Metal-Organic Framework-Derived Mesoporous B-Doped CoO/Co@N-Doped Carbon Hybrid 3D Heterostructured Interfaces with Modulated Cobalt Oxidation States for Alkaline Water Splitting.

Heteroatom-doped transition metal-oxides of high oxygen evolution reaction (OER) activities interfaced with metals of low hydrogen adsorption energy barrier for efficient hydrogen evolution reaction (HER) when uniformly embedded in a conductive nitrogen-doped carbon (NC) matrix, can mitigate the low-conductivity and high-agglomeration of metal-nanoparticles in carbon matrix and enhances their bifunctional activities. Thus, a 3D mesoporous heterostructure of boron (B)-doped cobalt-oxide/cobalt-metal nanohybrids embedded in NC and grown on a Ni foam substrate (B-CoO/Co@NC/NF) is developed as a binder-free bifunctional electrocatalyst for alkaline water-splitting via a post-synthetic modification of the metal-organic framework and subsequent annealing in different Ar/H2 gas ratios. B-CoO/Co@NC/NF prepared using 10% H2 gas (B-CoO/Co@NC/NF [10% H2 ]) shows the lowest HER overpotential (196 mV) and B-CoO/Co@NC/NF (Ar), developed in Ar, shows an OER overpotential of 307 mV at 10 mA cm-2 with excellent long-term durability for 100 h. The best anode and cathode electrocatalyst-based electrolyzer (B-CoO/Co@NC/NF (Ar)(+)//B-CoO/Co@NC/NF (10% H2 )(-)) generates a current density of 10 mA cm-2 with only 1.62 V with long-term stability. Further, density functional theory investigations demonstrate the effect of B-doping on electronic structure and reaction mechanism of the electrocatalysts for optimal interaction with reaction intermediates for efficient alkaline water-splitting which corroborates the experimental results.

High-Alkaline Water-Splitting Activity of Mesoporous 3D Heterostructures: An Amorphous-Shell@Crystalline-Core Nano-Assembly of Co-Ni-Phosphate Ultrathin-Nanosheets and V- Doped Cobalt-Nitride Nanowires.

Introducing amorphous and ultrathin nanosheets of transition bimetal phosphate arrays that are highly active in the oxygen evolution reaction (OER) as shells over an electronically modulated crystalline core with low hydrogen absorption energy for an excellent hydrogen evolution reaction (HER) can boost the sluggish kinetics of the OER and HER in alkaline electrolytes. Therefore, in this study, ultrathin and amorphous cobalt-nickel-phosphate (CoNiPOx ) nanosheet arrays are deposited over vanadium (V)-doped cobalt-nitride (V3% -Co4 N) crystalline core nanowires to obtain amorphous-shell@crystalline-core mesoporous 3D-heterostructures (CoNiPOx @V-Co4 N/NF) as bifunctional electrocatalysts. The optimized electrocatalyst shows extremely low HER and OER overpotentials of 53 and 270 mV at 10 mA cm-2 , respectively. The CoNiPOx @V3% -Co4 N/NF (+/-) electrolyzer utilizing the electrocatalyst as both anode and cathode demonstrates remarkable overall water-splitting activity, requiring a cell potential of only 1.52 V at 10 mA cm-2 , 30 mV lower than that of the RuO2 /NF (+)/20%-Pt/C/NF (-) electrolyzer. Such impressive bifunctional activities can be attributed to abundant active sites, adjusted electronic structure, lower charge-transfer resistance, enhanced electrochemically active surface area (ECSA), and surface- and volume-confined electrocatalysis resulting from the synergistic effects of the crystalline V3% -Co4 N core and amorphous CoNiPOx shells boosting water splitting in alkaline media.

Effect of reducing agents on the synthesis of anisotropic gold nanoparticles.

The seed-mediated method is a general procedure for the synthesis of gold nanorods (Au NRs), and reducing agents such as ascorbic acid (AA) and hydroquinone (HQ) are widely used for the growth process. Further, they are mild reducing agents; however, when AA is used, controlling the size of Au NRs with a higher aspect ratio (localized surface plasmon resonance (LSPR) peak, λLmax > 900 nm) is challenging because it results in a faster growth rate of Au NRs. In contrast, when HQ is used, Au NRs with a higher aspect ratio can be synthesized as it slows down the growth rate of the Au NRs and greatly enhanced the λLmax. However, the increase in λLmax is still needs not satisfactory due to the limited enhancement in the aspect ratio of Au NRs due to utilization of single reducing agent. The growth kinetics of the Au NRs can be modulated by controlling the reducing power of the reducing agents. In such scenario, judicious use of two reducing agents such as AA and HQ simultaneously can help us to design Au NRs of higher aspect ratio in a controlled manner due to the optimum growth rate resulting from the combined effect of both the reducing agents. In this study, we investigated the effect of the two reducing agents by controlling the volume ratios. When the growth solution contains both the reducing agents, the growth of Au NRs is first initiated by the fast reduction of Au3+ to Au+ due to stronger reducing power of the AA and when the AA in the growth solution is completely utilized, further growth of the Au NRs continues as a result of the HQ thereby resulting to high aspect ratio Au NRs. Consequently, the LSPR peak (λLmax > 1275 nm) can be tuned by controlling the volume ratios of the reducing agents.

Alkaline Water Splitting Enhancement by MOF-Derived Fe-Co-Oxide/Co@NC-mNS Heterostructure: Boosting OER and HER through Defect Engineering and In Situ Oxidation.

Introducing defects and in situ topotactic transformation of the electrocatalysts generating heterostructures of mixed-metal oxides(hydroxides) that are highly active for oxygen evolution reaction (OER) in tandem with metals of low hydrogen adsorption barrier for efficient hydrogen evolution reaction (HER) is urgently demanded for boosting the sluggish OER and HER kinetics in alkaline media. Ascertaining that, metal-organic-framework-derived freestanding, defect-rich, and in situ oxidized Fe-Co-O/Co metal@N-doped carbon (Co@NC) mesoporous nanosheet (mNS) heterostructure on Ni foam (Fe-Co-O/Co@NC-mNS/NF) is developed from the in situ oxidation of micropillar-like heterostructured Fe-Co-O/Co@NC/NF precatalyst. The in situ oxidized Fe-Co-O/Co@NC-mNS/NF exhibits excellent bifunctional properties by demanding only low overpotentials of 257 and 112 mV, respectively, for OER and HER at the current density of 10 mA cm-2 , with long-term durability, attributed to the existence of oxygen vacancies, higher specific surface area, increased electrochemical active surface area, and in situ generated new metal (oxyhydr)oxide phases. Further, Fe-Co-O/Co@NC-mNS/NF (+/-) electrolyzer requires only a low cell potential of 1.58 V to derive a current density of 10 mA cm-2 . Thus, the present work opens a new window for boosting the overall alkaline water splitting.

Freestanding 1T-Mnx Mo1- x S2- y Sey and MoFe2 S4- z Sez Ultrathin Nanosheet-Structured Electrodes for Highly Efficient Flexible Solid-State Asymmetric Supercapacitors.

Fabrication of hierarchical nanosheet arrays of 1T phase of transition-metal dichalcogenides is indeed a critical task, but it holds immense potential for energy storage. A single-step strategy is employed for the fabrication of stable 1T-Mnx Mo1- x S2- y Sey and MoFe2 S4- z Sez hierarchical nanosheet arrays on carbon cloth as positive and negative electrodes, respectively. The flexible asymmetric supercapacitor constructed with these two electrodes exhibits an excellent electrochemical performance (energy density of ≈69 Wh kg-1  at a power density of 0.985 kW kg-1 ) with ultralong cyclic stability of ≈83.5% capacity retention, after 10 000 consecutive cycles. Co-doping of the metal and nonmetal boosts the charge storage ability of the transition-metal chalcogenides following enrichment in the metallic 1T phase, improvement in the surface area, and expansion in the interlayer spacing in tandem, which is the key focus of the present study. This study explicitly demonstrates the exponential enhancement of specific capacity of MoS2 following intercalation and doping of Mn and Se, and Fe2 S3 following doping of Mo and Se could be an ideal direction for the fabrication of novel energy-storage materials with high-energy storage ability.

Metal-Organic Framework-Derived Fe/Co-based Bifunctional Electrode for H2 Production through Water and Urea Electrolysis.

Hollow-structured Fex Co2-x P, Fex Co3-x O4 , and Prussian blue analogue (FeCo-PBA) microbuilding arrays on Ni foam (NF) are derived from Co-based metal-organic frameworks (Co-MOF) using a simple room temperature and post-heat-treatment route. Among them, Fex Co2-x P/NF shows excellent bifunctional catalytic activities by demonstrating very low oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) overpotentials of 255/114 mV at a current density of 20/10 mA cm-2 respectively, whereas Fex Co3-x O4 /NF and FeCo-PBA/NF demand higher overpotentials. Remarkably, for water electrolysis, Fex Co2-x P/NF requires only 1.61 V to obtain 10 mA cm-2 . In contrast to water electrolysis, urea electrolysis reduces overpotential and simultaneously purifies the urea-rich wastewater. The urea oxidation reaction at the Fex Co2-x P/NF anode needs just 1.345 V to achieve 20 mA cm-2 , which is 140 mV less than the 1.48 V potential required for OER. Moreover, the generation of H2 through urea electrolysis needs only 1.42 V to drive 10 mA cm-2 .

Remarkable Bifunctional Oxygen and Hydrogen Evolution Electrocatalytic Activities with Trace-Level Fe Doping in Ni- and Co-Layered Double Hydroxides for Overall Water-Splitting.

Large-scale H2 production from water by electrochemical water-splitting is mainly limited by the sluggish kinetics of the nonprecious-based anode catalysts for oxygen evolution reaction (OER). Here, we report layer-by-layer in situ growth of low-level Fe-doped Ni-layered double hydroxide (Ni1- xFe x-LDH) and Co-layered double hydroxide (Co1- xFe x-LDH), respectively, with three-dimensional microflower and one-dimensional nanopaddy-like morphologies on Ni foam, by a one-step eco-friendly hydrothermal route. In this work, an interesting finding is that both Ni1- xFe x-LDH and Co1- xFe x-LDH materials are very active and efficient for OER as well as hydrogen evolution reaction (HER) catalytic activities in alkaline medium. The electrochemical studies demonstrate that Co1- xFe x-LDH material exhibits very low OER and HER overpotentials of 249 and 273 mV, respectively, at a high current density of 50 mA cm-2, whereas Ni1- xFe x-LDH exhibits 297 and 319 mV. To study the overall water-splitting performance using these electrocatalysts as anode and cathode, three types of alkaline electrolyzers are fabricated, namely, Co1- xFe x-LDH(+)∥Co1- xFe x-LDH(-), Ni1- xFe x-LDH(+)∥Ni1- xFe x-LDH(-), and Co1- xFe x-LDH(+)∥Ni1- xFe x-LDH(-). These electrolyzers require only a cell potential ( Ecell) of 1.60, 1.60, and 1.59 V, respectively, to drive the benchmark current density of 10 mA cm-2. Another interesting finding is that their catalytic activities are enhanced after stability tests. Systematic analyses are carried out on both electrodes after all electrocatalytic activity studies. The developed three types of electrolyzers to produce H2, are very efficient, cost-effective, and offer no complications in synthesis of materials and fabrication of electrolyzers, which can greatly enable the realization of clean renewable energy infrastructure.