Doctoral Dissertations

Keywords and Phrases

Cu-BTC; Electrochemistry; Epitaxy; MOFs; Thin films

Abstract

Electrochemical epitaxy is a facile and inexpensive soft-solution process to fabricate highly ordered thin films. This research focuses on the epitaxial growth of metal-organic framework (MOF) thin films by electrochemical methods which include electro-conversion and electrodeposition.

First, an electrochemical conversion pathway was invented to achieve epitaxial MOF thin films. Epitaxial single-domain Cu-BTC(111) thin films were manufactured by electrochemical oxidation of Cu2O(111) films electrodeposited on single-crystal Au(111). The single-crystal-like Cu-BTC(111) thin films with out-of-plane and in-plane order provide well-aligned 3.5 Å triangular windows along the [111] direction. Cu-BTC(111) foils were fabricated from the Cu-BTC/Cu2O system by electrochemical etching and epitaxial lift-off. Epitaxial two-domain Cu-BTC(111) films and textured Cu-BTC(111) films were produced by using low-cost and highly scalable substrates, Au on Si and Au on glass, respectively.

Second, a direct electrodeposition strategy was developed to attain epitaxial MOF thin films. Epitaxial Cu-BTC(100) thin films were electrodeposited from a water/ethanol solution on single-crystal Au(100). Epitaxial Cu-BTC(111) thin films were also electrodeposited on single-crystal Au(111) with Cu2O as a buffer layer. The single-crystal-like Cu-BTC(100) thin films with out-of-plane and in-plane order provide well-aligned 9 Å square windows along the [100] direction. The single-crystal-like Cu-BTC(111) thin films with out-of-plane and in-plane order provide well-aligned 3.5 Å triangular windows along the [111] direction.

Advisor(s)

Switzer, Jay A., 1950-

Committee Member(s)

Choudhury, Amitava
Miller, F. Scott, 1956-
Winiarz, Jeffrey G.
Nath, Manashi

Department(s)

Chemistry

Degree Name

Ph. D. in Chemistry

Publisher

Missouri University of Science and Technology

Publication Date

Summer 2025

Journal article titles appearing in thesis/dissertation

Paper I, found on pages 25–55, Epitaxial Single-Domain Cu-BTC Metal-Organic Framework Thin Films and Foils by Electrochemical Conversion of Cuprous Oxide, has been published in ACS Applied Materials & Interfaces 2023, 15(14), pp. 18440-18449.

Paper II, found on pages 56–86, Epitaxial Electrodeposition of Single-Domain Cu- BTC Metal-Organic Framework Thin Films, has been submitted to ACS Applied Materials & Interfaces. Manuscript ID: am-2025-05602z.

Pagination

x, 101 pages

Note about bibliography

Includes_bibliographical_references_(pages 89-98)

Rights

© 2025 Xiaoting Zhang , All Rights Reserved

Document Type

Dissertation - Open Access

File Type

text

Language

English

Thesis Number

T 12529

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Included in

Chemistry Commons

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