Intercalation of First Row Transition Metals inside Covalent-Organic Frameworks (COF): a Strategy to Fine Tune the Electronic Properties of Porous Crystalline Materials

2018 ◽  
Author(s):  
Srimanta Pakhira ◽  
Jose Mendoza-Cortes
Keyword(s):  
Transition Metal ◽  
Transition Metals ◽  
Electronic Properties ◽  
High Surface ◽  
Electronic Devices ◽  
High Surface Area ◽  
Main Role ◽  
Covalent Organic Frameworks ◽  
Porous Network ◽  
Crystalline Materials

<div>Covalent organic frameworks (COFs) have emerged as an important class of nano-porous crystalline materials with many potential applications. They are intriguing platforms for the design of porous skeletons with special functionality at the molecular level. However, despite their extraordinary properties, it is difficult to control their electronic properties, thus hindering the potential implementation in electronic devices. A new form of nanoporous material, COFs intercalated with first row transition metal is proposed to address this fundamental drawback - the lack of electronic tunability. Using first-principles calculations, we have designed 31 new COF materials <i>in-silico</i> by intercalating all of the first row transition metals (TMs) with boroxine-linked and triazine-linked COFs: COF-TM-x (where TM=Sc-Zn and x=3-5). This is a significant addition considering that only 187 experimentally COFs structures has been reported and characterized so far. We have investigated their structure and electronic properties. Specifically, we predict that COF's band gap and density of states (DOSs) can be controlled by intercalating first row transition metal atoms (TM: Sc - Zn) and fine tuned by the concentration of TMs. We also found that the $d$-subshell electron density of the TMs plays the main role in determining the electronic properties of the COFs. Thus intercalated-COFs provide a new strategy to control the electronic properties of materials within a porous network. This work opens up new avenues for the design of TM-intercalated materials with promising future applications in nanoporous electronic devices, where a high surface area coupled with fine-tuned electronic properties are desired.</div>

scholarly journals Intercalation of First Row Transition Metals inside Covalent-Organic Frameworks (COF): a Strategy to Fine Tune the Electronic Properties of Porous Crystalline Materials

2018 ◽  
Author(s):  
Srimanta Pakhira ◽  
Jose Mendoza-Cortes
Keyword(s):  
Transition Metal ◽  
Transition Metals ◽  
Electronic Properties ◽  
High Surface ◽  
Electronic Devices ◽  
High Surface Area ◽  
Main Role ◽  
Covalent Organic Frameworks ◽  
Porous Network ◽  
Crystalline Materials

<div>Covalent organic frameworks (COFs) have emerged as an important class of nano-porous crystalline materials with many potential applications. They are intriguing platforms for the design of porous skeletons with special functionality at the molecular level. However, despite their extraordinary properties, it is difficult to control their electronic properties, thus hindering the potential implementation in electronic devices. A new form of nanoporous material, COFs intercalated with first row transition metal is proposed to address this fundamental drawback - the lack of electronic tunability. Using first-principles calculations, we have designed 31 new COF materials <i>in-silico</i> by intercalating all of the first row transition metals (TMs) with boroxine-linked and triazine-linked COFs: COF-TM-x (where TM=Sc-Zn and x=3-5). This is a significant addition considering that only 187 experimentally COFs structures has been reported and characterized so far. We have investigated their structure and electronic properties. Specifically, we predict that COF's band gap and density of states (DOSs) can be controlled by intercalating first row transition metal atoms (TM: Sc - Zn) and fine tuned by the concentration of TMs. We also found that the $d$-subshell electron density of the TMs plays the main role in determining the electronic properties of the COFs. Thus intercalated-COFs provide a new strategy to control the electronic properties of materials within a porous network. This work opens up new avenues for the design of TM-intercalated materials with promising future applications in nanoporous electronic devices, where a high surface area coupled with fine-tuned electronic properties are desired.</div>

scholarly journals First Row Transition Metals Intercalation of Covalent-Organic Frameworks: A Promising Route to Tune the Material Structure and Electronic Properties

2018 ◽  
Author(s):  
Srimanta Pakhira ◽  
Jose Mendoza-Cortes
Keyword(s):  
Transition Metal ◽  
Transition Metals ◽  
Electronic Properties ◽  
Material Properties ◽  
Density Functional ◽  
Material Structure ◽  
Efficient Production ◽  
Nanoporous Material ◽  
Covalent Organic Frameworks ◽  
Porous Network

<div>Covalent organic frameworks (COFs) have emerged as an important class of nano-porous crystalline materials with many potential applications. They are intriguing platforms for the design of porous skeletons with special functionality at the molecular level. A new form of nanoporous material, transition metal intercalated COFs is proposed and its electronic properties are revealed. Using first-principles dispersion-corrected hybrid density functional theory (DFT-D), we have designed 31 new COF materials <i>in-silico</i> by intercalating all of the first row transition metals (TMs) with boroxine-linked and triazine-linked COFs. This is a significant addition considering that only 187 experimentally COFs structures has been reported and characterized so far. We have investigated their frameworks properties as well as material properties. Specifically, we predict that COF's band gap and density of states (DOSs) can be fine tuned by intercalating first row transition metal atoms (TM: Sc - Zn). The present DFT-D calculations showed that the <i>d</i>-subshell electron density of the TMs plays an important role in determining the material properties of the COFs. </div><div>The implications of controllable electronic structure and properties of intercalated COF materials for future device applications are discussed. Thus intercalated-COFs provide a new strategy to create semi-conducting and conducting materials within a rigid porous network in a highly controlled and predictable manner. This work opens up new avenues for the efficient production of TM-intercalated materials with promising future applications in nanoporous material science, electronics and chemical sensors. </div>

Intercalation of first row transition metals inside covalent-organic frameworks (COFs): a strategy to fine tune the electronic properties of porous crystalline materials

2019 ◽  
Vol 21 (17) ◽  
pp. 8785-8796 ◽  
Author(s):  
Srimanta Pakhira ◽  
Jose L. Mendoza-Cortes
Keyword(s):  
Transition Metals ◽  
Electronic Properties ◽  
Important Class ◽  
Covalent Organic Frameworks ◽  
Crystalline Materials ◽  
Potential Applications ◽  
Fine Tune

Covalent-organic frameworks (COFs) have emerged as an important class of nano-porous crystalline materials with many potential applications. Here we present an strategy to control their electronic properties.

scholarly journals Towards the room-temperature synthesis of covalent organic frameworks: a mini-review

2020 ◽  
Vol 56 (2) ◽  
pp. 1116-1132
Author(s):  
Ahmad Reza Bagheri ◽  
Nahal Aramesh
Keyword(s):  
Room Temperature ◽  
High Surface ◽  
Physical Stability ◽  
High Surface Area ◽  
Covalent Organic Frameworks ◽  
Temperature Synthesis ◽  
Crystalline Materials ◽  
Room Temperature Synthesis ◽  
Covalent Interactions ◽  
Synthesis Approach

Abstract Covalent organic frameworks (COFs) are porous and crystalline materials which are formed based on the covalent interactions between the building monomers. These materials possess fascinating properties in terms of predesignable structure, controllable morphology, and manageable functionality which distinguished them from other polymers. COFs have also high chemical and physical stability, high surface area, and high adsorption capacity that these attributes make them excellent candidates for use in different fields. However, there are several approaches for the synthesis of COFs among which room-temperature synthesis approach is a green, versatile, and popular method which is due to its exceptional properties including simplicity, easy operation, and cost-effectiveness. In this regard, this review article presents a comprehensive view of the synthesis of COFs at room temperature as well as their applications, their limitations, and also their future perspectives.

Electronic properties of quasi two-dimensional transition metals chalcogenides with low-dimensional magnetism

Doklady BGUIR ◽  
2020 ◽  
Vol 18 (7) ◽  
pp. 87-95
Author(s):  
M. S. Baranava ◽  
P. A. Praskurava
Keyword(s):  
Transition Metal ◽  
Transition Metals ◽  
Exchange Interaction ◽  
Electronic Properties ◽  
Metal Atom ◽  
Transition Metal Atom ◽  
Two Dimensional ◽  
Transition Metal Atoms ◽  
Ground Magnetic ◽  
Low Dimensional

The search for fundamental physical laws which lead to stable high-temperature ferromagnetism is an urgent task. In addition to the already synthesized two-dimensional materials, there remains a wide list of possible structures, the stability of which is predicted theoretically. The article suggests the results of studying the electronic properties of MAX3 (M = Cr, Fe, A = Ge, Si, X = S, Se, Te) transition metals based compounds with nanostructured magnetism. The research was carried out using quantum mechanical simulation in specialized VASP software and calculations within the Heisenberg model. The ground magnetic states of twodimensional MAX3 and the corresponding energy band structures are determined. We found that among the systems under study, CrGeTe3 is a semiconductor nanosized ferromagnet. In addition, one is a semiconductor with a bandgap of 0.35 eV. Other materials are antiferromagnetic. The magnetic moment in MAX3 is localized on the transition metal atoms: in particular, the main one on the d-orbital of the transition metal atom (and only a small part on the p-orbital of the chalcogen). For CrGeTe3, the exchange interaction integral is calculated. The mechanisms of the formation of magnetic order was established. According to the obtained exchange interaction integrals, a strong ferromagnetic order is formed in the semiconductor plane. The distribution of the projection density of electronic states indicates hybridization between the d-orbital of the transition metal atom and the p-orbital of the chalcogen. The study revealed that the exchange interaction by the mechanism of superexchange is more probabilistic.

Design of Transition Metal Oxide and Hybrid Mesoporous Materials

2002 ◽  
Vol 728 ◽  
Author(s):  
Clément Sanchez ◽  
Eduardo L. Crepaldi ◽  
Anne Bouchara ◽  
Florence Cagnol ◽  
David Grosso ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Oxide ◽  
High Surface ◽  
High Surface Area ◽  
Directed Assembly ◽  
Optical Quality ◽  
Hybrid Thin Films ◽  
Poly Ethylene ◽  
Inorganic Framework ◽  
Hybrid Mesoporous Materials

AbstractMesostructured transition metal (Ti, Zr, V, Al and Ce-Zr) oxide-based hybrid thin films, templated by poly(ethylene oxide)-based surfactants or block copolymers, have been prepared reproducibly, displaying 2D-hexagonal (p6m) or 2D-centred rectangular (c2m) structure. By carefully adjusting the variables involved it is possible to combine both high organisation and excellent optical quality. TiO2 and ZrO2-based materials show thermal stability up to 400-550°C. The elimination of the template can be conducted efficiently and gives rise to high surface area mesoporous films. For the other metal oxide hybrids the inorganic framework is much more fragile, and requires a precise sequence of post-treatments to be stabilised. In addition, original and homogeneous macrotextures shaped with coral-like, helical or macroporous sieves morphologies have been obtained following a nanotectonic approach based on the template-directed assembly by poly-γ-benzyl-L-glutamate (PBLG) of organically functionalised CeO2 crystalline nanoparticles.

scholarly journals Metal-Organic Framework-Based Engineered Materials—Fundamentals and Applications

Molecules ◽  
2020 ◽  
Vol 25 (7) ◽  
pp. 1598 ◽  
Author(s):  
Tahir Rasheed ◽  
Komal Rizwan ◽  
Muhammad Bilal ◽  
Hafiz M. N. Iqbal
Keyword(s):  
Drug Delivery ◽  
Metal Organic Framework ◽  
High Surface ◽  
High Surface Area ◽  
Co2 Reduction ◽  
Biological Species ◽  
Crystalline Materials ◽  
Potential Applications ◽  
Metal Organic ◽  
Catalytic Chemistry

Metal-organic frameworks (MOFs) are a fascinating class of porous crystalline materials constructed by organic ligands and inorganic connectors. Owing to their noteworthy catalytic chemistry, and matching or compatible coordination with numerous materials, MOFs offer potential applications in diverse fields such as catalysis, proton conduction, gas storage, drug delivery, sensing, separation and other related biotechnological and biomedical applications. Moreover, their designable structural topologies, high surface area, ultrahigh porosity, and tunable functionalities all make them excellent materials of interests for nanoscale applications. Herein, an effort has been to summarize the current advancement of MOF-based materials (i.e., pristine MOFs, MOF derivatives, or MOF composites) for electrocatalysis, photocatalysis, and biocatalysis. In the first part, we discussed the electrocatalytic behavior of various MOFs, such as oxidation and reduction candidates for different types of chemical reactions. The second section emphasizes on the photocatalytic performance of various MOFs as potential candidates for light-driven reactions, including photocatalytic degradation of various contaminants, CO2 reduction, and water splitting. Applications of MOFs-based porous materials in the biomedical sector, such as drug delivery, sensing and biosensing, antibacterial agents, and biomimetic systems for various biological species is discussed in the third part. Finally, the concluding points, challenges, and future prospects regarding MOFs or MOF-based materials for catalytic applications are also highlighted.

Porous-sheet-assembled Ni(OH)2/NiS arrays with vertical in-plane edge structure for supercapacitors with high stability

2019 ◽  
Vol 48 (46) ◽  
pp. 17364-17370 ◽  
Author(s):  
Lei Zhang ◽  
Hui Wang ◽  
Shan Ji ◽  
Xuyun Wang ◽  
Rongfang Wang
Keyword(s):  
Transition Metal ◽  
Surface Area ◽  
High Stability ◽  
High Surface ◽  
High Surface Area ◽  
Metal Compounds ◽  
Edge Structure ◽  
Hybrid Supercapacitors ◽  
Promising Strategy ◽  
Binder Free

The use of hierarchical arrays of transition metal compounds to fabricate a binder-free electrode is a promising strategy to achieve hybrid supercapacitors owing to their high surface area.

scholarly journals Three-Dimensional Large-Pore Covalent Organic Framework with Stp Topology

2020 ◽  
Author(s):  
Hui Li, ◽  
ding jiehua ◽  
Xinyu Guan ◽  
Fengqian Chen ◽  
Cuiyan Li ◽  
...  
Keyword(s):  
High Surface ◽  
High Surface Area ◽  
Three Dimensional ◽  
Biological Molecules ◽  
Low Density ◽  
Large Protein ◽  
Crystalline Materials ◽  
Crystalline Polymers ◽  
Large Pore ◽  
Large Pore Size

Three-dimensional (3D) covalent organic frameworks (COFs) are excellent porous crystalline polymers for numerous applications, but their building units and topological nets have been limited. Herein we report the first 3D large-pore COF with <b>stp</b> topology constructed with a 6-connected triptycene-based monomer. The new COF (termed JUC-564) has high surface area (up to 3300 m<sup>2 </sup>g<sup>-1</sup>), the largest pore (43 Å) among 3D COFs, and record-breaking low density in crystalline materials (0.108 g cm<sup>-3</sup>). The large pore size of JUC-564 is confirmed by the incorporation of a large protein. This study expands the structural varieties of 3D COFs as well as their applications for adsorption and separation of large biological molecules.

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