Epitaxial Single-Domain Cu-BTC Metal-Organic Framework Thin Films and Foils by Electrochemical Conversion of Cuprous Oxide

Author

Xiaoting Zhang
Bin Luo
Avishek Banik
John Z. Tubbesing
Jay A. Switzer, Missouri University of Science and TechnologyFollow

Abstract

Metal-Organic Frameworks (MOFs) Are an Important Class of Crystalline Porous Materials with Extensive Chemical and Structural Merits. However, the Fabrication of MOF Thin Films Oriented Along All Crystallographic Axes to Achieve Well-Aligned Nanopores and Nanochannels with Uniform Apertures Remains a Challenge. Here, We Achieved Highly Crystalline Single-Domain MOF Thin Films with the [111] Out-Of-Plane Orientation by Electrochemical Conversion of Cuprous Oxide. Copper(II)-Benzene-1,3,5-Tricarboxylate, Cu₃(BTC)₂ (Referred to as Cu-BTC), is a Well-Known Metal-Organic Open Framework Material with a Cubic Crystal System. Epitaxial Cu-BTC(111) Thin Films Were Manufactured by Electrochemical Oxidation of Cu₂O(111) Films Electrodeposited on Single-Crystal Au(111). the Cu-BTC(111) Shows an In-Plane Antiparallel Relationship with the Precursor Cu₂O(111) with a −0.91% Coincidence Site Lattice Mismatch. a Plausible Mechanism Was Proposed for the Electrochemical Conversion of Cu₂O into Cu-BTC, Indicating Formation of Intermediate CuO, Growth of Cu-BTC Islands, and Termination with Coalesce into a Dense Film with a Limiting Thickness of About 740 Nm. the Faradaic Efficiency for the Electrochemical Conversion Was 63%. in Addition, Epitaxial Cu-BTC(111) Foils Were Fabricated by Epitaxial Lift-Off Following the Electrochemical Etching of Residual Cu2O Underneath the Cu-BTC. It Was Also Demonstrated that Cu-BTC(111) Films with Two In-Plane Domains and Textured Cu-BTC(111) Films Can Be Achieved on a Large Scale using Electrodeposited Au/Si and Au-Coated Glass as Low-Cost Substrates.

Recommended Citation

X. Zhang et al., "Epitaxial Single-Domain Cu-BTC Metal-Organic Framework Thin Films and Foils by Electrochemical Conversion of Cuprous Oxide," ACS Applied Materials and Interfaces, vol. 15, no. 14, pp. 18440 - 18449, American Chemical Society, Apr 2023.

The definitive version is available at https://doi.org/10.1021/acsami.2c22983

Department(s)

Chemistry

Comments

U.S. Department of Energy, Grant DE-FG02-08ER46518

Keywords and Phrases

Cu-BTC; cuprous oxide; electrochemical conversion; epitaxial lift-off; foils; metal−organic frameworks; single-domain

International Standard Serial Number (ISSN)

1944-8252; 1944-8244

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2023 American Chemical Society, All rights reserved.

Publication Date

12 Apr 2023

PubMed ID

37011229