Oriented Growth of the Metal Organic Framework Cu₃(BTC)₂(H₂O)₃·xH₂O Tunable with Functionalized Self-Assembled Monolayers

Abstract

The tunable oriented growth of thin films of the porous framework HKUST-1 (Cu3(C9H3O6)2(H2O)3·xH2O) on different functionalized self-assembled monolayers (SAMs) is demonstrated. Films grown on carboxylate-terminated self-assembled monolayers are highly oriented along the [100] direction, while alcohol-terminated surfaces induce a completely different orientation along the [111] direction. Homogeneous but less oriented thin films are also obtained on methyl-terminated SAMs. A combination of X-ray diffraction and scanning electron microscopy was used to document the film growth on the self-assembled monolayers and to follow the morphological evolution of the crystalline phases.

Facile Syntheses of Metal-organic Framework Cu3(BTC)2(H2O)3under Ultrasound

“…The solvent is composed of water (4 mL) -ethanol (2 mL) -DMF (1 mL). In this study, in accord with previous works, all the diffraction peaks matched exactly with the pure Cu-BTC, [29][30][31][32] and no additional peak of impurities was detected. The result of the XRD patterns suggests that pure Cu-BTC can be synthesized by sonochemical method within 1 min at room temperature and atmospheric pressure.…”

“…There have been continuous efforts to improve the synthesis and activation of Cu-BTC. [30][31][32][33] Various MOFs have generally been synthesized widely by slow diffusion techniques, conventional hydrothermal and solvothermal methods. [1][2][3][4] However, the reactions used to synthesize many MOFs, particularly those with good thermal stability, require hydro/solvothermal synthesis conditions.…”

Mechanistic Insights into Growth of Surface‐Mounted Metal‐Organic Framework Films Resolved by Infrared (Nano‐) Spectroscopy

“…Subsequently, alternately immersing the SAM/Au substrates in separate metal and linker solutions, with solvent washing steps in between, assures controlled growth. Resulting SURMOF orientation is dictated by the terminating groups of the SAMs 14, 18, 19. The most studied example of a SURMOF is [Cu 3 (btc) 2 (H 2 O) n ], commonly known as HKUST‐1, which typically includes copper acetate (Cu(CH 3 COO) 2 , abbreviated here as CuAc 2 ) and 1,3,5‐benzenetricarboxylate (btc) as precursors 8, 20…”

“…for the Cu 2 (F 4 bdc) 2 ‐(dabco) SURMOF (dabco=1,4‐diazabicyclo[2.2.2]octane), but so far no conclusive results have been found for HKUST‐1 14. Therefore, fundamental understanding, and as a result further synthetic improvements, are needed in order to justify advantages of the LbL approach over other synthetic strategies 19, 24, 25, 26, 27…”

Thin Film Structures of Metal-Organic Framework [Cu3(BTC)2(H2O)3]n on TiO2(110)

“…[1][2][3] Recently, intensive studies have been reported towards MOF thin films with liquid phase epitaxy (LPE) and integration of LangmuirBlodgett film method with LPE, to control growth orientation, thickness, and morphology without losing bulk phase properties on oxide substrates, semiconductors, and self-assembled monolayers (SAMs). [4][5][6][7][8] However, these challenges have not been extended to an optically transparent semiconductor such as TiO 2 , ITO and FTO etc.…”