crystal as well as between different crystals taken from the same batch. Finally, we explore how multivariate data analysis can aid feature identification in Raman images of single MOF crystals. For enabling validation and reuse, we have made the spectroscopic data and simulation code publicly available.
format Preprint
id arxiv_https___arxiv_org_abs_2411_14644
institution arXiv
publishDate 2024
record_format arxiv
spellingShingle Mode-selective Raman imaging of metal-organic frameworks reveals surface heterogeneities of single HKUST-1 crystals
Ferreira, Matheus Esteves
Del Grande, Mariana
Oliveira, Felipe Lopes
Ferreira, Rodrigo Neumann Barros
da Silva, Ademir Ferreira
Carvalho, Pamela Costa
Lima, Geisa
Jorio, Ado
Steiner, Mathias
Materials Science
Chemical Physics
Metal organic frameworks (MOFs) are nanoporous materials with high surface-to-volume ratio that have potential applications as gas sorbents. Sample quality is, however, often compromised and it is unclear how defects and surface contaminants affect the spectral properties of single MOF crystals. Raman micro-spectroscopy is a powerful tool for characterizing MOFs, yet spatial spectral heterogeneity distributions of single MOF crystals have not been reported so far. In this work, we use Raman micro-spectroscopy to characterize spatially isolated, single crystals of the MOF species HKUST-1. In a first step, we validate HKUST-1's Raman spectrum based on DFT simulations and we identify a previously unreported vibrational feature. In a second step, we acquire diffraction-limited, mode-selective Raman images of a single HKUST-1 crystals that reveal how the spectral variations are distributed across the crystal surface. In a third step, we statistically analyze the measured spectral peak positions and line widths for quantifying the variability occurring within the same crystal as well as between different crystals taken from the same batch. Finally, we explore how multivariate data analysis can aid feature identification in Raman images of single MOF crystals. For enabling validation and reuse, we have made the spectroscopic data and simulation code publicly available.
title Mode-selective Raman imaging of metal-organic frameworks reveals surface heterogeneities of single HKUST-1 crystals
topic Materials Science
Chemical Physics
url https://arxiv.org/abs/2411.14644