A galvanic replacement reaction and the Kirkendall effect in the room-temperature synthesis of tubular NiSe2: a nanozyme catalyst with peroxidase-like activity.

The synthesis of nickel selenide nanostructures under ambient conditions remains fascinating, aesthetically beautiful, and energy efficient, as most reported methods involve high-temperature techniques. In this work, we have reported the wet chemical synthesis of NiSe2 nanostructures at room temperature. The approach starts with nickel nanowires (NiNW) and selenous acid as active ingredients. Upon the incubation of NiNW in selenous acid, zero-valent metallic nickel gradually oxidised with the successive deposition of nano-selenium, a reductive product, over the pristine NiNW surface. This thermodynamically controlled galvanic replacement reaction (GRR) is favourably governed by the reduction potential values of the Ni2+/Ni and SeO32-/Se redox couples. Moreover, the selenium nanoparticles over the NiNW surface and the oxidized Ni2+ underneath then interplay during inward and outward diffusion. The different diffusivities of the elements/ions cause the generation of void interiors, thus resulting in tubular nanostructures. Therefore, both the GRR and nanoscale Kirkendall effect jointly remain engaged, resulting in the formation of hollow NiSe2 nanotubular structures. Then, we ably exploit this heterogeneous chalcogenide nanostructure material as an artificial enzyme for peroxidase mimics. This provides a method for the naked-eye detection of peroxide in solution. The peroxidase activity was selectively restrained in the presence of glutathione. Hence, a colourimetric assay was simultaneously developed for the selective detection of this biothiol. The intrinsic nanozyme activity of the substrate is hitherto unknown and can, hence, be explored further with other nanostructured nickel selenide materials.

Electrochemical aspects of coinage metal nanoparticles for catalysis and spectroscopy.

Down scaling bulk materials can cause colloidal systems to evolve into microscopically dispersed insoluble particles. Herein, we describe the interesting applications of coinage metal nanoparticles (MNPs) as colloid dispersions especially gold and silver. The rich plasmon bands of gold and silver in the visible range are elaborated using the plasmon resonance and redox potential values of grown metal microelectrode (GME). The gradation of their standard reduction potential values (E 0), as evaluated from the Gibbs free energy change for bulk metal, is ascribed to the variation in their size. Also, the effect of nucleophiles in the electrolytic cell with metal nanoparticles (MNPs) is described. The nucleophile-guided reduction potential value is considered, which is applicable even for bulk noble metals. Typically, a low value (as low as E 0 = +0.40 V) causes the oxidation of metals at the O2 (air)/H2O interface. Under this condition, the oxidation of noble metal particles and dissolution of the noble metal in water are demonstrated. Thus, metal dissolution as a function of the size of metal nanoparticles becomes eventful and demonstrable with the addition of a surfactant to the solution. Interestingly, the reversal of the nobility of gold (Au) and silver (Ag) microelectrodes at the water/electrode interface is confirmed from the evolution of normal and inverted 'core-shell' structures, exploiting visible spectrophotometry and surface-enhanced Raman scattering (SERS) analysis. Subsequently, the effect of the size, shape, and facet- and support-selective catalysis of gold nanoparticles (NPs) and the effect of incident photons on current conversion without an applied potential are briefly discussed. Finally, the synergistic effect of the emissive behaviour of gold and silver clusters is productively exploited.

Supported metal and metal oxide particles with proximity effect for catalysis.

External influence is essential for any change to occur in this world. Similarly, the reaction path of a chemical reaction can be changed with the addition of a catalyst from outside. Sometimes a catalyst performs better when it remains associated with an inert substance, which is called a support material (SM). Improved catalyst accomplishment arises from the 'proximity effect'. Even inert supports play a role in better product formulation or environmental remediation. In this review, it has been shown how the SM, as a nest, aids the catalyst particle synergistically to perform a good job in a chemical reaction. The structure-function relationship of SM helps in catalyst activation to some extent, and produces active centres that are difficult to fully ascertain. In the text, Langmuir-Hinshelwood (L-H), Mars-van Krevelen (MVK), and Eley-Rideal (E-R) mechanisms are highlighted for the adsorption processes as the case may be. Again, the importance of SM for both catalyst and substrates has been consolidated here in the text. Finally, the role of the initiator and the promoter is also discussed in this review.

Ammonium phosphomolybdate: a material for dielectric crossover and resistive switching performance.

The yellow ammonium phosphomolybdate [(NH4)3PMo12O40] (YAPM) is a robust and elegant compound that has found innumerable field applications. Herein, we have shown that this inorganic polymer serves as a novel dielectric material and a compound for memory device fabrication. It displays changeable dielectric performance and ac conductivity under UV (∼365 nm) irradiation. Drastic lowering of the dielectric constant (ε') was observed with the increase in dielectric loss factor, which was ascertained due to electron accumulation under UV exposure producing green APM (GAPM). The contributions of the Maxwell-Wagner polarization and the dipolar relaxation are correlated with the charge transfer and dielectric contribution of the material. Interestingly, the pressure-induced reduction of Mo(vi) to Mo(v) is reported for the first time and is similar to UV-exposed mixed-valence GAPM, which was corroborated by EPR spectra. In the ac signal, the crossover from quantum mechanical tunneling to hopping conduction is an adequate explanation for YAPM under UV irradiation. The fabricated device Au‖YAPM‖Au on a flexible paper substrate shows a resistive memory behavior that is modeled as a Schottky-type emission (SE) and Poole-Frenkel (PF) carrier transport for the OFF and ON states, respectively. The device exhibited a constant ON-OFF current ratio of 2 × 102 for YAPM. The OFF state endurance of the device (with 3 V pulses having 1 s time-period) under UV showed a steady increment current strength with time. After 100 s of UV exposure, the Au‖YAPM‖Au device became Au‖GAPM‖Au, and the conductivity completely shifted to a stable ON-state (at 300 s).

Benzophenone assisted UV-activated synthesis of unique Pd-nanodendrite embedded reduced graphene oxide nanocomposite: a catalyst for C-C coupling reaction and fuel cell.

In this work we report the use of benzophenone (BP) for the synthesis of a palladium (Pd) embedded on reduced graphene oxide (rGO) nanocomposite (Pd/rGO) using a simple aqueous solution and UV irradiation. The simple and facile evolution of thermodynamically unstable branched Pd(0) nanodendrites was achieved by BP photoactivation, circumventing the growth of more stable nanomorphologies. The synthesis of Pd(0)-embedded rGO nanosheets (PRGO-nd) was made possible by the simultaneous reduction of both the GO scaffold and PdCl2 by introducing BP into the photoactivation reaction. The nanocomposites obtained in the absence of BP were common triangular and twinned Pd(0) structures which were also implanted on the rGO scaffold (PRGO-nt). The disparity in morphologies presumably occurs due to the difference in the kinetics of the reduction of Pd2+ to Pd0 in the presence and absence of the BP photoinitiator. It was observed that the PRGO-nd was composed of dense arrays of multiple Pd branches around nucleation site which exhibited (111) facet, whereas PRGO-nt showed a mixture of (100) and (111) facets. On comparing the catalytic efficiencies of the as-synthesized nanocatalysts, we observed a superiority in efficiency of the thermodynamically unstable PRGO-nd nanocomposite. This is due to the evolved active facets of the dendritic Pd(0) morphology with its higher surface area, as testified by Brunauer-Emmett-Teller (BET) analysis. Since both PRGO-nd and PRGO-nt contain particles of similar size, the dents and grooves in the structure are the cause of the increase in the effective surface area in the case of nanodendrites. The unique dendritic morphology of the PRGO-nd nanostructures makes them a promising material for superior catalysis, due to their high surface area, and the high density of surface atoms at their edges, corners, and stepped regions. We investigated the efficiency of the as-prepared PRGO-nd catalyst in the Suzuki-Miyaura coupling reaction and showed its proficiency in a 2 h reaction at 60 °C using 2 mol% catalyst containing 0.06 mol% active Pd. Moreover, the electrochemical efficiency for the catalytic hydrogen evolution reaction (HER) was demonstrated, in which PRGO-nd provided a decreased overpotential of 68 mV for a current density of 10 mA cm-2, a small Tafel slope of 57 mV dec-1 and commendable stability during chronoamperometric testing for 5 h.

Carbon dot-Au(i)Ag(0) assembly for the construction of an artificial light harvesting system.

Artificial light harvesting systems (LHS) with inorganic counterparts are considered to be robust as well as mechanistically simple, where the system follows the donor-acceptor principle with an unchanged structural pattern. Plasmonic gold or silver nanoparticles are mostly chosen as inorganic counterparts to design artificial LHS. To capitalize on its electron accepting capability, Au(i) has been considered in this work for the synergistic stabilization of a system with intriguingly fluorescing silver(0) clusters produced in situ. Thus a stable fluorescent Au(i)Ag(0) assembly is generated with electron accepting capabilities. On the other hand, carbon dots have evolved as new fluorescent probes due to their unique physicochemical properties. Utilizing the simple electronic behavior of carbon dots, an electronic interaction between the fluorescent Au(i)Ag(0) and a carbon dot has been investigated for the construction of a new artificial light harvesting system. This coinage metal assembly allows surface energy transfer where it acts as an acceptor, while the carbon dot behaves as a good donor. The energy transfer efficiency has been calculated experimentally to be significant (81.3%) and the Au(i)Ag(0)-carbon dot assembly paves the way for efficient artificial LHS.

Fluorescence enhancement via varied long-chain thiol stabilized gold nanoparticles: A study of far-field effect.

Metal enhanced fluorescence of carbon dots has been reported in aqueous solution. Moderately fluorescing carbon dots (λex=360nm and λem=440nm) of 6-8nm diameters (CDA) have been synthesized from freshly prepared aqueous ascorbic acid solution under modified hydrothermal treatment. The CDA fluorescence is quenched at the close proximity with gold nanoparticles (AuNPs). Here, a substrate specific near-field electric field distribution is pronounced. Anticipating distance dependent fluorescence enhancement phenomenon, long-chain aliphatic thiol capped AuNPs are introduced to improve fluorescence of moderately fluorescing CDAs. The long-chain aliphatic thiols act as spacers between CDA and AuNP. Interestingly, the fluorescence of CDA is observed to be enhanced successively as the chain lengths of aliphatic thiols are increased. Fluorescing CDA, upon excitation, transfers energy to the nearby AuNP and a plasmon is induced. This plasmon radiates in the far-field resulting in fluorescence enhancement of CDAs. Such an interesting enhancement in emission with metallic gold is termed as gold enhanced fluorescence. This far-field effect for fluorescence enhancement of CDA particles becomes a general consensus in solution with varied long-chain aliphatic amine ligand capped silver nanoparticles (AgNPs). Finally, consequence of far-field effect of fluorescence enhancement has been observed while derivatized AuNP and AgNP are introduced into the CDA solution simultaneously which is described as reinforced fluorescence enhancement due to coupled plasmonic radiation.

Evolution of Silver-Mediated, Enhanced Fluorescent Au-Ag Nanoclusters under UV Activation: A Platform for Sensing.

Here, we report the synthesis of dopamine (DA)-mediated Au-Ag bimetallic nanoclusters in aqueous solution under UV activation. The success story emerges from monometallic fluorescent nanocluster evolution from photoactivation of gold as well as silver precursor compounds along with DA. The intriguing fluorescence property of the nanocluster relates to facile incorporation of Ag in Au, showing a 6-fold enhancement of the emission profile than simply DA-mediated Au nanoclusters. Silver effect, which is classified under the synergism, is the main reason behind such enhancement of fluorescence. The as-synthesized nanoclusters are robust and can be vacuum-dried and redispersed for repetitive application. The intriguing fluorescence of bimetallic nanoclusters is found to be quenched selectively in the presence of sulfide ion in an aqueous medium, paving the way for nanomolar detection of sulfide in water. The utility of the sensing platform has been verified employing different environmental water effluents.

One-Pot Fabrication of Perforated Graphitic Carbon Nitride Nanosheets Decorated with Copper Oxide by Controlled Ammonia and Sulfur Trioxide Release for Enhanced Catalytic Activity.

In this article, we have judiciously interfaced copper oxides with graphitic carbon nitride (g-C3N4) from thermal reaction of melamine and copper sulfate in a one-pot protocol and manipulated the perforated sheet morphology thereafter. The CCN-X (X = 30, 40, 50, 60, and 70, depending on the wt % of CuSO4·5H2O) nanocomposites were prepared by homogenously mixing different percentages of CuSO4·5H2O with melamine from a solid-state thermal reaction in a furnace in air. Drastic lowering of CuSO4 decomposition temperature due to Cu(II)-amine complex formation and subsequent reduction of Cu(II) species by in situ produced ammonia (NH3) resulted in the production of CuO and catalytic amount of Cu2O, homogeneously dispersed within the perforated g-C3N4 nanosheet. How perforated sheet morphology evolved by combined effect of NH3, released from thermal condensation of melamine ensuring two-dimensional (2D) growth, and sulfur trioxide (SO3), expelled from CuSO4·5H2O facilitating the perforation, yielding better catalytic performance, has been elucidated. Excess NH3 from added NH4Cl removed perforation and ensued a marked decrease in efficacy. However, a high proportion of CuSO4·5H2O ruptured the framework of 2D sheets because of excess SO3 evolution. Among the different nanocomposites synthesized, CCN-40 (CuO-Cu2O/g-C3N4) showed the highest catalytic activity for 4-nitrophenol reduction. Thus, enhanced efficiency of the copper oxide catalyst by interfacing it with an otherwise inactive g-C3N4 platform was achieved.

Bond-Energy-Driven, Low- or High-Angle-Grain-Boundary-Movement-Mediated Synthesis of Porous Se-Te for Use in Water-Splitting Reactions.

Herein, for the first time, we applied the metal-metal-bond-energy factor to the evolution of a porous Se-Te alloy. The porous Se-Te material has been prepared from the constituents' elemental states, through only a heating-cooling process in silicone oil without the use of any reagent, surfactant, or capping agent. Surprisingly, the reaction occurred at a much lower temperature (240 °C) than the mp (450 °C) of Te0. The reaction's nucleation and growth by means of varied bond energy have been clarified for the first time. A difference in the bond energies of a hetero metal-metal bond (Se-Te) and a homo metal-metal bond (Se-Se) directs nucleation and growth toward the fabrication of a porous structure, even from the constituents' elemental states, in which low-angle-grain-boundary (LAGB) and high-angle-grain-boundary (HAGB) movements play governing roles. Proper band-gap alignment of Se and Te makes the alloy composite applicable to water-splitting reactions under Xe-arc-lamp illumination. PEC efficiency of Se-Te was found to be higher than those reported for Se and other composite materials.

Directional growth of Ag nanorod from polymeric silver cyanide: A potential substrate for concentration dependent SERS signal enhancement leading to melamine detection.

Attention has been directed to prepare exclusive one-dimensional silver nanostructure from the linear inorganic polymer AgCN. Successive color change from yellow to orange, to red and finally to green reflects the evolution of high yielding Ag nanorods (NRs) from well-known -[Ag-CN]- chains of polymeric AgCN at room temperature. The parental 1D morphology of AgCN is retained within the as-synthesized Ag NRs. So we could successfully exploit the Ag NR for surface-enhanced Raman scattering (SERS) studies for sensing a popular milk adulterant melamine down to picomolar level. We observed interesting concentration dependent selective SERS band enhancement of melamine. The enhanced ~1327cm-1 SERS signal intensity at lower concentration (10-9 and 10-12M) of melamine speaks for the preferential participation of -C-N of melamine molecule with Ag surface. On the other hand, '-NH2' group together with ring 'N' participation of melamine molecule onto Ag surface suggested an adsorptive stance at higher (10-3-10-7M) concentration range. Thus the binding modes of the molecule at the Ag surface justify its fluxional behavior.

Facile Synthesis of Unique Hexagonal Nanoplates of Zn/Co Hydroxy Sulfate for Efficient Electrocatalytic Oxygen Evolution Reaction.

Cost-effective, highly active water oxidation catalysts are increasingly being demanded in the field of energy conversion and storage. Herein, a simple modified hydrothermally (MHT) synthesized zinc and cobalt based hydroxyl double salt, that is, Zn4-xCoxSO4(OH)6·0.5H2O (ZCS), has been exfoliated for the first time as an efficient electrocatalyst for oxygen evolution reaction (OER) in alkaline medium. Morphology investigation suggests the evolution of unique hexagonal nanoplates of ZCS material. As OER catalyst, it requires only 370 and 450 mV overpotential to achieve 10 and 100 mA cm-2 current density, respectively. More importantly, performance at the overpotential over 400 mV and durability of the designed material have been found to be superior to those of commercial RuO2 catalyst. In the designed ZCS material trace amounts of cobalt species lead to higher mass activity of 146 A g-1, compared to that of the RuO2 catalyst (83 A g-1) at the same overpotential of 370 mV. The outstanding activity and stability of the cost-effective material emerges from the promotional effect of Zn ions, which are present as the principal constituent in the electrocatalyst, and they also protect the cobalt ions in the matrix during its long-term electrochemical test. It is important to note that an appropriate ratio of zinc and cobalt ions synergistically helps to create an economically viable and environmentally suitable electrocatalyst in comparison to other related transition metal based materials.

Micelle confined mechanistic pathway for 4-nitrophenol reduction.

The model 4-nitrophenol reduction has been carried out by different groups in presence of metallic or even non-metallic catalyst elaborating different mechanistic aspects. In the present investigation, we have thoroughly studied the hydrogenation of 4-nitrophenol in a completely metal free homogeneous condition. The introduction of a non-fluorescent probe unequivocally generates a fluorescent molecule that indirectly justifies the anion radical stabilization in the micelle. The reduction mechanism under metal-free condition was proposed and the concept of stabilization of anion radical transition state of 4-nitrophenol at the positively charged Stern layer of anionic micelle was established. The plausible reduction mechanism has also enlightened the graphene-like conducting property of Stern layer of the homogeneous micellar system. Furthermore, the confinement effect for catalysis has also been authenticated by supporting experimental evidences. The borrowed concept of catalysis in confinement drives the catalytic study to a new era of catalysis.

Advance Aqueous Asymmetric Supercapacitor Based on Large 2D NiCo2O4 Nanostructures and the rGO@Fe3O4 Composite.

NiCo2O4 nanostructure is a widely studied pseudocapacitor material because of its high specific capacitance value. Most of the time, the thickness of the nanostructure inhibits the electrode material from whole-body participation and causes sluggish charge transportation. These phenomena directly interfere with the electrochemical performance of the electrode, such as specific capacitance value, stability, energy density, and so forth. Here, two different thin two-dimensional morphologies (nanosheet and nanoplate) of the NiCo2O4 nanocomposite with a large lateral size are reported using ammonia as a hydrolyzing agent. The large size and flat surface of the as-synthesized materials offer enormous active sites during the electrochemical reaction, and the thin wall makes the ion penetration and transportation very effective and facile. Therefore, the NiCo2O4 nanosheet and nanoplate structures exhibited high specific capacitance values of 1540 and 1333 F/g, respectively, with excellent rate and good cycling stability. Here also, two different advance aqueous asymmetric supercapacitors have been reported utilizing two NiCo2O4 nanostructure materials as positive electrodes and the rGO@Fe3O4 composite as a negative electrode, which exhibited excellent rate and high specific energy without sacrificing the specific power. We also studied the electrochemical activity of the rGO@Fe3O4 composite at different compositions.

Solvent Polarity-Dependent Behavior of Aliphatic Thiols and Amines toward Intriguingly Fluorescent AuAgGSH Assembly.

Highly stable fluorescent glutathione (GSH)-protected AuAg assembly has been synthesized in water under UV irradiation. The assembly is composed of small Ag2/Ag3 clusters. These clusters gain stability through synergistic interaction with Au(I) present within the assembly. This makes the overall assembly fluorescent. Here, GSH acts as a reducing as well as stabilizing agent. The assembly is so robust that it can be vacuum-dried to solid particles. The as-obtained solid is dispersible in nonaqueous solvents. The interaction between solvent and the assembly provides stability to the assembly, and the assembly shows fluorescence. It is interesting to see that the behavior of long-chain aliphatic thiols or amines toward the fluorescent assembly is altogether a different phenomenon in aqueous and nonaqueous mediums. The assembly gets ruptured in water due to direct interaction with long-chain thiols or amines, whereas in nonaqueous medium, solvation of added thiols or amines becomes pronounced, which hinders the interaction of solvent with the assembly. However, the fluorescence of the assembly is always quenched with thiols or amines no matter what the solvent medium is. In aqueous medium, the fluorescence quenching by aliphatic thiol or amine becomes pronounced with successive decrease in their chain length, whereas in nonaqueous medium, the trend is just reversed with chain length. The reasons behind such an interesting reversal of fluorescence quenching in aqueous and nonaqueous solvents have been discussed explicitly. Again, in organic solvents, thiol or amine-induced quenched fluorescence is selectively recovered by Pb(II) ion without any alteration of excitation and emission maxima. This phenomenon is not observed in water because of the ruptured fluorescent assembly. The fluorescence recovery by Pb(II) and unaltered emission peak only in nonaqueous solvent unequivocally prove the engagement of Pb(II) with thiols or amines, which in turn revert the original solvent-supported stabilization of the assembly.

Remarkable Facet Selective Reduction of 4-Nitrophenol by Morphologically Tailored (111) Faceted Cu2O Nanocatalyst.

In this work, we have disclosed the facile syntheses of morphologically diverse Cu2O nanoparticles using our laboratory designed modified hydrothermal reactor employing low-cost copper (II) acetate precursor compounds. The reaction conditions dovetail the effect of ethylene glycol (EG) and glucose to exclusively evolve the morphology tuned Cu2O nanomaterial at different pHs. The morphology tuning produces octahedron (Oh), dwarf hexapod (DHP), and elongated hexapod (EHP) Cu2O structures only with the optimized reagent concentrations. Interestingly, all of them were bestowed with a (111) facet, a superlative facet for facile nitroarene reduction. Thus, the morphology reliant catalytic reaction becomes evident. However, when used individually, EG and glucose evolve ill-defined CuO/Cu2O and Cu2O structures, respectively. We have observed that a change in pH of the medium at the onset of the reaction is obligatory for the evolution of tailor-made morphologically diverse Cu2O nanoparticles. However, preformed Cu2O particles do not suffer further structure/morphology changes under deliberate pH (6.0-9.0) change. With the as-obtained Oh, DHP, and EHP Cu2O structures, we further delve into the realm of catalysis to understand the splendor of the nanocatalyst, morphology and surface area dependence, facet selective reactivity, and other factors affecting the catalytic efficiency. The remarkable rate of catalysis of 4-nitrophenol (4-NP), evident from the catalyst activity parameter (k a = 123.6 g-1 s-1), to produce 4-aminophenol in the presence of a reducing agent like sodium borohydride (NaBH4) of the as-prepared catalysts is evidence of the collaborative effects of the effective surface area, surface positive charge, and active (111) facet of the Cu2O nanocatalyst. We have also studied the effect of other common anions, namely, Cl-, NO2 -, NO3 -, CO3 2-, and SO4 2- on the reduction process. To obtain a general consensus about facets, we compared (100) and (111) faceted Cu2O nanocatalysts not only for 4-NP reduction but also for the reduction of toxic chromium Cr(VI) in the presence of formic acid to further emphasize the importance of facet selectivity in catalysis and the versatility of the morphology tuned as-prepared Cu2O.

Boron Precursor-Dependent Evolution of Differently Emitting Carbon Dots.

Attention has been directed toward electron-deficient boron doping in carbon dots (CDs) with the expectation of revealing new photophysical aspects in accordance with varying amounts of boron content. It has been emphatically shown that boron uptake in CDs varies with different boron precursors evolving altered emissive CDs. Boron doping in CDs causes definite surface defect due to the generation of electron-deficient states. Modified hydrothermal treatment of a mixture of ascorbic acid (AA) and different boron precursor compounds (borax/boric acid/sodium borate/sodium borohydride) produces different kinds of boron-doped CDs (BCDs). These BCDs (<6 nm) differ in size, emission maxima (∼15 nm), and fluorescence intensity but carry unchanged excitation maxima (365 nm). These differences are related to the nature of boron precursor compounds. The most fluorescing BCD (quantum yield ≈ 5%) is identified from the borax-mediated reaction and is used for the detection of Fe(III) on a nanomolar level in water via the fluorescence "Turn Off" phenomenon. Again, Fe(III)-infested CD solution regains its lost fluorescence, with AA paving the way for nanomolar level AA detection from the same pot. The proposed method has been tactfully made interference free for the quantitative measure of Fe(III) and AA in real samples. Furthermore, new photophysical properties of the CDs with variable boron contents supplement information that is hitherto unknown. Theoretical calculations also justify the observed optical behavior of the as-synthesized BCDs. The calculations describe the variable amount of boron doping-related huge charge polarization within the carbon surface, leading to the formation of surface defects. Thus, subsequent electronic transition-related red shift in the absorption spectrum authenticates experimental findings.

2D materials for renewable energy storage devices: Outlook and challenges.

Scientists are looking for cost-effective, clean and durable alternative energy devices. Superior charge storage devices can easily meet the demands of our daily needs. In this respect, a material with suitable dimensions for charge storage devices has been considered to be very important. Improved performance of charge storage devices has been derived from whole-body participation and the best are from 2D materials, which provide a viable and acceptable solution.

Metal Bromide Controlled Interfacial Aromatization Reaction for Shape-Selective Synthesis of Palladium Nanostructures with Efficient Catalytic Performances.

Herein, the effect of diverse metal bromides for the shape evolution of palladium nanostructures (Pd NS) has been demonstrated. Aromaticity-driven reduction of bromopalladate(II) is optimized to reproducibly obtain different Pd NS at the water/organic layer interface. In this soft interfacial strategy, a redox potential driven reaction has been performed, forming the thermodynamically more stable (>10(4) -fold) PdBr4 (2-) precursor from PdCl4 (2-) by adding extra metal bromides. In the process, the reductant, Hantzsch dihydropyridine ester (DHPE), is aromatized. Interestingly, alkali metal bromides devoid of coordination propensity exclusively evolve Pd nanowires (Pd NWs), whereas in the case of transition metal bromides the metal ions engage the 'N' donor of DHPE at the interface, making the redox reaction sluggish. Hence, controlled Pd nanoparticles growth is observed, which evolves Pd broccolis (Pd NBRs) and Pd nanorods (Pd NRs) at the interface in the presence of NiBr2 and CuBr2 , respectively, in the aqueous solution. Thus, the effect of diverse metal bromides in the reaction mixture for tailor-made growth of the various Pd NS is reported. Among the as-synthesized materials, the Pd NWs stand to be superior catalysts and their efficiency is almost 6 and 2.5 times higher than commercial 20 % Pd/C in the electrooxidation of ethanol and Cr(VI) reduction reaction by formic acid, respectively.

Suitable Morphology Makes CoSn(OH)6 Nanostructure a Superior Electrochemical Pseudocapacitor.

Morphology of a material with different facet, edge, kink, etc., generally influences the rate of a catalytic reaction.1,2 Herein, we account for the importance of altered morphology of a nanomaterial for a supercapacitor device and employed CoSn(OH)6 as an electrode material. Suitable fabrication of a stable aqueous asymmetric supercapacitor (AAS) using metal hydroxide as positive electrode can be beneficial if the high energy density is derived without sacrificing the power density. Here we have synthesized an uncommon hierarchical mesoporous nanostructured (HNS) CoSn(OH)6 to fabricate a pseudocapacitor. In this endeavor, NH3 is found to be a well-suited hydrolyzing agent for the synthesis.3 Serendipitously, HNS was transformed into favored cubic nanostructure (CNS) in NaOH solution. In solution, NaOH acts as a structure directing as well as an etching agent. Both the samples (HNS & CNS) were used as pseudocapacitor electrodes in KOH electrolyte independently, which is reported for the first time. The HNS exhibits very high specific capacitance value (2545 F/g at 2.5 A/g specific current) with better cyclic durability over CNS sample (851 F/g at 2.5 A/g specific current). To examine the real cell application, we used HNS sample as the positive electrode material with the activated carbon (AC) as the negative electrode material for the development of an aqueous asymmetric supercapacitor (AAS). The as-fabricated AAS exhibited very high specific capacitance value of 713 F/g at a specific current of 1.5 A/g and retained 92% specific capacitance value even after 10 000 charge-discharge cycles. A maximum energy density of 63.5 Wh kg(-1) and a maximum power density of 5277 W kg(-1) were ascertained from the as-fabricated AAS, HNS CoSn(OH)6//AC.