Vanadium-Doped Nickel Cobalt Layered Double Hydroxide: A High-Performance Oxygen Evolution Reaction Electrocatalyst in Alkaline Medium.

Vast attention from researchers is being given to the development of suitable oxygen evolution reaction (OER) electrocatalysts via water electrolysis. Being highly abundant, the use of transition-metal-based OER catalysts has been attractive more recently. Among the various transition-metal-based electrocatalysts, the use of layered double hydroxides (LDHs) has gained special attention from researchers owing to their high stability under OER conditions. In this work, we have reported the synthesis of trimetallic NiCoV-LDH via a simple wet-chemical method. The synthesized NiCoV-LDH possesses aggregated sheet-like structures and is screened for OER studies in alkaline medium. In the study of OER activity, the as-prepared catalyst demanded 280 mV overpotential and this was 42 mV less than the overpotential essential for pristine NiCo-LDH. Moreover, doping of a third metal into the NiCo-LDH system might lead to an increase in TOF values by almost three times. Apart from this, the electronic structural evaluation confirms that the doping of V3+ into NiCo-LDH could synergistically favor the electron transfer among the metal ions, which in turn increases the activity of the prepared catalyst toward the OER.

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.

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.

Cobalt tungsten oxide hydroxide hydrate (CTOHH) on DNA scaffold: an excellent bi-functional catalyst for oxygen evolution reaction (OER) and aromatic alcohol oxidation.

A material with interdisciplinary properties is of wide interest for use in environmental applications. Currently, hydrogen generation by electrolysis and formation of carbonyl derivatives from alcohols are two different fields that focus on energy and environmental applications. In this work, a new material, Cobalt Tungsten Oxide Hydroxide Hydrate (CTOHH) on deoxyribonucleic acid (DNA) scaffold having chain-like morphology has been prepared for the first time by a facile microwave heating method. The same CTOHH was also prepared without the DNA scaffold and resulted in irregular aggregated molecular structures. Further, both CTOHH-DNA and CTOHH were converted into CoWO4-DNA and CoWO4, respectively by annealing them at a temperature of 600 °C. All the four catalysts were used for electrocatalytic oxygen evolution reaction (OER) and for oxidation of aromatic alcohols. In OER, CTOHH-DNA delivered fruitful results compared to all other electrocatalysts. For attaining a current density of 10 mA cm-2, it just required an overpotential of 355 mV with a Tafel slope value of 47.5 mV dec-1. Similarly, all four catalysts were also analyzed for selective and controlled oxidation of aromatic alcohols to their respective aldehydes and ketones using molecular oxygen as a green oxidant where CTOHH-DNA showed better results. Chemo-selectivity has been observed for CTOHH-DNA in the co-presence of hydroxyl and cyano functional groups. The durability of CTOHH-DNA was analyzed and it showed excellent catalytic activity retention up to five cycles.