Surface‑Coordinated Metal‑Organic Framework Thin Film HKUST‑1 for Optoelectronic Applications

doi:10.19894/j.issn.1000-0518.210310

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (7): 1013-1025.DOI: 10.19894/j.issn.1000-0518.210310

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Surface‑Coordinated Metal‑Organic Framework Thin Film HKUST‑1 for Optoelectronic Applications

Xue-Xian YANG¹^,², Jian ZHANG¹^,², Zhi-Gang GU¹^,²()

^1.Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China，Fuzhou 350108，China
^2.State Key Laboratory of Chemistry for Structural Chemistry，Fujian Institute of Physical Structure，Chinese Academy of Sciences，Fuzhou 350002，China

Received:2021-06-23 Accepted:2021-10-25 Published:2022-07-01 Online:2022-07-11
Contact: Zhi-Gang GU
About author:zzgu@fjirsm.ac.cn
Supported by:
the National Natural Science Foundation of China(21872148);the Youth Innovation Promotion Association of the Chinese Academy of Sciences(2018339);the Director's Foundation of Fujian Optoelectronic Information Science and Technology Innovation Laboratory(2021ZR131)

Abstract

Abstract:

Metal-organic frameworks （MOFs） as a kind of inorganic-organic hybrid materials have potential applications in many fields due to their diverse structures and unique functionalities. In particular， liquid phase epitaxial layered MOFs films （called SURMOFs films， SURMOFs） have attracted much attention due to their controllable thickness， optimal growth orientation and uniform surface. This article summarizes the liquid phase epitaxy （LPE） layers of assembly MOFs thin film technology and methods， such as layer-by-layer （LBL） dipping method， LBL pump method， layer spray method and LBL spin coating method. The article also introduces the classical SURMOF layers of HKUST-1 assembly strategy and its related applications in photoluminescence， photochromic， photocatalytic and electrocatalysis. As one of the classical MOF materials， HKUST-1 has a wide range of applications in photoelectric field， and it has the unique properties： it can be used as a luminous carrier to achieve good optical properties； it has the advantage of unique Cu catalytic active site and can effectively degrade pollutants； it has potential applications in electronic devices because of its dielectric properties. Since SURMOF HKUST-1 has unique properties in many fields， it also faces some challenges： it needs to simplify the process of film synthesis； the structure of thin films and the mechanism of electrocatalysis also need further study； methods for reducing HKUST-1 internal resistance which can increase the conductivity also need to be improved. SURMOFs still has a long way to go for large-scale industrial applications and expansion to other unexplored areas.

Key words: Metal-organic framework HKUST-1 thin film, Liquid phase epitaxy, Layer-by-layer assembly, Optics, Electrics

CLC Number:

O611.4

Xue-Xian YANG, Jian ZHANG, Zhi-Gang GU. Surface‑Coordinated Metal‑Organic Framework Thin Film HKUST‑1 for Optoelectronic Applications[J]. Chinese Journal of Applied Chemistry, 2022, 39(7): 1013-1025.

Figures/Tables 11

Fig.1 Crystal Structure of HKUST-1

Fig.2 Illustration of the LPE layer-by-layer growth of SURMOFs［13］

Fig.3 Setup illustration for the automatic layer-by-layer dipping growth of SURMOFs［17］P0： Initial and final position of the sample holder； P1-P7： Containers of immersion solutions； 1.Teflon working table； 2. Container lid； 3. Gripper； 4. Sample holder； 5. Sample； 6. Position controller； 7. Ultrasonic bath； 8. Shower； 9. Parking position of container lid； 10. Pump and solution bottle for showering； 11. Computer

Fig.4 Setup of illustration LPE layer-by-layer pump growth of SURMOFs［19］

Fig.5 Setup illustration of LPE layer-by-layer spray growth method of SURMOFs［19］

Fig.6 Schematic representation of the setup employed for the fabrication of MOF thin films using the LPE approach adapted to the spin-coating method［20］

Fig.7 （A） Schematic diagram of Ln（pdc）3 encapsulated into SURMOF and grown insitu layer by layer using the liquid phase epitaxy method；（B） Schematic diagram of Ln（pdc）3 structure；（C） Photographs of Ln（pdc）3@HKUST-1 film on quartz glass under ultraviolet （365 nm） irradiation；（D） Solid-phase photoluminescence emission spectra of Eu（pdc）3@HKUST-1， Tb（pdc）3@HKUST-1，Gd（pdc）3@HKUST-1 films；（E） CIE chromaticity coordinate chart of red， green， blue and white emitting Ln（pdc）3@HKUST-1 film［27］

Fig.8 （A） Schematic diagram of CDs prepared by the MOF template method；（B） photos of the sample in the synthesis process；（C） photoluminescence of CD@HKUSTI-1-200 film；（D） open hole Z-sean data of CD@HKUST-1-200 film and HKUST-1 grown on quartz glass （point） and CDs aqueous solution made from G@HKUSTI-1 film with theoretical fitting data at 532 nm excitation wavelength［28］

Fig.9 （A） Schematic illustration of the preparation of hollow carbon nanospheres with Cu-TiO2 （Cu-TiO2/C） from core-shell structured SiO2@SURMOF nanospheres；（B） TEM image of SiO2@Cu-TiO2/C；（C） HRTEM image with lattice fringes of TiO2 nanoparticles existing within the sample；（D） TEM image of Cu-TiO2/C nanospheres；（E） TEM elemental mapping of C， O， Cu and Ti in hollow Cu-TiO2/C nanospheres；（F） Photocatalytic H2 production of HKUST-1-800， P25， SiO2@HKUST-1， SiO2@HKUST-1-Ti， SiO2@Cu-TiO2/C， Cu-TiO2/C and hollow Cu-TiO2/C nanospheres；（G） The recyclability of hollow Cu-TiO2/C nanospheres as photocatalysts in H2 production under simulated sunlight irradiation［33］

Fig.10 （A） Bi2O3@HKUST-1 SURMOF；（B） XRD patterns of Bi2O3@HKUST-1；（C） Photocatalytic decomposition data；（D） Carbon thin films with uniform size distribution were prepared by carbonizing SURMOF of supported metal oxygen clusters；（E） Calcinated thin films have high performance of methylene blue degradation；（F） Calcinated thin films have high performance of the reduction of nitrobenzene［34-35］

Fig.11 （A） Sample diagram of field effect transistor （OFET）；（B） Sketch diagram of HKUST-1 film modified SiO2 dielectric layer in the OFETs；（C） Structure of semiconductor polymer PTB7-Th；（D） Schematic diagram of liquid phase epitaxy layer by layer preparation of HKUST-1 and the structure；（E） The output characteristics of HKUST-1/SiO2/Si based OFETs；（F） The transmission characteristics of HKUST-1/SiO2/Si based OFETs［38］

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Surface‑Coordinated Metal‑Organic Framework Thin Film HKUST‑1 for Optoelectronic Applications

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