skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Electrochemistry-Induced Direct Deposition of Nanoscale Thin Zeolitic Imidazolate Framework-8 Films on Insulator Substrates

Journal Article · · Crystal Growth and Design
ORCiD logo [1];  [2];  [3]; ORCiD logo [3]
  1. Kansas State University, Manhattan, KS (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
  2. Kansas State University, Manhattan, KS (United States)
  3. Argonne National Laboratory (ANL), Argonne, IL (United States)

Electrochemical approaches have been explored as controlled means to prepare thin films of metal–organic frameworks (MOFs) on electrodes but have rarely been used to form insulator films on insulator surfaces. Herein, we report an electrochemistry-based approach to direct deposition of a thin film of zeolitic imidazolate framework-8 (ZIF-8) onto an insulator surface. The film deposition was induced by a cathodic reaction at an electrode that was placed above the insulator with a separation of ≈100 μm in a methanol solution containing ZnCl2 and 2-methylimidizole. The effects of the electrode and insulator material, applied potential, electrode–substrate distance, deposition time, and the number of deposition cycles were systematically investigated to gain insight into the deposition mechanism. The results of these measurements were consistent with a hypothesized mechanism involving cathodic base generation at the working electrode for ligand deprotonation, formation of intermediate species, their diffusion toward the substrate, and the formation of ZIF-8 on the substrate. Interestingly, the size, shape, and position of the film on the substrate replicated those of the working electrode, showing the applicability of this approach to the patterned deposition of a ZIF-8 film. In addition, film thickness could be easily controlled in the range of tens to hundreds of nanometers by adjusting the potential application conditions. Furthermore, this electrochemistry-induced method will provide a simple means for the patterned formation of a MOF film of controlled thickness on an insulator without metal precoating and thus will open the possibility of designing unique devices for various applications including chemical sensing and separations.

Research Organization:
Kansas State Univ., Manhattan, KS (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)
Grant/Contract Number:
SC0002362; AC02-567 06CH11357
OSTI ID:
1998549
Journal Information:
Crystal Growth and Design, Vol. 23, Issue 9; ISSN 1528-7483
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (53)

The Chemistry and Applications of Metal-Organic Frameworks journal August 2013
Surface-supported metal–organic framework thin films: fabrication methods, applications, and challenges journal January 2017
Metal–Organic Frameworks for Separations journal September 2011
MOF-Based Membranes for Gas Separations journal July 2020
Advances in metal–organic framework-based membranes journal January 2022
Metal–Organic Framework Materials as Chemical Sensors journal September 2011
Metal-organic framework functionalization and design strategies for advanced electrochemical energy storage devices journal July 2019
Step-by-Step Route for the Synthesis of Metal−Organic Frameworks journal December 2007
Interfacial synthesis of hollow metal–organic framework capsules demonstrating selective permeability journal April 2011
Directed Growth of Electroactive Metal-Organic Framework Thin Films Using Electrophoretic Deposition journal July 2014
Electrophoretic Nuclei Assembly for Crystallization of High-Performance Membranes on Unmodified Supports journal March 2018
Chemical vapour deposition of zeolitic imidazolate framework thin films journal December 2015
Electrosynthesis of Metal-Organic Frameworks: Challenges and Opportunities journal February 2015
Patterned Growth of Metal-Organic Framework Coatings by Electrochemical Synthesis journal July 2009
Electrochemical Synthesis of Some Archetypical Zn 2+ , Cu 2+ , and Al 3+ Metal Organic Frameworks journal June 2012
Reductive Electrosynthesis of Crystalline Metal–Organic Frameworks journal August 2011
Selective formation of biphasic thin films of metal–organic frameworks by potential-controlled cathodic electrodeposition journal January 2014
On the Mechanism of MOF-5 Formation under Cathodic Bias journal April 2015
Pt Electrodes Enable the Formation of μ 4 -O Centers in MOF-5 from Multiple Oxygen Sources journal February 2017
Oxygen‐Assisted Cathodic Deposition of Zeolitic Imidazolate Frameworks with Controlled Thickness journal January 2019
Oxygen-assisted Cathodic Deposition of Copper-Carboxylate Metal–Organic Framework Films journal April 2020
Cathodic Electrodeposition of MOF Films Using Hydrogen Peroxide journal October 2021
Electrodeposition of uranium and thorium onto small platinum electrodes
  • Reichenberger, Michael A.; Ito, Takashi; Ugorowski, Philip B.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 812 https://doi.org/10.1016/j.nima.2015.12.046
journal March 2016
Electroprecipitation of Nanometer-Thick Films of Ln(OH)3 [Ln = La, Ce, and Lu] at Pt Microelectrodes and Their Effect on Electron-Transfer Reactions journal June 2022
Paralyzed membrane: Current-driven synthesis of a metal-organic framework with sharpened propene/propane separation journal October 2018
Flexible Polypropylene-Supported ZIF-8 Membranes for Highly Efficient Propene/Propane Separation journal December 2020
Electrochemically Assisted Interfacial Growth of MOF Membranes journal November 2019
One-Step Reductive Electrodeposition of MOF Film on Polymer Membrane journal August 2022
Nanoscale Materials Patterning by Local Electrochemical Lithography : Nanoscale Materials Patterning journal January 2016
Solvent-free synthesis of supported ZIF-8 films and patterns through transformation of deposited zinc oxide precursors journal January 2013
Patterned growth of luminescent metal–organic framework films: a versatile electrochemically-assisted microwave deposition method journal January 2016
Patterned Deposition of Metal-Organic Frameworks onto Plastic, Paper, and Textile Substrates by Inkjet Printing of a Precursor Solution journal June 2013
Direct Patterning of Oriented Metal-Organic Framework Crystals via Control over Crystallization Kinetics in Clear Precursor Solutions journal March 2010
Engineering ZIF-8 Thin Films for Hybrid MOF-Based Devices journal June 2012
Lithographic Deposition of Patterned Metal-Organic Framework Coatings Using a Photobase Generator journal April 2014
Electron Beam Patterning of Metal–Organic Frameworks journal January 2021
Direct X-ray and electron-beam lithography of halogenated zeolitic imidazolate frameworks journal October 2020
Ligand-Directed Strategy for Zeolite-Type Metal–Organic Frameworks: Zinc(II) Imidazolates with Unusual Zeolitic Topologies journal February 2006
Exceptional chemical and thermal stability of zeolitic imidazolate frameworks journal June 2006
Synthesis, Structure, and Carbon Dioxide Capture Properties of Zeolitic Imidazolate Frameworks journal January 2010
Recent advances in the synthesis techniques for zeolitic imidazolate frameworks and their sensing applications journal November 2021
Zeolitic Imidazolate Framework Membranes: Novel Synthesis Methods and Progress Toward Industrial Use journal June 2022
In Situ, Time-Resolved, and Mechanistic Studies of Metal–Organic Framework Nucleation and Growth journal February 2018
Fast Nucleation and Growth of ZIF-8 Nanocrystals Monitored by Time-Resolved In Situ Small-Angle and Wide-Angle X-Ray Scattering journal July 2011
Early stage structural development of prototypical zeolitic imidazolate framework (ZIF) in solution journal January 2018
Control of Metal–Organic Framework Crystallization by Metastable Intermediate Pre‐equilibrium Species journal January 2019
In Situ Synchrotron X-ray Scattering Investigation of Cathodic ZIF-8 Deposition on Graphite Using 3D-Printed Cells journal May 2023
Tutorial on Powder X-ray Diffraction for Characterizing Nanoscale Materials journal July 2019
Structural characterization of polycrystalline thin films by X-ray diffraction techniques journal January 2021
NMR and X-ray Study Revealing the Rigidity of Zeolitic Imidazolate Frameworks journal June 2012
Contemporary Advances in the Use of Powder X-Ray Diffraction for Structure Determination journal May 2001
Self-Diffusion of Sodium, Chloride and Iodide Ions in Methanol-Water Mixture journal July 1986
Metal-Organic Frameworks for Batteries journal November 2018