Melamine-Based Hydrogen-bonded Systems as Organoelectrocatalysts for Water Oxidation Reaction.

Applications of small organic molecules and hydrogen-bonded aggregates, instead of traditional transition-metal-based electrocatalysts, are gaining momentum for addressing the issue of low-cost generation of H2 to power a sustainable environment. Such systems offer the possibility to integrate desired functional moieties with predictive structural repetition for modulating their properties. Despite these advantages, hydrogen-bonded organic systems have largely remained unexplored, especially as electrocatalysts. Melamine and adipic acid-based hydrogen-bonded organic ionic (BMA) and co-crystal systems developed under varying temperatures are explored as electrocatalysts for water oxidation reaction (WOR). These systems are easily modifiable with precisely designed molecular architecture and judiciously positioned nitrogen atoms. Combined effect of charge-assisted hydrogen bonding stabilizes the ionic BMA system under corrosive alkaline conditions and augments its remarkable electrocatalytic WOR activity, achieving a current density of 10 mA cm-2 at an overpotential of 387 mV and Faradaic efficiency ∼94.5 %. The enhanced electrocatalytic ability of BMA is attributed to its hydrophilic nature, unique molecular composition with complementary hydrogen-bonded motifs and a high density of positively charged nitrogen atoms on the surface, that facilitates electrostatic interactions and accelerate charge and mass transport processes culminating in a turnover frequency of ∼0.024 s-1 . This work validates the potential of hydrogen-bonded molecular organo-electrocatalysts towards WOR.

Brønsted Acid-Functionalized Ionic Co(II) Framework: A Tailored Vessel for Electrocatalytic Oxygen Evolution and Size-Exclusive Optical Speciation of Biothiols.

Metal-organic frameworks (MOFs) not only combine globally demanded renewable energy generation and environmental remediation onto a single platform but also rationalize structure-performance synergies to devise smarter materials with remarkable performance. The robust and non-interpenetrated cationic MOF exemplifies a unique bifunctional scaffold for the efficient electrochemical oxygen evolution reaction (OER) and ultrasensitive monitoring of biohazards. The microporous framework containing Brønsted acid-functionalized [Co2(µ2-OH)(CO2)2] secondary building units (SBUs) exhibits remarkable OER performance in 1 M KOH, requiring 410 mV overpotential to obtain 10 mA cm-2 anodic current density, and a low Tafel slope of 55 mV/dec with 93.1% Faradaic efficiency. Apart from the high turnover frequency and electrochemically assessable surface area, steady OER performance over 500 cycles under potentiodynamic and potentiostatic conditions result in long-term catalyst durability. The highly emissive attribute from nitrogen-rich fluorescent struts benefits the MOF in recyclable and selective fluoro-detection of three biothiols (l-cysteine, homocysteine, and glutathione) in water with a fast response time. In addition to colorimetric monitoring in the solid and solution phases, control experiments validate size-exclusive biothiol speciation through molecular-dimension-mediated pore diffusion. The role of SBUs in the OER mechanism is detailed from density functional theory-derived free energy analysis, which also validates the importance of accessible N-sites in sensing via portraying framework-analyte supramolecular interactions.

Tuning the Electronic Structure of a Ni-Vacancy-Enriched AuNi Spherical Nanoalloy via Electrochemical Etching for Water Oxidation Studies in Alkaline and Neutral Media.

Internal Ni-vacancy-enriched spherical AuNi nanoalloys (AuNi1-2-T) have been prepared via a noble electrochemical etching method. AuNi1.5-T showed the highest oxygen evolution reaction (OER) activity compared to bare AuNi1.5, and it demands only 239 mV overpotential, which was 134 mV lesser than the overpotential required by commercial RuO2 at 10 mA cm-2 current density in a 1 M KOH solution (pH = 14). The calculated turnover frequency (TOF) value for AuNi1.5-T (0.0229 s-1) was 11.74 times higher than that of AuNi1.5 (0.00195 s-1). Also, the electrochemically activated AuNi1.5-T showed superior neutral water oxidation activity by demanding only 335 mV overpotential with a TOF value of 0.000135 s-1 in a 1 M Na2SO4 solution (pH = 7) at 10 mA cm-2. The long-term stability studies (over 60 h) reveal the excellent robustness of an electrochemically treated alloy system. Density functional theory based electronic structure calculations showed that in the case of AuNi and AuNi1.5, Au d, Au s, and Ni d orbitals have significant contributions, whereas in the Ni-vacant systems, the density of states is mainly governed by d orbitals of Au and Ni. Also, the Ni-vacant system possesses a work function value of 4.96 eV, which is lower than that of the pristine system (5.27 eV) and thereby favored OH- binding with an optimum adsorption energy. This result is in reasonable agreement with the experimental outcome of an accelerated OER in a vacancy-enriched Ni-rich AuNi alloy system. Also, mechanistic analysis reveals that the creation of a Ni vacancy can effectively alter the overall mechanism of the OER and thereby facilitate the same with a lower applied energy.

Enhancement of the OER Kinetics of the Less-Explored α-MnO2 via Nickel Doping Approaches in Alkaline Medium.

Development of a low-cost transition metal-based catalyst for water splitting is of prime importance for generating green hydrogen on an industrial scale. Recently, various transition metal-based oxides, hydroxides, sulfides, and other chalcogenide-based materials have been synthesized for developing a suitable anode material for the oxygen evolution reaction (OER). Among the various transition metal-based catalysts, their oxides have received much consideration for OER, especially in lower pH condition, and MnO2 is one of the oxides that have widely been used for the same. The large variation in the structural disorder of MnO2 and internal resistance at the electrode-electrolyte interfaces have limited its large-scale application. By considering the above limitations of MnO2, here in this work, we have designed Ni-doped MnO2 via a simple wet-chemical synthetic route, which has been successfully applied for OER application in 0.1 M KOH solution. Doping of various quantities of Ni into the MnO2 lattices improved the OER properties, and for achieving 10 mA/cm2 current density, the Ni-doped MnO2 containing 0.02 M of Ni2+ ions (coined as MnO2-Ni0.002(M)) demands only 445 mV overpotential, whereas the bare MnO2 required 610 mV overpotential. It has been proposed that the incorporation of nickel ions into the MnO2 lattices leads to an electron transfer from the Ni3+ ions to Mn4+, which in turn facilitates the Jahn-Teller distortion in the Mn-O octahedral unit. This electron transfer and the creation of a structural disorder in the Mn sites result in the improvization of the OER properties of the MnO2 materials.

Advancing the extended roles of 3D transition metal based heterostructures with copious active sites for electrocatalytic water splitting.

The replacement of noble metals with alternative electrocatalysts is highly demanded for water splitting. From the exploration of 3D -transition metal based heterostructures, engineering at the nano-level brought more enhancements in active sites with reduced overpotentials for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). However, recent developments in 3D transition metal based heterostructures like direct growth on external substrates (Ni foam, Cu foam) gave highly impressive activities and stabilities. Research needs to be focused on how the active sites can be enhanced further with 3D heterostructures of transition metals by studying them with various counterparts like hydroxides, layered double hydroxides and phosphides for empowering both OER and HER applications. This perspective covers the way to enlarge the utilization of 3D heterostructures successfully in terms of reduced overpotentials, highly exposed active sites, increased electrical conductivity, porosity and high-rate activity. From the various approaches of growth of transition metal based 3D heterostructures, it is easy to fine tune the active sites to have a viable production of hydrogen with less applied energy input. Overall, this perspective outlines a direction to increase the number of active sites on 3D transition metal based heterostructures by growing on 3D foams for enhanced water splitting applications.

Metallic Gold-Incorporated Ni(OH)2 for Enhanced Water Oxidation in an Alkaline Medium: A Simple Wet-Chemical Approach.

The development of a highly efficient electrocatalyst for the oxygen evolution reaction (OER) with a lower overpotential and high intrinsic activity is highly challenging owing to its sluggish kinetic behavior. As an alternative to the state-of-the-art OER catalyst, recently, transition-metal-based hydroxide materials have been shown to play important roles for the same. Owing to the high earth abundance of various Ni-based hydroxide and its derivatives, these are known to be highly studied materials for the OER. Herein, we report a simple wet-chemical synthesis of metallic gold-incorporated (by varying the concentration of Au3+ ions) Ni(OH)2 nanosheets as an active and stable electrocatalyst for the OER in 1 M KOH medium. The Au-Ni(OH)2 (2) catalyst demanded a low overpotential of 288 mV to attain a geometric current density of 10 mA/cm2 with a lower Tafel value of 55 mV/dec compared to bare Ni(OH)2 with a lower mass loading of only 0.1 mg/cm2. Tafel slope analysis reveals that the incorporation of metallic gold on the hydroxide surfaces could alter the mechanistic pathways of the overall OER reaction. It has been proposed that the incorporation of metallic gold over the Ni(OH)2 surfaces led to a change in the electronic structure of the electroactive nickel sites (Jahn-Teller distortion), which favors the OER by electronic aspects.

DNA-Modified Cobalt Tungsten Oxide Hydroxide Hydrate Nanochains as an Effective Electrocatalyst with Amplified CO Tolerance during Methanol Oxidation.

Direct methanol fuel cell technology implementation mainly depends on the development of non-platinum catalysts with good CO tolerance. Among the widely studied transition-metal catalysts, cobalt oxide with distinctively higher catalytic efficiency is highly desirable. Here, we have evolved a simple method of synthesizing cobalt tungsten oxide hydroxide hydrate nanowires with DNA (CTOOH/DNA) and without incorporating DNA (CTOOH) by microwave irradiation and subsequently employed them as electrocatalysts for methanol oxidation. Following this, we examined the influence of incorporating DNA into CTOOH by cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy. The enhanced electrochemical surface area of CTOOH offered readily available electroactive sites and resulted in a higher oxidation current at a lower onset potential for methanol oxidation. On the other hand, CTOOH/DNA exhibited improved CO tolerance and it was evident from the chronoamperometric studies. Herein, we noticed only a 2.5 and 1.8% drop at CTOOH- and CTOOH/DNA-modified electrodes, respectively, after 30 min. Overall, from the results, it was evident that the presence of DNA in CTOOH played an important role in the rapid removal of adsorbed intermediates and regenerated active catalyst centers possibly by creating high density surface defects around the nanochains than bare CTOOH.

Temperature-Controlled Structural Variations of Meticulous Fibrous Networks of NiFe-Polymeric Zeolite Imidazolate Frameworks for Enhanced Performance in Electrocatalytic Water-Splitting Reactions.

Developing non-noble, earth-ample, and stable electrocatalysts are highly anticipated in oxygen-evolution reaction (OER) and hydrogen-evolution reaction (HER) at unique pH conditions. Herein, we have synthesized bimetallic (nickel and iron) zeolite imidazolate framework (ZIF)-based nanofibrous materials via a simple electrospinning (ES) process. The structural stability of the fibrous material is subjected to various calcination conditions. We have elaborated the structural importance of the one-dimensional (1D) fibrous materials in electrocatalytic water-splitting reactions. As a result, NiFe-ZIF-NFs (Nanofibers)-RT (Room Temperature) have delivered a small overpotential of 241 mV at 10 mA cm-2 current density in OER and 290 mV at a fixed current density of 50 mA cm-2 in HER at two different pH conditions with 1 M KOH and 0.5 M H2SO4, respectively. Furthermore, it exposes the actual surface area of 27.270 m2 g-1 and a high electrochemical active surface area (ECSA) of 50 µF in OER and 55 µF in HER, which is responsible for the electrochemical performance with better stability. This exceptional activity of the materials is mainly attributed to the structural dependency of the fibrous network through the polymeric architecture.

Electrospun Cobalt-Incorporated MOF-5 Microfibers as a Promising Electrocatalyst for OER in Alkaline Media.

Metal-organic framework (MOF)-based materials have attracted attention in recent times owing to their remarkable properties such as regulatable pore size, high specific surface area, and elasticity in their network topology, geometry, dimension, and chemical functionality. It is believed that the incorporation of a MOF network into a fibrous matrix results in the improvement of the electrocatalytic properties of the material. Herein, we have synthesized a Co-incorporated MOF-5-based fibrous material by a simple wet-chemical method, followed by an electrospinning (ES) process. The as-prepared Co-incorporated MOF-5 microfibers were employed as an electrocatalyst for the oxygen evolution reaction (OER) in 1 M KOH electrolyte. The catalyst demands a lower overpotential of 240 mV to attain a current density of 10 mA/cm2 with a lower Tafel slope value of 120 mV/dec along with a charge transfer resistance value of 2.9 Ω from electron impedance spectroscopy (EIS) analysis. From these results, it has been understood that the incorporation of Co metal into the MOF-5 microfibrous network has significantly improved the OER performance, which made them a potential entrant in other energy-related applications also.

In Situ Decorated Ni Metallic Layer with CoS2-Layered Thin Films via a Layer-by-Layer Strategy Using Pulsed Laser Deposition for Enhanced Electrocatalytic OER.

The catalytic activity of 3d-transition-metal-based electrocatalysts has exhibited considerable enhancements in electrocatalytic water splitting via pioneering modulations in the active sites. To overcome the energy loss because of the mechanic steps involved in a complex oxygen evolution reaction (OER), the electrode surface with only a few layers would be an advantage over multilayers for the ease of the electrolyte interaction and gas evolution. Here, for the first time, thin films of CoS2 are prepared on a carbon cloth via a pulsed laser deposition (PLD) technique via layer-by-layer deposition of Ni that tend to give Ni-CoS2 thin films. Based on varying the ablation of metallic Ni followed by CoS2 as a layer-by-layer assembly using PLD, three catalysts, namely, Ni5-CoS2, Ni10-CoS2, and Ni15-CoS2, were prepared. In OER, to achieve a benchmarking current density of 10 mA cm-2 in 1 M KOH, Ni10-CoS2 required a lesser overpotential of 304 mV, whereas others, namely, Ni5-CoS2, Ni15-CoS2, and CoS2, required overpotentials of 328, 336, and 373 mV, respectively, to attain the same current density. The charge transfer kinetics associated with all of the catalysts were analyzed, and the corresponding Tafel slope values for Ni5-CoS2 and Ni10-CoS2 were 75 and 98 mV/dec, respectively, ensuring the facile transfer of electrons at the interface. The assistance of metallic Ni sites also ensured stability for long-term applications. These findings will give a way for other earth-abundant catalysts for the increased electrocatalytic activity toward energy needs in future.

Fabrication of highly stable platinum organosols over DNA-scaffolds for enriched catalytic and SERS applications.

The use of nanomaterials (NMs) in various applications via multidisciplinary approaches is highly necessary in this era. In this line, the impact of noble metals in organic media for both catalysis and surface-enhanced Raman spectroscopic (SERS) studies is most interesting and also has a wider scope in various fields. Nonetheless, the catalytic reduction of aromatic nitro compounds is difficult with poor solubility in aqueous media, and reduction also is less feasible in the absence of noble metal-based catalysts. Thus, the choice of noble metal-based catalysts for the catalytic reduction of nitro compounds in organic media is one of the emerging methods with high selectivity towards products. Moreover, the superior catalytic activity of Pt NPs provides a higher rate constant value with a low dielectric constant of organic solvents. Herein, for the first time, we synthesised highly stable metallic Pt nanoparticles (NPs) anchored on bio-scaffold deoxyribonucleic acid (DNA) for two different applications. The advantage of highly controlled nucleation of NPs over DNA in organic media results in a spherical morphology with a particle diameter of 2.47 ± 2.11 nm and 2.84 ± 1.14 nm. A stable colloidal solution of Pt NPs was prepared by a simple wet chemical sodium borohydride reduction method within 15 minutes from the start of the reaction. Two sets of Pt NPs were synthesised by varying the molar ratio of the concentration of DNA to PtCl4 concentration and were named Pt@DNA (0.05 M) and Pt@DNA (0.06 M), respectively. The prepared Pt@DNA was effectively studied for two potential applications such as the SERS studies and catalytic reduction of nitro compounds. In catalysis, a higher catalytic rate was observed in the case of 4-nitrophenol (4-NP) at a rate of 8.43 × 10-2 min-1. In the SERS study, the reduction of the interparticle distance to below 5 nm facilitates the creation of a large number of hot spots for probe detection. Here, we used 10-3 M methylene blue (MB) as a probe molecule, and the enhancement factor (EF) value was calculated at different concentrations ranging from 10-3 M to 10-6 M. The highest enhancement factor (EF) value obtained was 2.91 × 105 for Pt@DNA (0.05 M). The as-synthesised stable Pt@DNA organosol can be exploited for other potential applications related to energy, sensor and medicinal fields in the near future.

Prospects in interfaces of biomolecule DNA and nanomaterials as an effective way for improvising surface enhanced Raman scattering: A review.

Surface Enhanced Raman Scattering (SERS) is a field of research that has shown promising application in the analysis of various substrate molecules by means of rough metallic surfaces. In directing the enhancement of substrate molecules in micro and nano-molar concentrations, plasmonic coupling of metal nanoparticles (NPs), morphology of metal NPs and the closely arrangement of rough metal surfaces that produces 'hot spots' can effectively increase the so-called enhancement factor (EF) that will be applicable in various fields. As the mechanistic aspects are still not clear, research has been triggered all over the world for the past two decades to have a clear understanding in chemical and electromagnetic effects. As the reproducibility of intensity of signals at low concentrations of probe molecules is of a big concern, metal NPs with various scaffolds were prepared and recently bio-molecule, DNA has been studied and showed promising advantages. This review first time highlights metal NPs with DNA interface as an effective rough metallic surface for SERS with high intensity and also with better reproducibility. Based on this review, similar kinds of scaffolds like DNA can be used to further analyze SERS activities of various metal NPs with different morphologies to have high intense signals at low concentrations of probe molecules.

Surface Decoration of DNA-Aided Amorphous Cobalt Hydroxide via Ag+ Ions as Binder-Free Electrodes toward Electrochemical Oxygen Evolution Reaction.

Out of various available methods, generation of hydrogen by electrocatalytic water splitting is the most accepted one which consists of two half-cell reactions, viz, oxygen evolution reaction (OER) at the anode and hydrogen evolution reaction at the cathode. OER is a complex four-electron transfer process, and to sustain the spontaneous generation of hydrogen at the cathode, it is urgent to develop some earth-abundant, low-cost electrode materials. Recently, use of cobalt-based hydroxide as the electrode substrate has taken much consideration and has been fabricated over various substrates. Because of various structural disorders, internal resistance, and dependence on the electrode, the binder substrate makes their applications limited. Here, in this work, to remove structural disorder and to increase electrical conductivity, we have incorporated silver ions into amorphous Co(OH)2, which turns to be a highly active OER electrocatalyst. Also, for the first time, we have developed hydroxide-based materials by using DNA as a stabilizer, and most importantly, using DNA gives an immense opportunity to run long-term OER applications without using an external binder such as nafion. Moreover, for the first time, these DNA-based materials were coated on nickel foam mainly to eliminate the low conductive nature of Ag2O. The synthesized catalyst showed a very high OER activity, and to reach 50 mA/cm2 current density, it needs only 260 mV as overpotential. The amorphous nature of hydroxide-based materials gives a higher opportunity toward the electrolyte to bind on the surface of a catalyst to run the OER with less applied overpotentials.

Enabling and Inducing Oxygen Vacancies in Cobalt Iron Layer Double Hydroxide via Selenization as Precatalysts for Electrocatalytic Hydrogen and Oxygen Evolution Reactions.

Production of hydrogen by water electrolysis is an environment-friendly method and comparatively greener than other methods of hydrogen production such as stream reforming carbon, hydrolysis of metal hydride, etc. However, sluggish kinetics of the individual half-cell reactions hinders the large-scale production of hydrogen. To minimize this disadvantage, finding an appropriate, competent, and low-cost catalyst has attracted attention worldwide. Layer double hydroxide (LDH)-based materials are promising candidates for oxygen evolution reaction (OER) but not fruitful and their hydrogen evolution reaction (HER) activity is very poor, due to the lack of ionic conductivity. The inclusion of chalcogenide and generation of inherent oxygen vacancies in the lattice of LDH lead to improvement of both OER and HER activities. The presence of rich oxygen vacancies was confirmed using both the Tauc plot (1.11 eV, vacancy induction) and the photoluminescence study (peak at 426 nm, photoregeneration of oxygen). In this work, we have developed vacancy-enriched, selenized CoFe-LDH by the consequent wet-chemical and hydrothermal routes, respectively, which was used for OER and HER applications in 1 M KOH and 0.5 M H2SO4 electrolytes, respectively. For OER, the catalyst required only 251 mV overpotential to reach a 50 mA/cm2 current density with a Tafel slope value of 47 mV/dec. For HER, the catalyst demanded only 222 mV overpotential for reaching a 50 mA/cm2 current density with a Tafel slope value of 126 mV/dec. Hence, generating oxygen vacancies leads to several advantages from enhancing the exposed active sites to high probability in obtaining electrocatalytically active species and subsequent assistance in oxygen and hydrogen molecule cleavage.

Green and sustainable route for oxidative depolymerization of lignin: New platform for fine chemicals and fuels.

Depolymerization of lignin biomass to its value-added chemicals and fuels is pivotal for achieving the goals for sustainable society, and therefore has acquired key interest among the researchers worldwide. A number of distinct approaches have evolved in literature for the deconstruction of lignin framework to its mixture of complex constituents in recent decades. Among the existing practices, special attention has been devoted for robust site selective chemical transformation in the complex structural frameworks of lignin. Despite the initial challenges over a period of time, oxidation and oxidative cleavage process of aromatic building blocks of lignin biomass toward the fine chemical synthesis and fuel generation has improved substantially. The development has improved in terms of cost effectiveness, milder reaction conditions, and purity of compound individuals. These aforementioned oxidative protocols mainly involve the breaking of C-C and C-O bonds of complex lignin frameworks. More precisely in the line with environmentally friendly greener approach, the catalytic oxidation/oxidative cleavage reactions have received wide spread interest for their mild and selective nature toward the lignin depolymerization. This mini-review aims to provide an overview of recent developments in the field of oxidative depolymerization of lignin under greener and environmentally benign conditions. Also, these oxidation protocols have been discussed in terms of scalability and recyclability as catalysts for different fields of applications.

Cubic Nanostructures of Nickel-Cobalt Carbonate Hydroxide Hydrate as a High-Performance Oxygen Evolution Reaction Electrocatalyst in Alkaline and Near-Neutral Media.

Catalyst development for the efficient direction of electrocatalytic water splitting with much less overpotential is crucial for meeting large-scale hydrogen generation. Being highly abundant and cost-effective, 3d transition-metal-based catalysts show promising activities in alkaline conditions. In this work, bimetallic nickel-cobalt carbonate hydroxide hydrate (NiCoCHH) was prepared by a co-precipitation method with varying molar ratios of Ni/Co of 0.5:1, 1:1, and 1.5:1, which were analyzed for oxygen evolution reaction (OER) study in both alkaline (1 M KOH) and near-neutral (1 M NaHCO3) media. For OER in 1 M KOH, NiCoCHH 1:1 required overpotential of just 238 mV at 10 mA cm-2 current density compared to other ratios of 0.5:1 and 1.5:1, which required 290 and 308 mV, respectively. Similarly, in 1 M NaHCO3, NiCoCHH 1:1 required an overpotential of 623 mV to reach 10 mA cm-2. A post-OER study confirmed the formation of NiOOH during OER. The observed faradaic efficiency was nearly 95.21% for the NiCoCHH 1:1 catalyst. A two-electrode setup with NiCoCHH 1:1∥Pt required just 312 mV as an overpotential at 10 mA cm-2. These kinds of comparative studies can be used in other 3d transition-metal-based catalysts for OER in the future.

Tuning Cu Overvoltage for a Copper-Telluride System in Electrocatalytic Water Reduction and Feasible Feedstock Conversion: A New Approach.

Highly efficient and earth-abundant elements capable of water reduction by electrocatalysis and are attractive for the sustainable generation of fuels. Among the earth-abundant metals, copper is one of the cheapest but often the most neglected choice for the hydrogen evolution reaction (HER) due to its high overvoltage. Herein, for the first time we have tuned the overpotential of copper by tellurizing it by two different methodologies, viz. hydrothermal and wet chemical methods, which form copper telluride nanochains and aggregates. The application of copper telluride as an electrocatalyst for the HER gave fruitful results in terms of both activity and stability. The hydrothermally synthesized catalyst Cu2-xTe/hyd shows a low overpotential (347 mV) at 10 mA cm-2 toward the HER. In addition, the catalyst showed a very low charge transfer resistance (Rct) of 24.4 Ω and, as expected, Cu2-xTe/hyd exhibited a lower Tafel slope value of 188 mV/dec in comparison to Cu2-xTe/wet (280 mV/dec). A chronoamperometry study reveals the long-term stability of both catalysts even up to 12 h. The Faradaic efficiency of Cu2-xTe/hyd was calculated and found to be 95.06% by using gas chromatographic (GC) studies. Moreover, with the idea of utilizing produced hydrogen (H2) from electrocatalysis, for the first time we have carried out feedstock conversion to platform chemicals in water under eco-friendly green conditions. We have chosen cinnamaldehyde, 2-hydroxy-1-phenylethanone, 4-(benzyloxy)benzaldehyde, and 2-(3-methoxyphenoxy)-1-phenylethanone (ß-O-4) as model compounds for feedstock conversion by hydrogenation and/or hydrogenolysis reactions in aqueous medium using external hydrogen pressure. This protocol could also be scaled up for large-scale conversion and the catalyst is likely to find industrial application since it requires an inexpensive catalyst and an easily available, mild reducing agent. The robustness of the developed catalyst is proven by recyclability experiments and its possibility of use in real-life applications.

Developments in DNA metallization strategies for water splitting electrocatalysis: A review.

The biomolecule DNA with the presence of different functionalities found to interact with different kinds of metal ions and show relatively higher stability over a long period of time when optimized appropriately. With the presence of A-T and G-C pairs, sugar moieties, phosphate functional groups and the double-helical structure, it can assemble both cationic and anionic species and forms a perfect metal-DNA self-assembly. Depending upon the aspect ratio of metal-DNA self-assemblies, metal content and their morphological outcomes, they could deliver variance in the catalytic activities. Such differences can be brought out by varying the synthesis reaction parameters focusing on a specific electrocatalytic application. In this review, recent developments in DNA metallization is elaborated first highlighting the underlying interactions between DNA and cationic/anionic species of various metals following which application of metal-DNA assemblies in electrocatalytic water oxidation and reduction are discussed critically. Knowledge provided in this review thus acts as the guide to various DNA metallization strategies and their subsequent application to water electrolysis for hydrogen generation.

Enhancing Hydrogen Evolution Reaction Activities of 2H-Phase VS2 Layers with Palladium Nanoparticles.

Effective hydrogen (H2) production with surface engineering of less active catalysts by an innovative approach is followed here. In this work, a non-noble 2H phase of VS2 layers, which showed poor activity for hydrogen evolution reaction (HER) in 0.5 M H2SO4, was made highly active by decorating palladium (Pd) nanoparticles (NPs) over VS2 layers. A density functional theory (DFT) study confirmed the successful binding of Pd with VS2, and the bond length in a Pd4 tetrahedron was measured to be 2.60 Å. In VS2-Pd, Pd as a Pd4 tetrahedron is pointed toward the VS2 layer, and the calculated Pd-S bond distance is 2.42 Å with some expansion of three Pd-Pd bonds (2.85 Å). From the density of states, it was confirmed that the band gap was too high for VS2 (0.2 eV; 2H phase) and was reduced to nearly zero in VS2-Pd (0.05 eV). In the electrocatalytic HER part, the obtained ΔGH values from DFT were 0.05, -0.45, and 0.22 eV for VS2/Pd4, Pd4, and VS2, respectively, which imply that VS2-Pd4 had improved HER activity compared to pristine VS2 and Pd4. A concentration-dependent study was carried out with molar ratios of Pd at 0.01, 0.05, and 0.1 M with VS2 layers. From the HER polarization study, VS2-Pd (0.05 M) showed an overpotential of 157 mV at 20 mA cm-2, which is 373 mV less than only VS2 with a Tafel slope of 75 mV dec-1 with overwhelming stability. These highly promising results will be interesting to make less active stable phases by incorporating metal NPs for efficient and stable H2 production.

Transition-Metal-Based Zeolite Imidazolate Framework Nanofibers via an Electrospinning Approach: A Review.

Zeolite imidazolate frameworks (ZIFs) are a subclass of metal organic frameworks (MOFs) and have been considered as a special finding in the current platform of the research arena. ZIFs have been comprised of metal ions with imidazolate linkers. In recent times, ZIFs have been predominately utilized for various applications. This excellent feature is because of its fascinating properties. During the evolution of the materials era, one-dimensional (1-D) fibrous materials are also considered as an important area of research. In order to make the fibrous materials, electrospinning (ES) is considered as a more reliable way for their synthesis. 1-D material has also been utilized for various applications owing to their abnormal physicochemical properties. In this mini-review, the recent developments with various processes have been followed for the synthesis of ZIF materials and 1-D fibrous materials. We elaborated their advantages over their applications in the past years which are discussed and reviewed. More importantly, we have proposed a new area for the incorporation of transition-metal-based ZIF materials into the 1-D fibrous materials, which confers the new direction to the research community to explore its use in various applications.