Structure sensitivity in gas sorption and conversion on metal-organic frameworks

Guusje Delen; Matteo Monai; Katarina Stančiaková; Bettina Baumgartner; Florian Meirer; Bert M Weckhuysen

doi:10.1038/s41467-022-35762-9

Structure sensitivity in gas sorption and conversion on metal-organic frameworks

Guusje Delen
, Matteo Monai
, Katarina Stančiaková
, Bettina Baumgartner
, Florian Meirer
, Bert M Weckhuysen^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

Many catalytic processes depend on the sorption and conversion of gaseous molecules on the surface of (porous) functional materials. These events often preferentially occur on specific, undercoordinated, external surface sites. Here we show the combination of in situ Photo-induced Force Microscopy (PiFM) with Density Functional Theory (DFT) calculations to study the site-specific sorption and conversion of formaldehyde on the external surfaces of well-defined faceted ZIF-8 microcrystals with nanoscale resolution. We observed preferential adsorption of formaldehyde on high index planes. Moreover, in situ PiFM allowed us to visualize unsaturated nanodomains within extended external crystal planes, showing enhanced sorption behavior on the nanoscale. Additionally, on defective ZIF-8 crystals, structure sensitive conversion of formaldehyde through a methoxy- and a formate mechanism mediated by Lewis acidity was found. Strikingly, sorption and conversion were influenced more by the external surface termination than by the concentration of defects. DFT calculations showed that this is due to the presence of specific atomic arrangements on high-index crystal surfaces. With this research, we showcase the high potential of in situ PiFM for structure sensitivity studies on porous functional materials.

Original language	English
Article number	129
Number of pages	11
Journal	Nature Communications
Volume	14
Issue number	1
DOIs	https://doi.org/10.1038/s41467-022-35762-9
Publication status	Published - 9 Jan 2023

Bibliographical note

Publisher Copyright:
© 2023, The Author(s).

Funding

This work was performed with funding from the European Research Council (ERC) Advanced grant 321140 (B.M.W.) and funding through the Gravity program of the Multiscale Catalytic Energy Conversion (MCEC) Consortium (BMW). Additionally, this work was carried out on the Dutch national e-infrastructure with the support of SURF Cooperative. Furthermore, the authors kindly acknowledge Max Kiffen (Utrecht University, UU) for his help in establishing synthesis parameters for the Layer-by-Layer SURZIF-8 deposition. This work was performed with funding from the European Research Council (ERC) Advanced grant 321140 (B.M.W.) and funding through the Gravity program of the Multiscale Catalytic Energy Conversion (MCEC) Consortium (BMW). Additionally, this work was carried out on the Dutch national e-infrastructure with the support of SURF Cooperative. Furthermore, the authors kindly acknowledge Max Kiffen (Utrecht University, UU) for his help in establishing synthesis parameters for the Layer-by-Layer SURZIF-8 deposition.

Funders	Funder number
Multiscale Catalytic Energy Conversion
SURF Cooperative
European Research Council	321140

Keywords

Adsorption
Catalysis
Formaldehyde
Formic-acid
Ft-ir
Methanol
Quality
Spectroscopy
Stability
Zif-8

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s41467-022-35762-9Final published version, 2.1 MBLicence: CC BY

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title = "Structure sensitivity in gas sorption and conversion on metal-organic frameworks",

abstract = "Many catalytic processes depend on the sorption and conversion of gaseous molecules on the surface of (porous) functional materials. These events often preferentially occur on specific, undercoordinated, external surface sites. Here we show the combination of in situ Photo-induced Force Microscopy (PiFM) with Density Functional Theory (DFT) calculations to study the site-specific sorption and conversion of formaldehyde on the external surfaces of well-defined faceted ZIF-8 microcrystals with nanoscale resolution. We observed preferential adsorption of formaldehyde on high index planes. Moreover, in situ PiFM allowed us to visualize unsaturated nanodomains within extended external crystal planes, showing enhanced sorption behavior on the nanoscale. Additionally, on defective ZIF-8 crystals, structure sensitive conversion of formaldehyde through a methoxy- and a formate mechanism mediated by Lewis acidity was found. Strikingly, sorption and conversion were influenced more by the external surface termination than by the concentration of defects. DFT calculations showed that this is due to the presence of specific atomic arrangements on high-index crystal surfaces. With this research, we showcase the high potential of in situ PiFM for structure sensitivity studies on porous functional materials.",

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AU - Weckhuysen, Bert M

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N2 - Many catalytic processes depend on the sorption and conversion of gaseous molecules on the surface of (porous) functional materials. These events often preferentially occur on specific, undercoordinated, external surface sites. Here we show the combination of in situ Photo-induced Force Microscopy (PiFM) with Density Functional Theory (DFT) calculations to study the site-specific sorption and conversion of formaldehyde on the external surfaces of well-defined faceted ZIF-8 microcrystals with nanoscale resolution. We observed preferential adsorption of formaldehyde on high index planes. Moreover, in situ PiFM allowed us to visualize unsaturated nanodomains within extended external crystal planes, showing enhanced sorption behavior on the nanoscale. Additionally, on defective ZIF-8 crystals, structure sensitive conversion of formaldehyde through a methoxy- and a formate mechanism mediated by Lewis acidity was found. Strikingly, sorption and conversion were influenced more by the external surface termination than by the concentration of defects. DFT calculations showed that this is due to the presence of specific atomic arrangements on high-index crystal surfaces. With this research, we showcase the high potential of in situ PiFM for structure sensitivity studies on porous functional materials.

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KW - Quality

KW - Spectroscopy

KW - Stability

KW - Zif-8

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Structure sensitivity in gas sorption and conversion on metal-organic frameworks

Abstract

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Keywords

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