Unusual enhancement in efficiency of DSSCs upon modifying photoanodes with reduced graphene oxide.

Reduced graphene oxide (rGO) has emerged as an excellent interfacial material for improvising the performance of dye-sensitized solar cells (DSSC). Herein, we have applied rGO as interfacial layers between a fluorine doped tin oxide (FTO) coated glass substrate and semiconducting material TiO2 in a photoanode of a DSSC which showed an unusual enhancement in generating a photocurrent in comparison to the control (without rGO layers). An electrochemical impedance spectroscopy (EIS) study was performed to gain the mechanistic insights into such a remarkable enhancement of photoelectric conversion efficiency (PCE) which revealed improved charge transfer and suppressed charge recombination due to high-electrical conductivity and probably more negative work function of our rGO material compared to the bare TiO2 photoanode.

Exploring Magnetic XY Behavior in a Quasi-2D Anisotropic Triangular Lattice of Cu(II) by Functionalized Graphene.

Study on magnetism in two-dimensional (2D) spin-lattices is advancing rapidly. In this work, phase-pure botallackite (Bo) (Cu2(OH)3Br), a quasi-2D S = 1/2 anisotropic triangular spin-lattice is stabilized over 2D reduced graphene oxide (rGO) nanosheets via simple oxidation-reduction reaction chemistry. In comparison to polycrystalline Bo, such an anchoring resulted in the oriented growth of Bo crystallites in the Bo-rGO system. The Bo-rGO nanocomposite was found to be magnetically active with a Néel transition at ∼8.9 K, crossing over to possible XY anisotropy at ∼5 K-as revealed by complementary dc and ac susceptibility measurements-an unprecedented observation in the field assigned to an interfacial effect. This work demonstrates the potential usage of nonmagnetic 2D functionalized graphene to significantly modulate the magnetic properties of 2D spin-lattices.

Embedding S = 1/2 Kagome-like Lattice in Reduced Graphene Oxide.

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 [Cu2(OH)3Cl] 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.

Metamagnetism in Nanosheets of CoII-MOF with TN at 26 K and a Giant Hysteretic Effect at 5 K.

Herein, we have synthesized at room-temperature two-dimensional nanosheets of a MOF comprised of cobalt(II) ion with benzenedicarboxylic acid  ligand, which exhibited unusual magnetic properties. Direct-current magnetic susceptibility revealed an antiferromagnetic (AFM) transition at 26 K (Néel temperature,  TN) followed by a canting of the spin moments along with the concomitant appearance of a sigmoidal-shaped magnetization versus field ( M- H) curve at 15 K. Such a canted AFM ordering led to nonzero remnant magnetization with a remarkably high coercive field of ∼10 kOe at 5 K. Metamagnetism was further substantiated by the alternating-current magnetic susceptibility measurements.

Spontaneous Reduction of Copper(II) to Copper(I) at Solid-Liquid Interface.

Oxidation and reduction reactions are of central importance in chemistry as well as vital to the basic functions of life and such chemical processes are generally brought about by oxidizing and reducing agents, respectively. Herein, we report the discovery of an interfacial reduction reaction (IRR) - without the use of any external reducing agent. In course of metal-ligand coordination, spontaneous reduction of Cu(II) to Cu(I) at a solid-liquid interface was observed-unlike in a liquid-phase reaction where no reduction of Cu(II) to Cu(I) was occurred. High-quality thin films of a new coordination network compound bearing a Fe(II)-CN-Cu(I) link were fabricated by IRR and employed for efficient electro-catalysis in the form of oxygen reduction reaction. Also, thermally activated reversible structural phase transition modulated the electron transport property in thin film. This work unveils the importance of chemical reactions at solid-liquid interfaces that can lead to the development of new functional thin film materials.

Thermally Driven Resistive Switching in Solution-Processable Thin Films of Coordination Polymers.

Metal-organic coordination polymers (CPs) downsized to thin films with controllable electrical conductivity are promising for electronic device applications. Here we demonstrate, for the first time, thermally driven resistive switching in thin films of semiconducting CPs consisting of silver ion and tetracyanoquinodimethane ligand (Ag-TCNQ). High-quality and highly hydrophobic thin films of Ag-TCNQ were fabricated through a layer-by-layer approach upon sacrificing a predeposited layer of Cu-TCNQ on a thiolated Au substrate. Reversible switching between the high-resistance state (HRS) at 300 K and the low-resistance state (LRS) at 400 K with an enhancement factor of as high as ∼106 in the electrical resistance was realized. The phenomenon is attributed to the alternation of the Schottky barrier at the metal-semiconductor interface by thermal energy and not due to the formation of a conductive filament. Our discovery of thermally driven resistive switching as well as sacrificial growth of CP thin films on an organically modified substrate holds promise for the development of solution-processable nonvolatile memory devices.

Giant Enhancement of Carrier Mobility in Bimetallic Coordination Polymers.

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 102 and 104 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.

Increase in Electrical Conductivity of MOF to Billion-Fold upon Filling the Nanochannels with Conducting Polymer.

Redox-active pyrrole (Py) monomers were intercalated into 1D nanochannels of [Cd(NDC)0.5(PCA)]·Gx (H2NDC = 2,6-napthalenedicarboxylic acid, HPCA = 4-pyridinecarboxylic acid, G = guest molecules) (1) - a fluorescent 3D MOF (λem = 385 nm). Subsequent activation of 1⊃Py upon immersing into iodine (I2) solution resulted in an increment of the bulk electrical conductivity by ∼9 orders of magnitude. The unusual increase in conductivity was attributed to the formation of highly oriented and conducting polypyrrole (PPy) chains inside 1D nanochannels and specific host-guest interaction in 1⊃PPy thereof. The Hall-effect measurements suggested 1⊃PPy to be an n-type semiconductor material with remarkably high-carrier density (η) of ∼1.5 × 10(17) cm(-3) and mobility (µ) of ∼8.15 cm(2) V(-1) s(-1). The fluorescence property of 1 was almost retained in 1⊃PPy with concomitant exciplex-type emission at higher wavelength (λem = 520 nm). The here-presented results on [MOF⊃Conducting Polymer] systems in general will serve as a prototype experiment toward rational design for the development of highly conductive yet fluorescent MOF-based materials for various optoelectronic applications.