Optically Active MXenes in Van der Waals Heterostructures.

The vertical integration of distinct 2D materials in van der Waals (vdW) heterostructures provides the opportunity for interface engineering and modulation of electronic as well as optical properties. However, scarce experimental studies reveal many challenges for vdW heterostructures, hampering the fine-tuning of their electronic and optical functionalities. Optically active MXenes, the most recent member of the 2D family, with excellent hydrophilicity, rich surface chemistry, and intriguing optical properties, are a novel 2D platform for optoelectronics applications. Coupling MXenes with various 2D materials into vdW heterostructures can open new avenues for the exploration of physical phenomena of novel quantum-confined nanostructures and devices. Therefore, the fundamental basis and recent findings in vertical vdW heterostructures composed of MXenes as a primary component and other 2D materials as secondary components are examined. Their robust designs and synthesis approaches that can push the boundaries of light-harvesting, transition, and utilization are discussed, since MXenes provide a unique playground for pursuing an extraordinary optical response or unusual light conversion features/functionalities. The recent findings are finally summarized, and a perspective for the future development of next-generation vdW multifunctional materials enriched by MXenes is provided.

Ambient Processed rGO/Ti3CNTx MXene Thin Film with High Oxidation Stability, Photosensitivity, and Self-Cleaning Potential.

Solution-based processing offers advantages for producing thin films due to scalability, low cost, simplicity, and benignity to the environment. Here, we develop conductive and photoactivated self-cleaning reduced graphene oxide (rGO)/Ti3CNTx MXene thin films via spin coating under ambient conditions. The addition of a thin rGO layer on top of Ti3CNTx resulted in up to 45-fold improvement in the environmental stability of the film compared to the bare Ti3CNTx film. The optimized rGO/Ti3CNTx thin film exhibits an optical transmittance of 74% in the visible region of the spectrum and a sheet resistance of 19 kΩ/sq. The rGO/Ti3CNTx films show high rhodamine B discoloration activity upon light irradiation. Under UV irradiation, the electrically conductive MXene in combination with in situ formed semiconducting titanium oxide induces photogenerated charge carriers, which could potentially be used in photocatalysis. On the other hand, due to film transparency, white light irradiation can bleach the adsorbed dye via photolysis. This study opens the door for using MXene thin films as multifunctional coatings with conductive and potentially self-cleaning properties.

A "One-Pot" Route for the Synthesis of Snowflake-like Dendritic CoNi Alloy-Reduced Graphene Oxide-Based Multifunctional Nanocomposites: An Efficient Magnetically Separable Versatile Catalyst and Electrode Material for High-Performance Supercapacitors.

In this paper, a simple "one pot" methodology to synthesize snowflake-like dendritic CoNi alloy-reduced graphene oxide (RGO) nanocomposites has been reported. First-principles quantum mechanical calculations based on density functional theory (DFT) have been conducted to understand the electronic structures and properties of the interface between Co, Ni, and graphene. Detailed investigations have been conducted to evaluate the performance of CoNi alloy and CoNi-RGO nanocomposites for two different types of applications: (i) as the catalyst for the reduction reaction of 4-nitrophenol and Knoevenagel condensation reaction and (ii) as the active electrode material in the supercapacitor applications. Here, the influence of microstructures of CoNi alloy particles (spherical vs snowflake-like dendritic) and the effect of immobilization of CoNi alloy on the surface of RGO on the performance of CoNi-RGO nanocomposites have been demonstrated. CoNi alloy having a snowflake-like dendritic microstructure exhibited better performance than that of spherical CoNi alloy, and CoNi-RGO nanocomposites showed improved properties compared to CoNi alloy. The k app value of the (CoNiD)60RGO40-catalyzed reduction reaction of 4-nitrophenol is 20.55 × 10-3 s-1, which is comparable and, in some cases, superior to many RGO-based catalysts. The (CoNiD)60RGO40-catalyzed Knoevenagel condensation reaction showed the % yield of the products in the range of 80-93%. (CoNiD)60RGO40 showed a specific capacitance of 501 F g-1 (at 6 A g-1), 21.08 Wh kg-1 energy density at a power density of 1650 W kg-1, and a retention of ∼85% of capacitance after 4000 cycles. These results indicate that (CoNiD)60RGO40 could be considered as a promising electrode material for high-performance supercapacitors. The synergistic effect, derived from the hierarchical structure of CoNiD-RGO nanocomposites, is the origin for its superior performance. The easy synthetic methodology, high catalytic efficiency, and excellent supercapacitance performance make (CoNiD)60RGO40 an appealing multifunctional material.

Barium Hexaferrite (BaFe12O19) Nanoparticles as Highly Active and Magnetically Recoverable Catalyst for Selective Epoxidation of Styrene to Styrene Oxide.

Herein, we are reporting the use of pure single phase barium hexaferrite (BaFe12O19) nanoparticles as an efficient catalyst for epoxidation of styrene. BaFe12O19 nanocatalysts exhibit high conversion of styrene with excellent selectivity of styrene oxide formation. Easy method of preparation, capability of catalyzing the epoxide reaction of styrene to styrene oxide with excellent styrene conversion (~91%) and high styrene oxide selectivity (~86.5%), easy magnetic separation and very good reusability make the synthesized BaFe12O19 nanocatalyst an excellent catalyst for this reaction. To the best of our knowledge, this is the first time the use of BaFe12O19 as catalyst for this reaction has been reported.

Synthesis of Various Ferrite (MFe2O4) Nanoparticles and Their Application as Efficient and Magnetically Separable Catalyst for Biginelli Reaction.

Herein, we reports the application of various spinel ferrite nanoparticles, MFe2O4 (M = Co, Ni, Cu, Zn), as efficient catalyst for Biginelli reaction. All ferrite nanoparticles were synthesized using a novel aqueous solution based method. It was observed that, the catalytic activity of the ferrite nanoparticles followed the decreasing order of CoFe2O4 > CuFe2O4 > NiFe2O4 > ZnFe2O4. The most important feature of these ferrite nanocatalysts is that, these nanoparticles can directly be used as catalyst and no surface modification or functionalization is required. These ferrite nanoparticles are easily separable from reaction mixture after reaction by using a magnet externally. Easy synthesis methodology, high catalytic activity, easy magnetic separation and good reusability make these ferrite nanoparticles attractive catalysts for Biginelli reaction.

Influence of ligand chemistry on silver nanoparticles for colorimetric detection of Cr3+ and Hg2+ ions.

In this work, we describe the role of ligand chemistry on the surfaces of silver nanoparticles (Ag NPs) for tuning their analytical applications. The citrate and melamine (MA) molecules were used as ligands for the surface modification of Ag NPs. The addition of Cr3+ ion in citrate-Ag NPs (Cit-Ag NPs) and of Hg2+ ion in melamine-Ag NPs (MA-Ag NPs) cause Ag NPs aggregation, and are accompanied by a color change and a red-shift. The resulting distinctly visual readouts are favorable for colorimetric detection of Cr3+ and Hg2+ ions. Under optimal conditions, the linear ranges are observed in the concentration ranges of 1.0-50.0 and of 10.0-100.0 µM, and with detection limit of 0.52 and 1.80 µM for Cr3+ and Hg2+ ions. The simultaneous detection of Cr3+ and Hg2+ ion is driven by the changing the ligand chemistry on the surfaces of Ag NPs that allows to tune their specific interactions with target analytes. Finally, the functionalized Ag NPs were successfully applied to detect Cr3+ and Hg2+ ions in water samples with satisfactory recoveries.

Synthesis of multifunctional CuFe2O4-reduced graphene oxide nanocomposite: an efficient magnetically separable catalyst as well as high performance supercapacitor and first-principles calculations of its electronic structures.

Here, we report an 'in situ' co-precipitation reduction based synthetic methodology to prepare CuFe2O4 nanoparticle-reduced graphene oxide (CuFe2O4-RGO) nanocomposites. First principles calculations based on Density Functional Theory (DFT) were performed to obtain the electronic structures and properties of CuFe2O4, graphene and CuFe2O4-graphene composites, and to understand the interfacial interaction between CuFe2O4 and graphene in the composite. The synergistic effect, which resulted from the combination of the unique properties of RGO and CuFe2O4 nanoparticles, was exploited to design a magnetically separable catalyst and high performance supercapacitor. It has been demonstrated that the incorporation of RGO in the composite enhanced its catalytic properties as well as supercapacitance performance compared with pure CuFe2O4. The nanocomposite with 96 wt% CuFe2O4 and 4 wt% RGO (96CuFe2O4-4RGO) exhibited high catalytic efficiency towards (i) reduction of 4-nitrophenol to 4-aminophenol, and (ii) epoxidation of styrene to styrene oxide. For both of these reactions, the catalytic efficiency of 96CuFe2O4-4RGO was significantly higher than that of pure CuFe2O4. The easy magnetic separation of 96CuFe2O4-4RGO from the reaction mixture and good reusability of the recovered catalyst also showed here. 96CuFe2O4-4RGO also demonstrated better supercapacitance performance than pure CuFe2O4. 96CuFe2O4-4RGO showed specific capacitance of 797 F g-1 at a current density of 2 A g-1, along with ∼92% retention for up to 2000 cycles. To the best of our knowledge, this is the first investigation on the catalytic properties of CuFe2O4-RGO towards the reduction of 4-nitrophenol and the epoxidation reaction, and DFT calculations on the CuFe2O4-graphene composite have been reported.

A facile synthesis methodology for preparation of Ag-Ni-reduced graphene oxide: a magnetically separable versatile nanocatalyst for multiple organic reactions and density functional study of its electronic structures.

Here, we report a simple 'in situ' co-precipitation reduction synthesis method for the preparation of nanocatalysts composed of Ag, Ni nanoparticles, and reduced graphene oxide (RGO). First-principles calculations based on Density Functional Theory (DFT) were performed to obtain the electronic structures and properties of Ag-Ni-graphene superlattice and to understand the interfacial interactions which exist at the interface between Ag, Ni, and graphene. The catalytic performance of the synthesized catalysts (Ag x Ni(1-x)) y RGO(100-y) were evaluated for four reactions (i) reduction of 4-nitrophenol (4-NP) in the presence of excess NaBH4 in aqueous medium, (ii) A3 coupling reaction for the synthesis of propargylamines, (iii) epoxidation of styrene, and (iv) 'Click reaction' for the synthesis of 1,2,3-triazole derivatives. For all of these reactions the catalyst composed of Ag, Ni, and RGO, exhibited significantly higher catalytic activity than that of pure Ag, Ni, and RGO. Moreover, an easy magnetic recovery of this catalyst from the reaction mixture after completion of the catalytic reactions and the good reusability of the recovered catalyst is also reported here. To the best of our knowledge, this is the first time the demonstration of the versatile catalytic activity of (Ag x Ni(1-x)) y RGO(100-y) towards multiple reactions, and the DFT study of its electronic structure have been reported.