Functionality Modulation Toward Thianthrene-based Metal-Free Electrocatalysts for Water Splitting.

The development of metal-free bifunctional electrocatalysts for hydrogen and oxygen evolution reactions (HER and OER) is significant but rarely demonstrated. Porous organic polymers (POPs) with well-defined electroactive functionalities show superior performance in hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Precise control of the active sites' local environment requires careful modulation of linkers through the judicious selection of building units. Here, a systematic strategy is introduced for modulating functionality to design and synthesize a series of thianthrene-based bifunctional sp2 C═C bonded POPs with hollow spherical morphologies exhibiting superior electrocatalytic activity. This precise structural tuning allowed to gain insight into the effects of heteroatom incorporation, hydrophilicity, and variations in linker length on electrocatalytic activity. The most efficient bifunctional electrocatalyst THT-PyDAN achieves a current density of 10 mA cm─2 at an overpotential (η10) of ≈65 mV (in 0.5 m H2SO4) and ≈283 mV (in 1 m KOH) for HER and OER, respectively. THT-PyDAN exhibits superior activity to all previously reported metal-free bifunctional electrocatalysts in the literature. Furthermore, these investigations demonstrate that THT-PyDAN maintains its performance even after 36 h of chronoamperometry and 1000 CV cycling. Post-catalytic characterization using FT-IR, XPS, and microscopic imaging techniques underscores the long-term durability of THT-PyDAN.

Trapping and exciton-exciton annihilation assisted ultrafast carrier dynamics in nanosheets of 2H-MoSe2 and Cr doped 1T/2H-MoSe2.

Nanosheets of transition metal dichalcogenides with prospects of photocatalysis and optoelectronics applications have significant potential in device fabrication due to their low-cost production and easily controllable morphology. Here, non-degenerate pump-probe differential transmission studies with varying pump-fluence have been carried out on single-phase 2H-MoSe2 and mixed-phase 1T/2H-MoSe2 nanosheets to characterize their excited carrier dynamics. For both the samples, the differential probe transmission data show photo-induced bleaching at earlier pump-probe delay followed by photo-induced absorption unveiling signatures of exciton-state filling, exciton trapping, defect-mediated photo-induced probe absorption and recombination of defect bound excitons. The exciton trapping and photo-induced absorption by the trapped-carriers are estimated to occur with time constant of ∼430 to 500 fs based on multi-exponential modelling of the differential transmission till pump-probe delay of ∼3.5 ps. Biexponential modeling of the subsequent slow-recovery of the negative differential transmission at pump-probe delay ≳3.5 ps reveals that the exciton recombination happens via two distinct decay channels with ∼25 to 55 ps (τ1) and ≳1 ns (τ2) time constants. Pump-fluence dependent reduction in τ1 and further modelling of exciton population using higher order kinetic rate equation reveals that the two-body exciton-exciton annihilation governs the exciton recombination initially with a decay rate of ∼10-8 cm3s-1. The detailed analysis suggests that the fraction of total excitons that decay via long decay channel decreases with increasing exciton density for 2H-MoSe2, in contrast to 1T/2H-MoSe2 where the fraction of excitons decaying via long decay channel remains constant.

Chitosan-Derived N-Doped Carbon for Light-Mediated Carbon Dioxide Fixation into Epoxides.

A series of calcined Chitosan (CS) photothermal catalysts are prepared by heating the biopolymer at different temperatures. The photothermal conversion (light to heat) ability of these calcined CS materials is evaluated by measuring the temperature change with respect to time and lamp power. The material prepared at 300 °C (Cal-CS-300) shows excellent photothermal conversion ability which is explored for the CO2 cycloaddition reaction with epoxides to produce cyclic carbonates under mild reaction parameters (1 atm CO2 pressure, 25 °C). The study reveals the importance of defects present in the material on both photothermal conversion and CO2 fixation efficiency. Under optimized reaction conditions, Cal-CS-300 is able to convert a range of epoxides into their respective cyclic carbonates (>97 % selectivity) and retains its catalytic activity (~86 %) for 5 cycles of catalysis without losing its chemical integrity. The use of ubiquitously available biopolymer together with light makes this approach sustainable for preparing value added chemicals.

Phosphorus-Induced One-Step Synthesis of NiCo2S4 Electrode Material for Efficient Hydrazine-Assisted Hydrogen Production.

Rational control of the reaction parameters is highly important for synthesizing active electrocatalysts. NiCo2S4 is an excellent spinel-based electrocatalyst that is usually prepared through a two-step synthesis. Herein, a one-step hydrothermal route is reported to synthesize P-incorporated NiCo2S4. We discovered that the inclusion of P caused formation of the NiCo2S4 phase in a single step. Computational studies were performed to comprehend the mechanism of phase formation and to examine the energetics of lattice formation. Upon incorporation of the optimum amount of P, the stability of the NiCo2S4 lattice was found to increase steadily. In addition, the Bader charges on both the metal atoms Co and Ni in NiCo2S4 and P-incorporated NiCo2S4 were compared. The results show that replacing S with the optimal amount of P leads to a reduction in charge on both metal atoms, which can contribute to a more stable lattice formation. Further, the electrochemical performance of the as-synthesized materials was evaluated. Among the as-synthesized nickel cobalt sulfides, P-incorporated NiCo2S4 exhibits excellent activity toward hydrazine oxidation with an onset potential of 0.15 V vs RHE without the assistance of electrochemically active substrates like Ni or Co foam. In addition to the facile synthesis method, P-incorporated NiCo2S4 requires a very low cell voltage of 0.24 V to attain a current density of 10 mA cm-2 for hydrazine-assisted hydrogen production in a two-electrode cell. The free energy profile of the stepwise HzOR has been investigated in detail. The computational results suggested that HzOR on P-incorporated NiCo2S4 was more feasible than HzOR on NiCo2S4, and these findings corroborate the experimental evidence.

Sustainable Enhanced Sodium-Ion Storage at Subzero Temperature with LiF Integration.

Though layered sodium oxide materials are identified as promising cathodes in sodium-ion batteries, biphasic P3/O3 depicts improved electrochemical performance and structural stability. Herein, a coexistent P3/O3 biphasic cathode material was synthesized with "LiF" integration, verified with X-ray diffraction and Rietveld refinement analysis. Furthermore, the presence of Li and F was deduced by inductively coupled plasma-optical emission spectrometry (ICP-OES) and energy dispersive X-ray spectroscopy (EDS). The biphasic P3/O3 cathode displayed an excellent capacity retention of 85% after 100 cycles (0.2C/30 mA g-1) at room temperature and 94% at -20 °C after 100 cycles (0.1C/15 mA g-1) with superior rate capability as compared to the pristine cathode. Furthermore, a full cell comprising a hard carbon anode and a biphasic cathode with 1 M NaPF6 electrolyte displayed excellent cyclic stabilities at a wider temperature range of -20 to 50 °C (with the energy density of 151.48 Wh kg-1) due to the enhanced structural stability, alleviated Jahn-Teller distortions, and rapid Na+ kinetics facilitating Na+ motion at various temperatures in sodium-ion batteries. The detailed post-characterization studies revealed that the incorporation of LiF accounts for facile Na+ kinetics, boosting the overall Na storage.

Alumina-Based Bifunctional Catalyst for Efficient CO2 Fixation into Epoxides at Atmospheric Pressure.

The quest toward sustainability and decarbonization demands the development of methods for efficient carbon dioxide capture and utilization. The nonreductive CO2 fixation into epoxides to prepare cyclic carbonates has gained attention in recent years. In this work, we report the development of guanidine hydrochloride-functionalized γ alumina (γ-Al2O3), prepared using green solvents, as an efficient bifunctional catalyst for CO2 fixation. The resulting guanidine-grafted γ-Al2O3 (Al-Gh) proved to be an excellent catalyst to prepare cyclic carbonates from epoxides and CO2 with high selectivity. The nitrogen-rich Al-Gh shows increased CO2 adsorption capacity compared to that of γ-Al2O3. The as-prepared catalyst was able to carry out CO2 fixation at 85 °C under atmospheric pressure in the absence of solvents and external additives (e.g., TBAI or KI). The material showed negligible loss of catalytic activity even after five cycles of catalysis. The catalyst successfully converted many epoxides into their respective cyclic carbonates under the optimized conditions. The gram-scale synthesis of commercially important styrene carbonates from styrene oxide and CO2 using Al-Gh was also achieved. Density functional theory (DFT) calculations revealed the role of alumina in activating the epoxide. This activation facilitated the chloride ion to open the ring to react with CO2. The DFT studies also validated the role of alumina in stabilizing the electron-rich intermediates during the course of the reaction.

Ligand-Tuned Energetics for the Selective Synthesis of Ni2P and Ni12P5 Possessing Bifunctional Electrocatalytic Activity toward Hydrogen Evolution and Hydrazine Oxidation Reactions.

The occurrence of many phases and stoichiometries of nickel phosphides calls for the development of synthetic levers to selectively produce phases with purity. Herein, thiol (-SH) and carboxylate (-COO-) functional groups in ligands were found to effectively tune the energetics of nickel phosphide phases during hydrothermal synthesis. The initial kinetic product Ni2P transforms into thermodynamically stable Ni12P5 at longer reaction times. The binding of carboxylate onto Ni2P promotes this phase transformation to produce pure-phase Ni12P5 within 5 h compared to previous reports (∼48 h). Thiol-containing ligands inhibit this transformation process by providing higher stability to the Ni2P phase. Cysteine-capped Ni2P showed excellent geometric and intrinsic electrocatalytic activity toward both hydrogen evolution and hydrazine oxidation reactions under alkaline conditions. This bifunctional electrocatalytic nature enables cysteine-capped Ni2P to promote hydrazine-assisted hydrogen generation that requires lower energy (0.46 V to achieve 10 mA/cmgeo2) compared to the conventional overall water splitting (1.81 V to achieve 10 mA/cmgeo2) for hydrogen generation.

para-Aminobenzoic acid-capped hematite as an efficient nanocatalyst for solvent-free CO2 fixation under atmospheric pressure.

Utilization of carbon dioxide by converting it into value-added chemicals is a sustainable remedy approach that stipulates abundant, cheap, non-toxic and efficient catalytic materials. In this study, we have demonstrated the use of para-aminobenzoic acid-capped hematite (PABA@α-Fe2O3) as an efficient nanocatalyst for the conversion of epoxides to cyclic carbonates utilizing CO2. The developed PABA@α-Fe2O3 nanocatalyst along with a cocatalyst, tetrabutylammonium iodide (TBAI), was able to convert a variety of epoxide substrates into their corresponding cyclic carbonates under atmospheric pressure and solvent-free conditions. The efficient catalytic activity of the material is attributed to the synergistic effect between α-Fe2O3 and the amine group of the PABA molecule present on the surface. Furthermore, the recyclability study and post-catalytic analysis revealed that the developed catalyst can be used for multiple catalytic cycles due to the stable and robust nature of the nanocatalyst. The choice of the PABA@α-Fe2O3 nanocatalyst is indeed a sustainable approach from the CO2 capture and utilization point of view.

Design Principle of Monoclinic NiCo2Se4 and Co3Se4 Nanoparticles with Opposing Intrinsic and Geometric Electrocatalytic Activity toward the OER.

Despite predictions of high electrocatalytic OER activity by selenide-rich phases, such as NiCo2Se4 and Co3Se4, their synthesis through a wet-chemical route remains a challenge because of the high sensitivity of the various oxidation states of selenium to the reaction conditions. In this work, we have determined the contribution of individual reactants behind the maintenance of conducive solvothermal reaction conditions to produce phase-pure NiCo2Se4 and Co3Se4 from elemental selenium. The maintenance of reductive conditions throughout the reaction was found to be crucial for their synthesis, as a decrease in the reductive conditions over time was found to produce nickel/cobalt selenites as the primary product. Further, the reluctance of Ni(II) to oxidize into Ni(III) in comparison to the proneness of Co(II) to Co(III) oxidation was found to have a profound effect on the final product composition, as a deficiency of ions in the III oxidation state under nickel-rich reaction conditions hindered the formation of a monoclinic "Co3Se4-type" phase. Despite its lower intrinsic OER activity, Co3Se4 was found to show geometric performance on a par with NiCo2Se4 by virtue of its higher textural and microstructural properties.

Ethylene glycol-mediated one-pot synthesis of Fe incorporated α-Ni(OH)2 nanosheets with enhanced intrinsic electrocatalytic activity and long-term stability for alkaline water oxidation.

Sustainable electrocatalytic water splitting stipulates the development of cheap, efficient and stable electrocatalysts to promote comparatively sluggish oxygen evolution reaction. We have synthesized iron-incorporated pure phase α-nickel hydroxide, Ni0.8Fe0.2(OH)2 electrocatalyst utilizing N,N,N',N'-Tetramethylethane-1,2-diamine (TMEDA) and ethylene glycol (EG) following a simple one-pot synthesis process. PXRD and FTIR data suggest that the intercalation of EG in the interlayer spacing promotes amorphousness of the material. FESEM and TEM analyses suggest that the catalyst possesses hierarchical sheet-like morphology and BET measurements indicated the surface area of 50 m2 g-1 with high mesoporosity. Electrochemical studies suggest that Ni0.8Fe0.2(OH)2 prepared using water-EG mixture is the most efficient electrocatalyst for OER activity as it requires only 258 mV overpotential (considering backward LSV) on a glassy carbon electrode to achieve the benchmark current density of 10 mA cm-2geo. Additionally, the catalyst shows remarkable long-term stability for up to 7 days. The efficiency of Ni0.8Fe0.2(OH)2 electrocatalyst is reflected in its low Tafel slope (43 mV dec-1) and high OER faradaic efficiency (93%). The enhanced activity is attributed to the increase in the interlayer spacing due to the intercalation of EG into the material, which facilitates the transport of ions during the OER process. The overall improved catalytic property is due to the enhanced ionic mobility, controllable textural property, higher per-site activity and increased conductivity for the Ni0.8Fe0.2(OH)2 catalytic network.

Rejuvenating the Geometric Electrocatalytic OER Performance of Crystalline Co3 O4 by Microstructure Engineering with Sulfate.

Despite significant research on its electrocatalytic OER activity, the geometric performance of Co3 O4 has remained unsatisfactory compared to relatively amorphous Co-based materials. In particular, the activity of Co3 O4 prepared through annealing always gets inferior compared to its amorphous precursor. This demands the development of synthetic techniques to prepare Co3 O4 with superior activity as the unpredictable crystal structure of the amorphous materials makes it difficult to understand their structure-activity relationships despite higher geometric activity. In this article, we have shown that incorporation of sulfate in pre-annealed materials plays a pivotal role in boosting the OER activity of annealed Co3 O4 irrespective of the pre-annealed phase. In contrast to commonly used nitrate or carbonate that leaves the structure upon annealing and renders the resulting Co3 O4 with poor activity, sulfate remains in the annealed structure due to its thermal stability and causes a dramatic enhancement in the geometric electrocatalytic OER activity of resulting Co3 O4 compared to the pre-annealed phase. This was due to the "pore-alteration ability" and "crystallization hindrance effect" of sulfate ions that significantly alter the microstructure of the resulting Co3 O4 during annealing process by dramatically improving the surface area, pore size, and pore volume. Moreover, sulfate incorporation provided structures with considerably higher mesoporosity that is known to be conducive for reactant and product diffusion within the network. The improved textural properties led to better exposure of the catalytic centres to the electrolyte leading to higher geometric OER activity despite identical intrinsic activity of both sulfate free and incorporated Co3 O4 as confirmed from their specific activities. Further, the Co3 O4 synthesized by annealing sulfate incorporated precursor was found to be rich with oxygen defects that are known to increase the potency of a material towards electrocatalytic OER. The sulfate ions also etched out in the electrolyte during electrocatalysis leading to complete unblocking of the pores thereby helping in sustaining the high geometric OER activity. To our knowledge, this is the first report where the geometric electrocatalytic OER activity of an annealed Co3 O4 is significantly better compared to its pre-annealed phase and is in fact comparable to the activity of amorphous Co-hydroxide based compounds.

Nickel-cobalt oxalate as an efficient non-precious electrocatalyst for an improved alkaline oxygen evolution reaction.

The quest for developing next-generation non-precious electrocatalysts has risen in recent times. Herein, we have designed and developed a low cost electrocatalyst by a ligand-assisted synthetic strategy in an aqueous medium. An oxalate ligand-assisted non-oxide electrocatalyst was developed by a simple wet-chemical technique for alkaline water oxidation application. The synthetic parameters for the preparation of nickel-cobalt oxalate (Ni2.5Co5C2O4) were optimized, such as the metal precursor (Ni/Co) ratio, oxalic acid amount, reaction temperature, and time. Microstructural analysis revealed a mesoporous block-like architecture for nickel-cobalt oxalate (Ni2.5Co5C2O4). The required overpotential of Ni2.5Co5C2O4 for the alkaline oxygen evolution reaction (OER) was found to be 330 mV for achieving 10 mA cmgeo -2, which is superior to that of NiC2O4, CoC2O4, NiCo2O4 and the state-of-the-art RuO2. The splendid performance of Ni2.5Co5C2O4 was further verified by its low charge transfer resistance, impressive stability performance, and 87% faradaic efficiency in alkaline medium (pH = 14). The improved electrochemical activity was further attributed to double layer capacitance (C dl), which indefinitely divulged the inferiority of NiCo2O4 compared to Ni2.5Co5C2O4 for the alkaline oxygen evolution reaction (OER). The obtained proton reaction order (ρ RHE) was about 0.80, thus indicating the proton decoupled electron transfer (PDET) mechanism for OER in alkaline medium. Post-catalytic investigation revealed the formation of a flake-like porous nanostructure, indicating distinct transformation in morphology during the alkaline OER process. Further, XPS analysis demonstrated complete oxidation of Ni2+ and Co2+ centres into Ni3+ and Co3+, respectively under high oxidation potential, thereby indicating active site formation throughout the microstructural network. Additionally, from BET-normalised LSV investigation, the intrinsic activity of Ni2.5Co5C2O4 was also found to be higher than that of NiCo2O4. Finally, Ni2.5Co5C2O4 delivered a TOF value of around 3.28 × 10-3 s-1, which is 5.56 fold that of NiCo2O4 for the alkaline OER process. This report highlights the unique benefit of Ni2.5Co5C2O4 over NiCo2O4 for the alkaline OER. The structure-catalytic property relationship was further elucidated using density functional theory (DFT) study. To the best of our knowledge, nickel-cobalt oxalate (Ni2.5Co5C2O4) was introduced for the first time as a non-precious non-oxide electrocatalyst for alkaline OER application.

Inception of Co3O4 as Microstructural Support to Promote Alkaline Oxygen Evolution Reaction for Co0.85Se/Co9Se8 Network.

Developing electrocatalysts with abundant active sites is a substantial challenge to reduce the overpotential requirement for the alkaline oxygen evolution reaction (OER). In this work, we have aimed to improve the catalytic activity of cobalt selenides by growing them over the self-supported Co3O4 microrods. Initially, Co3O4 microrods were synthesized through annealing of an as-prepared cobalt oxalate precursor. The subsequent selenization of Co3O4 resulted in the formation of a grainy rodlike Co3O4/Co0.85Se/Co9Se8 network. The structural and morphological analysis reveals the presence of Co3O4 even after the selenization treatment where the cobalt selenide nanograins are randomly covered over the Co3O4 support. The resultant electrode shows superior electrocatalytic activity toward OER in alkaline medium by delivering a benchmark current density of 10 mA/cm2geo at an overpotential of 330 mV. As a comparison, we have developed Co0.85Se/Co9Se8 under similar conditions and evaluated its OER activity. This material consumes an overpotential of 360 mV to deliver the benchmark current density, which signifies the role of the Co3O4 support to improve the electrocatalytic activity of Co0.85Se/Co9Se8. Despite having a low TOF value for Co3O4/Co0.85Se/Co9Se8 (0.0076 s-1) compared to Co0.85Se/Co9Se8 (0.0102 s-1), the improved catalytic activity of Co3O4/Co0.85Se/Co9Se8 is attributed to the presence of a higher number of active sites rather than the improved per site activity. This is further supported from the Cdl (double layer capacitance) measurements where Co3O4/Co0.85Se/Co9Se8 and Co0.85Se/Co9Se8 tender Cdl values of about 8.19 and 1.08 mF/cm2, respectively, after electrochemical precondition. As-prepared Co3O4/Co0.85Se/Co9Se8 also manifests rapid kinetics (low Tafel slope ∼ 91 mV/dec), long-term stability, low charge-transfer resistance, and 82% Faradaic efficiency for alkaline electrocatalysis (pH = 14). Furthermore, the proton reaction order (ρRHE) is found to be 0.65, indicating a proton decoupled electron transfer (PDET) mechanism for alkaline OER. Thus, the Co3O4 support helps in the exposure of more catalytic sites of Co0.85Se/Co9Se8 to deliver the improved catalytic activities in alkaline medium.

Highly Sensitive Upconverting Nanoplatform for Luminescent Thermometry from Ambient to Cryogenic Temperature.

Precise assessment of temperature is crucial in many physical, technological, and biological applications where optical thermometry has attracted considerable attention primarily due to fast response, contactless measurement route, and electromagnetic passivity. Rare-earth-doped thermographic phosphors that rely on ratiometric sensing are very efficient near and above room temperature. However, being dependent on the thermally-assisted migration of carriers to higher excited states, they are largely limited by the quenching of the activation mechanism at low temperatures. In this paper, we demonstrate a strategy to pass through this bottleneck by designing a linear colorimetric thermometer by which we could estimate down to 4 K. The change in perceptual color fidelity metric provides an accurate measure for the sensitivity of the thermometer that attains a maximum value of 0.86 K-1 . Thermally coupled states in Er3+ are also used as a ratiometric sensor from room temperature to ∼140 K. The results obtained in this work clearly show that Yb3+ -Er3+ co-doped NaGdF4 microcrystals are a promising system that enables reliable bimodal thermometry in a very wide temperature range from ultralow (4 K) to ambient (290 K) conditions.

Triazine-based Organic Polymer-catalysed Conversion of Epoxide to Cyclic Carbonate under Ambient CO2 Pressure.

In this work we have achieved epoxide to cyclic carbonate conversion using a metal-free polymeric catalyst under ambient CO2 pressure (1.02 atm) using a balloon setup. The triazine containing polymer (CYA-ANIS) was prepared from cyanuric chloride (CYA-Cl) and o-dianisidine (ANIS) in anhydrous DMF as solvent by refluxing under the N2 gas environment. The presence of triazine and amine functional groups in the polymer results in the adsorption of CO2 up to 7 cc/g at 273 K. This inspired us to utilize the polymer for the conversion of a series of functionalised epoxides into their corresponding cyclic carbonates in the presence of tetrabutyl ammonium iodide (TBAI) as co-catalyst. The product has wide range of applications like solvent in lithium ion battery, precursor for polycarbonate, etc. The catalyst was efficient for the conversion of different mono and di-epoxides into their corresponding cyclic carbonates under atmospheric pressure in the presence of TBAI as co-catalyst. The study indicates that epoxide attached with electron withdrawing groups (like, CH2 Cl, glycidyl ether, etc.) displayed better conversion compared to simple alkane chain attached epoxides. This is mainly due to the stabilization of electron rich intermediates produced during the reaction (e. g. epoxide ring opening or CO2 incorporation into the halo-alkoxide anion). This catalyst mixture was capable to maintain its reactivity up to five cycles without losing its activity. Post catalytic characterization clearly supports the heterogeneous and recyclable nature of the catalyst.

Prudent electrochemical pretreatment to promote the OER by catalytically inert "Iron incorporated metallic Ni nanowires" synthesized via the "non-classical" growth mechanism.

This study provides new insight towards the non-classical "amorphous to crystalline" growth mechanism for metal nanowire synthesis and reports an electrochemical strategy to activate inactive materials into efficient electrocatalysts for the OER. Despite considerable research on transition metal oxides/hydroxides, especially NiFe based hydroxides as OER electrocatalysts, poor conductivity of these materials plagues their catalytic efficiency. In contrast, lack of catalytic centers hinders the OER performance of conductive metals. Herein, we devised a suitable precondition strategy to transform only the surface of conductive metallic Ni nanowires into active catalytic centers. The resulting material with intimate contact between the electrically conductive core and electrocatalytically active surface showed promising "specific" and "geometric" electrocatalytic activity towards the alkaline OER at different pH. Upon iron incorporation, the Fe centers incorporated at the surface as well as in the bulk of the nanowires were found to further boost the OER activity of these materials. A one-pot strategy was adopted to produce iron free/incorporated Ni nanowires covered with nano-spikes. Growth analysis revealed a unique "non-classical amorphous-to-crystalline transformation" to be responsible for the formation of metallic nanowires.

Inception of molybdate as a "pore forming additive" to enhance the bifunctional electrocatalytic activity of nickel and cobalt based mixed hydroxides for overall water splitting.

Development of low-cost transition metal based electrocatalysts on inexpensive substrates for overall water splitting is essential to meet the future energy storage demand. In this article, we have synthesized a molybdate incorporated nickel cobalt hydroxide material on Cu mesh with nickel : cobalt : molybdenum in a 13.25 : 21.42 : 1 ratio and the electrode has shown excellent bifunctional electrocatalytic activity as it demonstrates overpotentials as low as 290 mV and 125 mV to reach 10 mA cm-2geo for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively (after both iR and capacitance correction). Control studies with fourteen other nickel-cobalt based hydroxides and rigorous post-catalytic analysis suggested that though molybdate was not the active catalytic centre, it played a pivotal role in enhancing the activity of the material as - (i) it significantly improved the surface area and porosity of the as-synthesized material and (ii) owing to its continuous etching during electrochemical testing, it was found to increase the accessibility of electrochemically active catalytic sites lying in the bulk. Thus, molybdate acts as a "pore forming additive" during both synthesis and electrochemical treatment. Furthermore, the combination of nickel and molybdate helped in the formation of a 2D-sheet like morphology which in turn improves accessibility to catalytically active centres. In addition, the Cu mesh substrate notably lowers the charge transfer resistance. To the best of our knowledge, this is the first ever report of molybdate as a "pore forming additive" and will enthuse the designing of electrocatalytic materials with enhanced performance based on this strategy.

Methylene Blue-Loaded Upconverting Hydrogel Nanocomposite: Potential Material for Near-Infrared Light-Triggered Photodynamic Therapy Application.

The property of upconverting nanoparticles to convert the low-energy near-infrared (NIR) light into high-energy visible light has made them a potential candidate for various biomedical applications including photodynamic therapy (PDT). In this work, we show how a surface functionalization approach on the nanoparticle can be used to develop a nanocomposite hydrogel which can be of potential use for the PDT application. The upconverting hydrogel nanocomposite was synthesized by reacting 10-undecenoic acid-capped Yb3+/Er3+-doped NaYF4 nanoparticles with the thermosensitive N-isopropylacrylamide monomer. The formation of hydrogel was completed within 15 min and hydrogel nanocomposites showed strong enhancement in the visible light emission compared to the emission obtained from 10-undecenoic acid-capped Yb3+/Er3+-doped NaYF4 nanoparticles via the upconversion process (under 980 nm laser excitation). The upconverting hydrogel nanocomposites displayed high swelling behavior in water because of their porous nature. The porous structure ensured a higher loading of methylene blue dye (∼78% in 1 h) into the upconverting hydrogel, which was achieved via the swelling diffusion phenomenon. Upon excitation with the NIR light, the visible light emitted from the hydrogel activated the photosensitizer methylene blue which generated reactive oxygen species. Our results were able to show that the methylene blue-loaded composite hydrogel can be a potential platform for the future of NIR-triggered PDT in skin cancer treatment.

4-Mercaptobenzoic acid capped terbium(III)-doped CaF2 nanocrystals: a fluorescent probe for nitroaromatic pollutants.

The authors report on an energy transfer based fluorometric approach for the detection of nitroaromatic pollutants. This is achieved using 4-mercaptobenzoic acid (4-MBA)-capped CaF2:Tb3+ nanocrystals that were synthesized by a microwave procedure. 4-MBA acts as both a capping agent and a sensitizer for the Tb3+ ions in CaF2 host matrix. This approach is different from the earlier studies where Ce3+ is generally used as the sensitizer for the Ln3+ ions. The use of capping ligand as sensitizer has the feature that binding of nitroaromatics directly to the sensitizer can alter the energy transfer efficiency between the sensitizer and the Tb3+ ions. The fluorescent nanocrystal probe doped with 2% of Tb3+ displays green emission with a peak at 542 nm if photoexcited at 311 nm. The emission is quenched if the nanocrystals are exposed to nitroaromatic compounds such as 4-nitrophenol, 2,4-dinitrophenol, 2,4,6-trinitrophenol (picric acid), 4-nitrotoluene, 2,4-dinitrotoluene and 2,4,6-trinitrotoluene. These analytes also cause a (longwave/shortwave) shift in the excitation maxima which helps in identifying the individual nitroaromatic compound using single nanoprobe. The respective detection limits (by applying the 3σ/K criterion) are 0.86 µM, 0.83 µM, 0.78 µM, 0.36 µM, 1.5 µM, and 1.96 µM. Graphical abstract Schematic illustration of the use of 4-mercaptobenzoic acid (MBA)-capped CaF2:Tb3+ nanocrystals as a fluorescent nanoprobe for the detection of nitroaromatic analytes. The Tb3+ ions show strong green fluorescence via 4-MBA-induced ligand sensitization. The specific π interaction between 4-MBA capped CaF2 nanocrystals and nitroaromatics leads to reduction in the fluorescence intensity by inhibiting the energy transfer from 4-MBA to Tb3+ ion in CaF2 nanocrystals.

Classification of Transitions in Upconversion Luminescence of Lanthanides by Two-Dimensional Correlation Analysis.

Upconversion luminescence bands from Yb3+/Er3+ codoped into a matrix such as NaGdF4 can show a very complex structure on account of multiple intra-f shell transitions occurring in the presence of random crystal fields. We demonstrate that two-dimensional correlation analysis, applied to such time-integrated luminescence spectra measured as a function of excitation power, allows us to gain substantial information about the states involved in transitions, without any additional theoretical input. The detailed correlation analysis allows us not only to identify the location of various transitions but further to club them into groups on the basis of their quantum mechanical origin, and finally subclassify the transitions with each group depending on whether they have a common initial or final state.