Highly Porous Nanocrystalline UiO-66 Thin Films via Coordination Modulation Controlled Step-by-Step Liquid-Phase Growth

A.L. Semrau, Suttipong Wannapaiboon*, Sidharam P. Pujari, Pia Vervoorts, Bauke Albada, Han Zuilhof, Roland A. Fischer

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

3 Citations (Scopus)

Abstract

Metal-organic frameworks (MOFs) possess exciting properties, which can be tailored by rational material design approaches. Integration of MOFs in functional nano- and mesoscale systems require selective crystallite positioning and thin-film growth techniques. Stepwise layer-by-layer liquid-phase epitaxy (LPE) emerged as one of the methods of choice to fabricate MOF@substrate systems. The layer-by-layer approach of LPE allows a precise control over the film thickness and crystallite orientation. However, these advantages were mostly observed in cases of tetra-connected dinuclear paddle-wheel MOFs and Hoffmann-type MOFs. Higher connected MOFs (consisting of nodes with 8-12 binding sites), such as the Zr-oxo cluster based families, are notoriously hard to deposit in an acceptable quality by the stepwise liquid-phase process. Herein, we report the use of coordination modulation (CM) to assist and enhance the LPE growth of UiO-66, Zr 6 O 4 (OH) 4 (bdc) 6 (bdc 2- = 1,4-benzene-dicarboxylate) films. Highly porous and crystalline thin films were obtained with good control of the crystallite domain size and film thickness in the nanoscale regime. The crystallinity (by grazing incidence X-ray diffraction), morphology (by scanning electron microscopy, atomic form microscopy), elemental composition (by X-ray photoelectron spectroscopy), binding properties (by infrared spectroscopy), and adsorption capacity (by quartz crystal microbalance adsorption experiments) for volatile organic compounds (e.g. CH 3 OH) of the fabricated thin films were investigated. These results substantiate a proof-of-concept of CM-LPE of MOFs and could be the gateway to facilitate in general the deposition of chemically very robust and higher-connected MOF thin films with automatic process-controlled LPE techniques under mild synthetic conditions.

Original languageEnglish
Pages (from-to)1738-1747
JournalCrystal Growth and Design
Volume19
Issue number3
DOIs
Publication statusPublished - Mar 2019

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liquid phases
Liquid phase epitaxy
Metals
Modulation
liquid phase epitaxy
modulation
Thin films
Liquids
thin films
metals
Film thickness
film thickness
paddles
Adsorption
Volatile Organic Compounds
adsorption
Quartz crystal microbalances
volatile organic compounds
Film growth
Binding sites

Cite this

@article{191dd6bc0b5143f8ac143a1409ca350c,
title = "Highly Porous Nanocrystalline UiO-66 Thin Films via Coordination Modulation Controlled Step-by-Step Liquid-Phase Growth",
abstract = "Metal-organic frameworks (MOFs) possess exciting properties, which can be tailored by rational material design approaches. Integration of MOFs in functional nano- and mesoscale systems require selective crystallite positioning and thin-film growth techniques. Stepwise layer-by-layer liquid-phase epitaxy (LPE) emerged as one of the methods of choice to fabricate MOF@substrate systems. The layer-by-layer approach of LPE allows a precise control over the film thickness and crystallite orientation. However, these advantages were mostly observed in cases of tetra-connected dinuclear paddle-wheel MOFs and Hoffmann-type MOFs. Higher connected MOFs (consisting of nodes with 8-12 binding sites), such as the Zr-oxo cluster based families, are notoriously hard to deposit in an acceptable quality by the stepwise liquid-phase process. Herein, we report the use of coordination modulation (CM) to assist and enhance the LPE growth of UiO-66, Zr 6 O 4 (OH) 4 (bdc) 6 (bdc 2- = 1,4-benzene-dicarboxylate) films. Highly porous and crystalline thin films were obtained with good control of the crystallite domain size and film thickness in the nanoscale regime. The crystallinity (by grazing incidence X-ray diffraction), morphology (by scanning electron microscopy, atomic form microscopy), elemental composition (by X-ray photoelectron spectroscopy), binding properties (by infrared spectroscopy), and adsorption capacity (by quartz crystal microbalance adsorption experiments) for volatile organic compounds (e.g. CH 3 OH) of the fabricated thin films were investigated. These results substantiate a proof-of-concept of CM-LPE of MOFs and could be the gateway to facilitate in general the deposition of chemically very robust and higher-connected MOF thin films with automatic process-controlled LPE techniques under mild synthetic conditions.",
author = "A.L. Semrau and Suttipong Wannapaiboon and Pujari, {Sidharam P.} and Pia Vervoorts and Bauke Albada and Han Zuilhof and Fischer, {Roland A.}",
year = "2019",
month = "3",
doi = "10.1021/acs.cgd.8b01719",
language = "English",
volume = "19",
pages = "1738--1747",
journal = "Crystal Growth and Design",
issn = "1528-7483",
publisher = "American Chemical Society",
number = "3",

}

Highly Porous Nanocrystalline UiO-66 Thin Films via Coordination Modulation Controlled Step-by-Step Liquid-Phase Growth. / Semrau, A.L.; Wannapaiboon, Suttipong; Pujari, Sidharam P.; Vervoorts, Pia; Albada, Bauke; Zuilhof, Han; Fischer, Roland A.

In: Crystal Growth and Design, Vol. 19, No. 3, 03.2019, p. 1738-1747.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Highly Porous Nanocrystalline UiO-66 Thin Films via Coordination Modulation Controlled Step-by-Step Liquid-Phase Growth

AU - Semrau, A.L.

AU - Wannapaiboon, Suttipong

AU - Pujari, Sidharam P.

AU - Vervoorts, Pia

AU - Albada, Bauke

AU - Zuilhof, Han

AU - Fischer, Roland A.

PY - 2019/3

Y1 - 2019/3

N2 - Metal-organic frameworks (MOFs) possess exciting properties, which can be tailored by rational material design approaches. Integration of MOFs in functional nano- and mesoscale systems require selective crystallite positioning and thin-film growth techniques. Stepwise layer-by-layer liquid-phase epitaxy (LPE) emerged as one of the methods of choice to fabricate MOF@substrate systems. The layer-by-layer approach of LPE allows a precise control over the film thickness and crystallite orientation. However, these advantages were mostly observed in cases of tetra-connected dinuclear paddle-wheel MOFs and Hoffmann-type MOFs. Higher connected MOFs (consisting of nodes with 8-12 binding sites), such as the Zr-oxo cluster based families, are notoriously hard to deposit in an acceptable quality by the stepwise liquid-phase process. Herein, we report the use of coordination modulation (CM) to assist and enhance the LPE growth of UiO-66, Zr 6 O 4 (OH) 4 (bdc) 6 (bdc 2- = 1,4-benzene-dicarboxylate) films. Highly porous and crystalline thin films were obtained with good control of the crystallite domain size and film thickness in the nanoscale regime. The crystallinity (by grazing incidence X-ray diffraction), morphology (by scanning electron microscopy, atomic form microscopy), elemental composition (by X-ray photoelectron spectroscopy), binding properties (by infrared spectroscopy), and adsorption capacity (by quartz crystal microbalance adsorption experiments) for volatile organic compounds (e.g. CH 3 OH) of the fabricated thin films were investigated. These results substantiate a proof-of-concept of CM-LPE of MOFs and could be the gateway to facilitate in general the deposition of chemically very robust and higher-connected MOF thin films with automatic process-controlled LPE techniques under mild synthetic conditions.

AB - Metal-organic frameworks (MOFs) possess exciting properties, which can be tailored by rational material design approaches. Integration of MOFs in functional nano- and mesoscale systems require selective crystallite positioning and thin-film growth techniques. Stepwise layer-by-layer liquid-phase epitaxy (LPE) emerged as one of the methods of choice to fabricate MOF@substrate systems. The layer-by-layer approach of LPE allows a precise control over the film thickness and crystallite orientation. However, these advantages were mostly observed in cases of tetra-connected dinuclear paddle-wheel MOFs and Hoffmann-type MOFs. Higher connected MOFs (consisting of nodes with 8-12 binding sites), such as the Zr-oxo cluster based families, are notoriously hard to deposit in an acceptable quality by the stepwise liquid-phase process. Herein, we report the use of coordination modulation (CM) to assist and enhance the LPE growth of UiO-66, Zr 6 O 4 (OH) 4 (bdc) 6 (bdc 2- = 1,4-benzene-dicarboxylate) films. Highly porous and crystalline thin films were obtained with good control of the crystallite domain size and film thickness in the nanoscale regime. The crystallinity (by grazing incidence X-ray diffraction), morphology (by scanning electron microscopy, atomic form microscopy), elemental composition (by X-ray photoelectron spectroscopy), binding properties (by infrared spectroscopy), and adsorption capacity (by quartz crystal microbalance adsorption experiments) for volatile organic compounds (e.g. CH 3 OH) of the fabricated thin films were investigated. These results substantiate a proof-of-concept of CM-LPE of MOFs and could be the gateway to facilitate in general the deposition of chemically very robust and higher-connected MOF thin films with automatic process-controlled LPE techniques under mild synthetic conditions.

U2 - 10.1021/acs.cgd.8b01719

DO - 10.1021/acs.cgd.8b01719

M3 - Article

VL - 19

SP - 1738

EP - 1747

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 3

ER -