J. Am. Chem. Soc.: Ligand-Oxidation-Based Anodic Synthesis of Oriented Films of Conductive M‑Catecholate Metal−Organic Frameworks with Controllable Thickness

Title：

Ligand-Oxidation-Based Anodic Synthesis of Oriented Films of Conductive M‑Catecholate Metal−Organic Frameworks with Controllable Thickness

Authors：

Min Song^1#, Jingjing Jia^1#, Pingping Li¹, Jiahao Peng¹, Xinghan Pang¹, Meiling Qi², Yulong Xu³, Long Chen^2,3, Lifeng Chi^1,4*, and Guang Lu¹*

Institutions：

¹Institute of Functional Nano & Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soo-chow University, Suzhou 215123, China

²State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, China

³Department of Chemistry, Tianjin Key Laboratory of Molecular Optoelectronic Science, Tianjin University, Tianjin 300072, China

⁴Macao Institute of Materials Science and Engineering (MIMSE), MUST-SUDA Joint Research Center for Advanced Functional Materials, Macau University of Science and Technology, Taipa 999078, Macao, China

Abstract：

Effective control over the crystallization of metal–organic framework (MOF) films is of great importance not only for the performance study and optimization in related applications but also for the fundamental understanding of the involved reticular chemistry. Featuring many technological advantages, electrochemical synthesis has been extensively reported for many MOF materials but is still challenged by the production of dense oriented films with a large-range tuning of thickness. Here, we report a ligand-oxidation-based anodic strategy capable of synthesizing oriented films of two-dimensional (2D) and three-dimensional (3D) conductive M-catecholate MOFs (2D Cu₃(HHTP)₂, 2D Zn₃(HHTP)₂, 2D Co₃(HHTP)₂, 3D YbHHTP, and 2D Cu₂TBA) with tunable thicknesses up to tens of micrometers on commonly used electrodes. This anodic strategy relies on the oxidation of redox-active catechol ligands and follows a stepwise electrochemical-chemical reaction mechanism to achieve effective control over crystallizing M-catecholate MOFs into films oriented in the [001] direction. Benefiting from the electrically conductive nature, Cu₃(HHTP)₂ films could be thickened at a steady rate (17.4 nm·min^–1) from ∼90 nm to 10.7 μm via a growth mechanism differing from those adopted in previous electrochemical synthesis of dense MOF films with limited thickness due to the self-inhibition effect. This anodic synthesis could be further combined with a templating strategy to fabricate not only films with well-defined 2D features in sizes from micrometers to millimeters but also high aspect ratio mesostructures, such as nanorods, of Cu₃(HHTP)₂.

IF：

16.383

Link：

https://doi.org/10.1021/jacs.3c05606