Self‐Assembly and Oriented Growth of Conductive Ni‐CAT‐1 Metal‐Organic Framework at Solid–Liquid Interfaces. Issue 4 (4th December 2022)

• Record Type: Journal Article
• Authors: Shin, Sun Hae Ra; Tao, Jinhui; Canfield, Nathan L.; Bowden, Mark E.; Heo, Jaeyoung; Li, Dongsheng; Liu, Jun; De Yoreo, James J.; Thallapally, Praveen K.; Sushko, Maria L.
• Is Part Of: Advanced materials interfaces. Volume 10:Issue 4(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-12-04
• Subjects: 2D materials -- heterogeneous nucleation -- metal‐organic frameworks -- oriented growth; Materials science -- Periodicals; 620.11
• DOI: 10.1002/admi.202202031
• Languages: English
• ISSNs: 2196-7350

Abstract

Abstract: Two‐dimensional (2D) conductive metal‐organic frameworks (MOF) represent a unique class of electrode materials with high capacity and power density. Understanding molecular mechanisms and pathways for heterogeneous nucleation of 2D π‐conjugated MOFs is highly desirable for controlling the structure and properties of conductive MOFs on solid substrates. Herein, a systematic study of nucleation and growth of 2D π‐conjugated Ni‐catecholate (Ni‐CAT‐1) MOFs on highly oriented pyrolytic graphite (HOPG) and copper substrates is reported. It is discovered that the nucleation density and growth kinetics of the MOF film can be controlled by varying substrate interactions with the organic linker. Specifically, π–π interactions between the linker and the HOPG dictate lower nucleation density, whereas π–metal interactions between the linker and the copper substrate dictate faster nucleation and higher nucleation densities. These studies reveal the key mechanism for Ni‐CAT‐1 nucleation on different surfaces and provide insights into interfacial control over the growth of other 2D π‐conjugated MOF films on solid substrates to inform synthesis of functional materials. Abstract : Nucleation and growth of conductive Ni‐catecholate (Ni‐CAT‐1) metal organic frameworks at a solid/liquid interface is controlled by interactions of p‐conjugated linkers with either a p‐structure graphite or delocalized electrons of the copper substrate. These interactions dictate the preferential growth of Ni‐CAT‐1 crystals with pores vertically aligned with respect to the substrates.