Two-dimensional metal–organic
frameworks (2D MOFs) are the
next-generation 2D crystalline solids. Integrating 2D MOFs with conventional
2D materials like graphene is promising for a variety of applications,
including energy or gas storage, catalysis, and sensing. However,
unraveling the importance of chemical interaction over an additive
effect is essential. Here, we present an unconventional chemistry
to integrate a Cu-based 2D MOF, Cu-HHTP (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene),
with 2D functionalized graphene, reduced graphene oxide (rGO), by
an in situ oxidation–reduction reaction. Combined Raman spectroscopy,
electron spin resonance (ESR) spectroscopy, and X-ray photoelectron
spectroscopy (XPS) measurements along with structural analysis evidenced
the chemical interaction between Cu-HHTP and rGO, which was subsequently
assigned to be the key for the manifestation of significantly modified
physical properties. Of particular mention is the conversion of an
n-type crystalline solid to a p-type crystalline solid upon the chemical
integration of Cu-HHTP with rGO, as revealed by Seebeck coefficient.
More importantly, the thermoelectric power factor exhibited an increasing
trend with increasing temperature, unlike an opposite trend observed
due to an additive effect. The results anticipate the ability of a
redox reaction to chemically integrate other 2D MOFs with rGO and
show how an in situ synthesis can trigger chemical interaction between
two distinctive 2D materials.
Molecule-based materials exhibiting room-temperature ferromagnetism and semiconducting property are promising for molecular spintronic applications. Chemically tunable electronic and magnetic properties of metallo-phthalocyanine (MPc) molecules make them potential candidates in the frame. Here, we show room-temperature ferromagnetism in supramolecular aggregates of two diamagnetic MPcs, nickel(II) phthalocyanine (NiPc; S = 0) and zinc(II) hexadecafluorophthalocyanine (ZnFPc; S = 0). In the magnetization versus applied field (M−H) plot, recorded at room temperature, the supramolecular NiPc•••ZnFPc aggregate revealed a clear hysteresis loop with coercive field (H c ) of ∼180 Oe. The H c values were further increased with decreasing the temperature down to 95 K. The direct current (DC) electrical conductivity value of the supramolecular NiPc•••ZnFPc system was observed to be significantly higher than that of a mechanical mixture of NiPc+ZnFPc. An optical band gap of ∼1.25 eV for the supramolecular solid was estimated from the Tauc plot, and no appreciable charge-transfer interaction between NiPc and ZnFPc was detected. The origin of such unusual ferromagnetism is understood with the help of Goodenough−Kanamori−Anderson (GKA) empirical rules and the Zener model of sp−d exchange interaction.
In this work, we have synthesized nanocomposites made up of a metal–organic framework (MOF) and conducting polymers by polymerization of specialty monomers such as pyrrole (Py) and 3,4‐ethylenedioxythiophene (EDOT) in the voids of a stable and biporous Zr‐based MOF (UiO‐66). FTIR and Raman data confirmed the presence of polypyrrole (PPy) and poly3,4‐ethylenedioxythiophene (PEDOT) in UiO‐66‐PPy and UiO‐66‐PEDOT nanocomposites, respectively, and PXRD data revealed successful retention of the structure of the MOF. HRTEM images showed successful incorporation of polymer fibers inside the voids of the framework. Owing to the intrinsic biporosity of UiO‐66, polymer chains were observed to selectively occupy only one of the voids. This resulted in a remarkable enhancement (million‐fold) of the electrical conductivity while the nanocomposites retain 60–70 % of the porosity of the original MOF. These semiconducting yet significantly porous MOF nanocomposite systems exhibited ultralow thermal conductivity. Enhanced electrical conductivity with lowered thermal conductivity could qualify such MOF nanocomposites for thermoelectric applications.
In this work, we have synthesized nanocomposites made up of a metal–organic framework (MOF) and conducting polymers by polymerization of specialty monomers such as pyrrole (Py) and 3,4‐ethylenedioxythiophene (EDOT) in the voids of a stable and biporous Zr‐based MOF (UiO‐66). FTIR and Raman data confirmed the presence of polypyrrole (PPy) and poly3,4‐ethylenedioxythiophene (PEDOT) in UiO‐66‐PPy and UiO‐66‐PEDOT nanocomposites, respectively, and PXRD data revealed successful retention of the structure of the MOF. HRTEM images showed successful incorporation of polymer fibers inside the voids of the framework. Owing to the intrinsic biporosity of UiO‐66, polymer chains were observed to selectively occupy only one of the voids. This resulted in a remarkable enhancement (million‐fold) of the electrical conductivity while the nanocomposites retain 60–70 % of the porosity of the original MOF. These semiconducting yet significantly porous MOF nanocomposite systems exhibited ultralow thermal conductivity. Enhanced electrical conductivity with lowered thermal conductivity could qualify such MOF nanocomposites for thermoelectric applications.
An elegant platform to explore frustrated magnetism is the kagome spin lattice. In this work, clinoatacamite, a naturally occurring S = 1/2 kagome-like antiferromagnetic insulator, is synthesized in water at ambient pressure for the first time from a cuprous chloride (CuCl) precursor whereby Cu(I) was spontaneously oxidized to Cu(II) in the form of clinoatacamite [Cu 2 (OH) 3 Cl] with a simultaneous reduction of graphene oxide (GO) to reduced graphene oxide (rGO) in one pot. A stable nanocomposite of phase-pure clinoatacamite nanocrystals embedded in the rGO matrix was isolated. The clinoatacamite−rGO nanocomposite was determined to be magnetically active with a markedly enhanced coercive field of ∼2500 Oe at 5 K as well as electronically active with a conductivity value of ∼200 S•m −1 at 300 K. Our results illustrate an avenue of combining exotic magnetic and electronic lattices without impeding their individual characteristics and synergistically generating a new class of magnetic semiconductors.
Electrically
conductive metal–organic coordination polymers
(CPs) are promising candidates for a variety of technological applications.
However, poor energetic and spatial overlap between the
sp
-electrons of organic ligands and the
d
-electrons
of metal ion often blocks an effective charge transport (mobility)
across CPs. Herein, we present a bimetallic design principle for enhancing
carrier mobility in CPs. Bimetallic CPs of Fe(III) and Cr(III) ions
coordinated to 1,3,5-benzenetricarboxylic acid (BTC) ligand (Fe–BTC–Cr)
exhibited remarkably high carrier mobility at the matching mole ratio
(1:1) with enhancement factors of 10
2
and 10
4
in comparison to those of monometallic parents, Fe–BTC and
Cr–BTC, respectively. The observation was substantiated by
lowering of the band gap between the valence band and the conduction
band upon the formation of a hybrid
p
–
n
-type structure in the bimetallic CPs. The direct current
conductivity values of the CPs measured by four-probe technique were
in good agreement with the alternating current conductivity values
obtained from the electrochemical impedance spectroscopy. Our flexible
approach of picking and choosing the appropriate combination of metal
ions from the periodic table is expected to generate various CPs with
desirable semiconducting properties.
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