Periodic Reporting for period 2 - FC2DMOF (Development of Functional Conjugated Two-Dimensional Metal-Organic Frameworks)
Okres sprawozdawczy: 2021-08-01 do 2023-01-31
Semiconductors are essential components of most electronic circuits. As their name implies, their conductivity range lies between that of an insulator and most metals. While the movement of electrons in a circuit generates electricity, the intrinsic spin of an electron generates a magnetic moment. Given the importance of conductivity and magnetic interactions to numerous fields, the low conductivity and weak magnetic interaction of promising metal-organic frameworks (MOFs) in 3D form has limited their commercial application. 2D MOF films appear to overcome these issues but their study has been challenging. FC2DMOF plans to break the barriers to realisation of novel electronics and spintronics with the creation and characterisation of conjugated 2D MOFs exhibiting unprecedented electronic and magnetic structures, properties, and performance. The expect is to shape new discipline about MOFtronics and provide a unique class of electronic materials as complementary candidates for addressing the limits in the currently dominated silicon electronics and organic electronics.
The 21st century has seen a reinvention of how modern electronics impact our daily lives; silicon-electronics and organic electronics are currently at the core of modern electronics. Recent advances have demonstrated that conductive two-dimensional conjugated metal–organic frameworks (2D c-MOFs), as another unique class of electronic materials, are emerging to provide additional possibility for multifunctional electronic devices that brings us “MOFtronics”. The 2D c-MOFs have similar structural features to graphite and other van der Waals layer-stacked materials, and in recent years have displayed much higher conductivities (up to 2,500 S cm-1) than conventional 3D MOFs (<10-8 S cm-1) or demonstrated charge mobility of 220 cm2 V s-1 with band-like transport (Nat. Mater. 2018,17,1027). So far, around 30 2D c-MOFs have been reported based on planar polycyclic aromatic ligands with symmetrical functional groups (Nat. Mater. 2021,20,122; Chem. Soc. Rev. 2021,50,2764). However, chemical knowledge of how to construct single-crystalline 2D c-MOF bulk and film samples by molecular and synthetic design has remained a mystery. The development on reliable electronic and spintronic devices with superior performances has been rather limited.
In the half phase of FC2DMOF project, we have made fruitful achievements on 1) design and synthesis of novel conjugated ligands for the fine engineering of lattice structures and the tailoring of the electronic and magnetic structures; 2) development of highly efficient synthetic methodologies toward bulk and thin-film 2D c-MOFs, such as solution synthesis, delamination strategies, liquid-interface-assisted synthesis and chemical vapour deposition (CVD) synthesis; 3) construction of unprecedented van der Waals heterostructures; 4) discovering unique property and functions related to (opto)electronics and electrochemical energy storage/conversion devices as power sources. In the following, a brief summary is present according to the tasks of the working packages.
WP1 (Solvothermal synthesis and exfoliation): We have developed novel conjugated ligands based on benzene, phthalocyanine (Pc), Triindole and hexa-catahexabenzocoronene modified with symmetrical –OH, –NH2 and –SH functional groups. The related bulk 2D c-MOFs were constructed through the solvothermal method; some of them have been published (Adv. Mater. 2020,32,1905316; J. Am. Chem. Soc. 2021, 143, 10168; J. Am. Chem. Soc. 2020, 142, 12930). Particularly, bimetallic 2D c-MOFs with defined structures could be established based on metal-Pc ligands (Nat. Commun. 2020,11,1490). Different exfoliation approaches have been developed for the delamination of the bulk samples into nanoplates and few-layer nanosheets, such as surfactant-assisted solution exfoliation (Chem. Sci. 2020,11,7665) and sodium-assisted mechanical exfoliation (Adv. Funct. Mater. 2020,30,2002664). WP2 (Interfacial synthesis): Through the on-water surface synthesis, we have successfully prepared monolayer 2D c-MOF film based on hexathiolbenzene ligands. In addition, in combination of supramolecular chemistry and coordination polymerization on water, we have achieved the control of the layer orientation in Pc-based 2D c-MOF films toward the directional charge transport to dial-in the lateral/vertical electronic devices (J. Am. Chem. Soc. 2021, 143, 13624-13632). WP3 (CVD synthesis): TUD and CFAED have assigned an independent cleaning lab for the FC2DMOF project, which is utilized for CVD synthesis of 2D c-MOFs. Four CVD facilities have been set up during the pandemic time. The preliminary experiments have demonstrated the feasibility that we could construct few-layer 2D c-MOF films on solid substrate by CVD method. Further studies on the optimization of the CVD reaction conditions are required to develop 2D c-MOF monolayers. WP4 (Assembly of vdWs heterostructures): The interface-assisted synthetic strategy toward vdWHs has been developed (Angew. Chem. Int. Ed. 2021,60,13859). With this method, we recently constructed 2D c-MOF/graphene bilayer vdWH, which displayed ultrafast interlayer charge transfer revealed by THz spectroscopy. WP5 (characterization) and WP6 (Transport and magnetism): Chemical and physical properties have been investigated on the achieved 2D c-MOF samples. Particularly, 2D c-MOF based photodetectors have been firstly developed and could detect a broad wavelength range from UV to NIR (Adv.Mater.2020,32,1907063). In addition, the synthetic Pc-based 2D c-MOF films have been integrated into chemiresistive devices, which displayed high-performance methanol and humidity sensing with fast response/recovery and a low detection limit. Moreover, we also demonstrated that the 2D c-MOFs could act as highly efficient electrode materials for electrochemical energy storage/conversion devices.
In the half phase of FC2DMOF project, we have made fruitful achievements on 1) design and synthesis of novel conjugated ligands for the fine engineering of lattice structures and the tailoring of the electronic and magnetic structures; 2) development of highly efficient synthetic methodologies toward bulk and thin-film 2D c-MOFs, such as solution synthesis, delamination strategies, liquid-interface-assisted synthesis and chemical vapour deposition (CVD) synthesis; 3) construction of unprecedented van der Waals heterostructures; 4) discovering unique property and functions related to (opto)electronics and electrochemical energy storage/conversion devices as power sources. In the following, a brief summary is present according to the tasks of the working packages.
WP1 (Solvothermal synthesis and exfoliation): We have developed novel conjugated ligands based on benzene, phthalocyanine (Pc), Triindole and hexa-catahexabenzocoronene modified with symmetrical –OH, –NH2 and –SH functional groups. The related bulk 2D c-MOFs were constructed through the solvothermal method; some of them have been published (Adv. Mater. 2020,32,1905316; J. Am. Chem. Soc. 2021, 143, 10168; J. Am. Chem. Soc. 2020, 142, 12930). Particularly, bimetallic 2D c-MOFs with defined structures could be established based on metal-Pc ligands (Nat. Commun. 2020,11,1490). Different exfoliation approaches have been developed for the delamination of the bulk samples into nanoplates and few-layer nanosheets, such as surfactant-assisted solution exfoliation (Chem. Sci. 2020,11,7665) and sodium-assisted mechanical exfoliation (Adv. Funct. Mater. 2020,30,2002664). WP2 (Interfacial synthesis): Through the on-water surface synthesis, we have successfully prepared monolayer 2D c-MOF film based on hexathiolbenzene ligands. In addition, in combination of supramolecular chemistry and coordination polymerization on water, we have achieved the control of the layer orientation in Pc-based 2D c-MOF films toward the directional charge transport to dial-in the lateral/vertical electronic devices (J. Am. Chem. Soc. 2021, 143, 13624-13632). WP3 (CVD synthesis): TUD and CFAED have assigned an independent cleaning lab for the FC2DMOF project, which is utilized for CVD synthesis of 2D c-MOFs. Four CVD facilities have been set up during the pandemic time. The preliminary experiments have demonstrated the feasibility that we could construct few-layer 2D c-MOF films on solid substrate by CVD method. Further studies on the optimization of the CVD reaction conditions are required to develop 2D c-MOF monolayers. WP4 (Assembly of vdWs heterostructures): The interface-assisted synthetic strategy toward vdWHs has been developed (Angew. Chem. Int. Ed. 2021,60,13859). With this method, we recently constructed 2D c-MOF/graphene bilayer vdWH, which displayed ultrafast interlayer charge transfer revealed by THz spectroscopy. WP5 (characterization) and WP6 (Transport and magnetism): Chemical and physical properties have been investigated on the achieved 2D c-MOF samples. Particularly, 2D c-MOF based photodetectors have been firstly developed and could detect a broad wavelength range from UV to NIR (Adv.Mater.2020,32,1907063). In addition, the synthetic Pc-based 2D c-MOF films have been integrated into chemiresistive devices, which displayed high-performance methanol and humidity sensing with fast response/recovery and a low detection limit. Moreover, we also demonstrated that the 2D c-MOFs could act as highly efficient electrode materials for electrochemical energy storage/conversion devices.
1. We have developed novel conjugated ligands based on benzene, phthalocyanine (Pc), Triindole and hexa-catahexabenzocoronene modified with symmetrical –OH, –NH2 and –SH functional groups. New 2D c-MOFs were constructed through the solvothermal method. Particularly, bimetallic 2D c-MOFs with defined structures could be established based on metal-Pc ligands.
2. Different exfoliation approaches have been developed for the delamination of the bulk samples into nanoplates and few-layer nanosheets, such as surfactant-assisted solution exfoliation and sodium-assisted mechanical exfoliation.
3. Through the on-water surface synthesis, we have successfully prepared monolayer 2D c-MOF film based on hexathiolbenzene ligands. In addition, in combination of supramolecular chemistry and coordination polymerization on water, we have achieved the control of the layer orientation in Pc-based 2D c-MOF films toward the directional charge transport to dial-in the lateral/vertical electronic devices.
4. TUD and CFAED have assigned an independent cleaning lab for the FC2DMOF project, which is utilized for CVD synthesis of 2D c-MOFs. Four CVD facilities have been set up during the pandemic time. The preliminary experiments have demonstrated the feasibility that we could construct few-layer 2D c-MOF films on solid substrate by CVD method. Further studies on the optimization of the CVD reaction conditions are required to develop 2D c-MOF monolayers.
5. The interface-assisted synthetic strategy toward vdWHs has been developed. With this method, we recently constructed 2D c-MOF/graphene bilayer vdWH, which displayed ultrafast interlayer charge transfer revealed by THz spectroscopy.
6. Chemical and physical properties have been investigated on the achieved 2D c-MOF samples. Particularly, 2D c-MOF based photodetectors have been firstly developed and could detect a broad wavelength range from UV to NIR. In addition, the synthetic Pc-based 2D c-MOF films have been integrated into chemiresistive devices, which displayed high-performance methanol and humidity sensing with fast response/recovery and a low detection limit. Moreover, we also demonstrated that the 2D c-MOFs could act as highly efficient electrode materials for electrochemical energy storage/conversion devices.
Expected results till the end of the project: As key achievements, we expect to establish novel electronic and magnetic structures and reliable synthesis strategies, delineation of reliable structure-transport relationships and superior transport performance of C2DMOFs. The consequence is that we approach the most promising semi-conductive C2DMOF as the advanced material for electronics and spintronics. Thus this project constitutes a great synthetic/polymer chemistry challenge, but also holds tremendous promise for condensed matter physics, materials science and electronic devices.
2. Different exfoliation approaches have been developed for the delamination of the bulk samples into nanoplates and few-layer nanosheets, such as surfactant-assisted solution exfoliation and sodium-assisted mechanical exfoliation.
3. Through the on-water surface synthesis, we have successfully prepared monolayer 2D c-MOF film based on hexathiolbenzene ligands. In addition, in combination of supramolecular chemistry and coordination polymerization on water, we have achieved the control of the layer orientation in Pc-based 2D c-MOF films toward the directional charge transport to dial-in the lateral/vertical electronic devices.
4. TUD and CFAED have assigned an independent cleaning lab for the FC2DMOF project, which is utilized for CVD synthesis of 2D c-MOFs. Four CVD facilities have been set up during the pandemic time. The preliminary experiments have demonstrated the feasibility that we could construct few-layer 2D c-MOF films on solid substrate by CVD method. Further studies on the optimization of the CVD reaction conditions are required to develop 2D c-MOF monolayers.
5. The interface-assisted synthetic strategy toward vdWHs has been developed. With this method, we recently constructed 2D c-MOF/graphene bilayer vdWH, which displayed ultrafast interlayer charge transfer revealed by THz spectroscopy.
6. Chemical and physical properties have been investigated on the achieved 2D c-MOF samples. Particularly, 2D c-MOF based photodetectors have been firstly developed and could detect a broad wavelength range from UV to NIR. In addition, the synthetic Pc-based 2D c-MOF films have been integrated into chemiresistive devices, which displayed high-performance methanol and humidity sensing with fast response/recovery and a low detection limit. Moreover, we also demonstrated that the 2D c-MOFs could act as highly efficient electrode materials for electrochemical energy storage/conversion devices.
Expected results till the end of the project: As key achievements, we expect to establish novel electronic and magnetic structures and reliable synthesis strategies, delineation of reliable structure-transport relationships and superior transport performance of C2DMOFs. The consequence is that we approach the most promising semi-conductive C2DMOF as the advanced material for electronics and spintronics. Thus this project constitutes a great synthetic/polymer chemistry challenge, but also holds tremendous promise for condensed matter physics, materials science and electronic devices.