Electrocatalytic Activity Research Articles

Research Progress on Ni-based Electrocatalysts for Electrochemical Reduction of Nitrogen to Ammonia.

The electrochemical NRRto synthesize ammoniais considered as a promising method due to its approvable advantages of zero-pollution emission, feasible reaction proceedings, good safety and easy management. The multiple efforts have been devoted to the exploration of earth-abundant-element-based nanomaterials as high-efficiency electrocatalysts for realizing their industrial applications. Among these, the Ni-based nanomaterials is prioritized as an attractive non-noble-metal electrocatalysts for catalyzing NRR because they are earth-abundance and exceedingly easy to synthesize as well as also delivers the potential of high electrocatalytic activity and durability. In this review, after briefly elucidating the underlying mechanisms of NRR during the electrochemical process, we systematically sum up the recent research progress in representative Ni-based electrocatalysts, including monometallic Ni-based nanomaterials, bimetallic Ni-based nanomaterials, polymetallic Ni-based nanomaterials, etc. In particular, we discuss the effects of physicochemical properties, such as phases, crystallinity, morphology, composition, defects, heteroatom doping, and strain engineering, on the comprehensive performance of the abovementioned electrocatalysts, with the aim of establishing the nanostructure-function relationships of the electrocatalysts. In addition, the promising directions of Ni-based electrocatalysts for NRR are also pointed out and highlighted. The generic approach in this review may expand the frontiers of NRR and provides the inspiration for developing high-efficiently Ni-based electrocatalysts.

Effect of sulfidation and phosphidation on Fe doped Co LDH/nickel foam for efficient multifunctional water splitting electrodes, urea oxidation reaction, and seawater splitting: An experimental and computational study

In this work, the binder-free Fe-doped cobalt LDH/nickel foam (CoFe LDH/NF) electrode was prepared using the hydrothermal method. To achieve higher electrocatalyst activity of CoFe LDH/NF, sulfurization was conducted using the hydrothermal method, while the phosphidation was performed through a chemical vapor deposition (CVD) technique. The CoFeS/NF and CoFeP/NF electrodes exhibited significantly higher electrocatalytic activity than CoFe LDH/NF electrode. The CoFeP/NF electrode with a specific surface area of 6.8 m2 g−1 had lower overpotentials of 120 and 236 mV for hydrogen (HER) and oxygen (OER) evolution reactions, respectively. Additionally, the CoFeP/NF electrode exhibited a low potential of 1.32 V vs. RHE at a current density of 10 mA cm−2 for urea oxidation reaction (UOR). The CoFeP/NF electrode demonstrated low overpotentials of 224 and 273 mV in a seawater solution for HER and OER, respectively. The density functional theory (DFT) calculations confirmed the experimental results in which the CoFeP/NF material had promising electrocatalytic activity for renewable energy applications.

Nickel phosphide: the Effect of Phosphorus Content on the Activity and Stability toward Oxygen Evolution Reaction in Alkaline Medium.

In this work, a systematic study of the effect of the metal to phosphorus ratio in Ni-P nanoparticles on their catalytic activity with respect to the OER is reported. To this end, nickel phosphide nanoparticles are synthesized through two different synthesis routes, one involving in-situ phosphidation and one involving ex-situ phosphidation. In-situ phosphidation is performed via two steps route in a one-pot synthesis, in which Ni nanoparticles are formed at 220 ◦C, but not isolated, and then transformed to phase pure either Ni12P5 or Ni2P nanocrystallites. In the second synthesis method (ex-situ phosphidation), nickel nanoparticles with an excess amount of trioctylphosphine (TOP) as a capping agent were synthesized and separated from the solution, then subsequently annealed in three different atmospheres, leading to the formation of three types of NixPy viz.[NixPy-H2/Ar], [NixPy-Ar], and [NixPy -air ], [NixPy -air ] nanoparticles showed the best electrocatalytic activity among the annealed nanoparticles in Ar and H2/Ar but lower than Ni12P5 nanoparticles. However, [NixPy -air ] showed very high stability in comparison with other synthesized nanoparticles. Moreover, the effect of the adventitious and spiked Fe in the electrolyte was studied on the electrocatalytic activity of all synthesized nanoparticles.

Revealing the Effect of Anion Regulation in NiCo2X4 (X = O, S, Se, Te) on Photoassisted Methanol Electrocatalytic Oxidation.

Designing nonprecious metal anode catalysts for photoassisted direct methanol fuel cells (PDMFCs) remains a challenge. As a semiconductor catalyst with a spinel structure, NiCo2O4 has good methanol catalytic oxidation activity and photocatalytic activity, making it a highly promising anode non-noble metal catalyst for PDMFCs. However, compared with the noble metal catalyst, the photoelectrocatalytic activity remained to be improved. In this report, an anion regulation strategy was adopted to improve the photoassisted methanol electrocatalytic activity. Using a CoNi-Aspartic (CoNi-Asp) nanorod as the precursor, the anion-regulated NiCo2X4 (X = O, S, Se, Te) was prepared by oxidation, sulfuration, selenization, and telluridation reactions. The regulation of anions and their effects on the electronic structure, intermediate product, and photoelectric catalytic performance of NiCo2X4 (X= O, S, Se, Te) was systematically discussed. Photoelectrochemical characterization and adsorption energy of •OH revealing the volcano-like correlation between the anion in NiCo2X4 (X = O, S, Se, Te) and their photoelectrocatalytic performance. The narrowest band gap (2.239 eV), the highest •OH adsorption energy (-3.32 eV), and the highest ratio of Co3+/Co2+ (2.19) ensure the best photoelectric catalytic performance of NiCo2S4, under the visible light irradiation, the photoresponse current density was 1.9 A g-1, the current density at 0.6 V was up to 21.9 A g-1. After 9 h of stability testing, the current retention rate was 80%. This report sheds an idea for the rational design of non-noble anode catalysts for PDMFCs.

Developments in Nanostructured MoS2-Decorated Reduced Graphene Oxide Composite Aerogel as an Electrocatalyst for the Hydrogen Evolution Reaction

Developing lightweight, highly active surfaces with a high level of performance and great stability is crucial for ensuring the dependability of energy harvesting and conversion devices. Aerogel-based electrocatalysts are an efficient option for electrocatalytic hydrogen production because of their numerous benefits, such as their compatibility with interface engineering and their porous architecture. Herein, we report on the facile synthesis of a nanorod-like molybdenum sulfide–reduced graphene oxide (M-rG) aerogel as an electrocatalyst for the hydrogen evolution reaction (HER). The 3D architecture of the network-like structure of the M-rG hybrid aerogel was created via the hydrothermal technique, using a saturated NaCl solution-assisted process, where the MoS2 was homogeneously incorporated within the interconnected rGO aerogel. The optimized M-rG-300 aerogel electrocatalyst had a significantly decreased overpotential of 112 mV at 10 mA/cm2 for the HER in alkaline conditions. The M-rG-300 also showed a higher level of reliability. The remarkable efficiency of the HER involving the M-rG-300 is principally attributed to the excellent connectivity between the rGO and MoS2 in the aerogel structure. The efficient interconnection influenced the achievement of a larger electrochemically active surface area, increased electrical conductivity, and the exposure of more active sites for the HER. Furthermore, the creation of a synergistic effect in the M-rG-300 aerogel is the most probable mechanism to boost the electrocatalytic activity.

Synergistic Effects of the Electric Field Induced by Imidazolium Rotation and Hydrogen Bonding in Electrocatalysis of CO2.

The roles of the ionic liquid (IL), 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]), and water in controlling the mechanism, energetics, and electrocatalytic activity of CO2 reduction to CO on silver in nonaqueous electrolytes were investigated. The first electron transfer occurs to CO2 at reduced overpotentials when it is trapped between the planes of the [EMIM]+ ring and the electrode surface due to cation reorientation as determined from voltammetry, in situ surface-enhanced Raman spectroscopy, and density functional theory calculations. Within this interface, water up to 0.5 M does not induce significant Faradaic activity, opposing the notion of it being a free proton source. Instead, water acts as a hydrogen bond donor, and the proton is sourced from [EMIM]+. Furthermore, this study demonstrates that alcohols with varying acidities tune the hydrogen bonding network in the interfacial microenvironment to lower the energetics required for CO2 reduction. The hydrogen bonding suppresses the formation of inactive carboxylate species, thus preserving the catalytic activity of [EMIM]+. The ability to tune the hydrogen bonding network opens new avenues for advancing IL-mediated electrocatalytic reactions in nonaqueous electrolytes.

Highly stable and efficient Sb doped Ti/RuO2-IrO2-SnO2 electrode toward organic pollutants degradation by in situ generated oxidizing species

Electrochemical oxidation (ECO) technology has proven to be efficient for organic wastewater treatment. Given the strong demand for the development of anodes with superior stability, high activity, and low cost that can be applied industrially, herein, a stable Sb-doped Ti/RuO2-IrO2-SnO2 electrode (SSE) is fabricated and served as an anode for the degradation of aniline using diverse power supply modes. The SSE shows better performance than the Ti/RuO2-IrO2-SnO2 electrode (SE) in facilitating electron transport, enlarging the electrochemical active surface area, enhancing stability, and increasing electrocatalytic activity. Theoretical calculations reveal the stability and electronic properties of the synthesized electrodes. Furthermore, by degrading complex molecules and real wastewater, the practical industrial application of SSE is explored. Subsequently, the active species and possible degradation pathways are systematically elucidated. Therefore, this work provides a promising and superior-performance electrode with attractive application prospects for the high-efficient degradation of refractory organic wastewater.

Interfacial coupling of Ce-CoSe2 nanoneedle arrays with MXene for efficient overall water splitting

Designing highly effective, low-cost bifunctional electrocatalysts without noble metals for overall water splitting remains a significant challenge. In this work, interfacial coupling of Ce-doped CoSe2 nanoneedle arrays with MXene (Ce-CoSe2/MXene) is developed via the facile hydrothermal and selenization methods. The extensive specific surface area and favorable hydrophilicity of Ti3AlC2, combined with the optimized electronic structure and abundant active sites from Ce-doping and selenization, contribute to the exceptional bifunctional electrocatalytic performance of the Ce-CoSe2/MXene electrode. Specifically, this heterostructure achieves a low hydrogen evolution reaction (HER) overpotential of 34 mV at 10 mA cm−2, an oxygen evolution reaction (OER) overpotential of 279 mV at 100 mA cm−2, and an overall water splitting (OWS) potential as low as 1.45 V at 10 mA cm−2. In-situ Raman spectroscopy reveals that surface reconstruction would improve catalytic activity and stability. Theoretical calculations indicate that the Ce-CoSe2/MXene can improve the adsorption of intermediates and facilitate HER/OER process by lowering the kinetic barrier, thereby enhancing electrocatalytic activity. This research marks a substantial advancement in the development of low-cost, efficient electrocatalysts for overall water splitting.

Layered Porous Ring-Like Carbon Network Protected FeNi Metal Atomic Pairs for Bifunctional Oxygen Electrocatalysis and Rechargeable Zn-Air Batteries.

Bimetallic atom catalysts exhibit ultra-high oxygen electrocatalytic activity by harnessing mutual promotion and synergistic effects between adjacent metal active centers, surpassing the performance of single metal atomic catalysts. Herein, FeNi atom pairs protected by hierarchical porous annular carbon grids (P-FeNi-NPC) are introduced using a mediator-assisted MOFs-derived strategy. The introduction of the multi-block copolymer P123 ensures the uniform confinement and dispersion of metal ions, followed by thermal decomposition to form a "planetary-ring-like" carbon framework that anchors the bimetallic atomic pairs in the active region. The homogeneous distribution of adjacent Fe-N4 and Ni-N4 active sites significantly enhances catalytic activity and stability. Leveraging unique electronic and geometric structures, the resulting P-FeNi-NPC catalyst demonstrates exceptional ORR and OER activities with an ΔE value of 0.705 (E1/2 = 0.845V, Ej = 10 = 1.55V). Theoretical calculations unveil that FeNi bimetallic sites loaded on nitrogen-doped carbon frameworks with specific curvature effectively modulate the energy of d-band centers, thus balancing the free energy of oxygen-containing intermediates. This study presents a novel and versatile approach for synthesizing advanced bifunctional catalysts, poised to drive the future development of Zn-air batteries.

Accelerating gas escape efficiency by parallel alignment of nanosheets arrays for high-current oxygen evolution and urea oxidation

Electrocatalysts play a crucial role in energy production and chemical oxidation. Nonetheless, the efficacy of catalysts in expediting reactions is notably affected by the escape of bubbles and the re-exposure of active sites, particularly under high-current-density conditions. Herein, parallel-aligned Ni(OH)2 nanosheets array is anchored on nickel foam as substrate to verify mass transfer enhancement theory. Compare with disordered and interconnected nanosheets structures, parallel alignment of nanosheets array with superior mass transfer capability, larger exposed surface area, and spatial confinement effects is demonstrated to boost effective removal of in situ generated gas bubbles. Moreover, carbon coating layer with high electrical conductivity and nickel-iron-based composite with high activity is simultaneously anchored on parallel-aligned nanosheets surface (C@FeNi/NF-P). As illustration of application viability, C@FeNi/NF-P exhibits overpotential of 317 mV and potential of 1.45 V at 500 mA cm−2, respectively, for oxygen evolution (OER) and urea oxidation (UOR) with good stability. Moreover, the mass transfer enhancement effect of parallel aligned structure for the high active electrodes is also discussed. This work provides new insight for physical structural modulation of active materials to strengthen electrocatalytic activity with high mass-transfer efficiency, further ensuring high-efficient and stable water splitting and urea oxidation.

Influence of Bi3+ Doping on Electrochemical Properties of Ti/Sb-SnO2/PbO2 Electrode for Zinc Electrowinning.

Bi3+ doped Ti/Sb-SnO2/PbO2 electrode materials were fabricated by electrodeposition to improve their electrochemical performance in zinc electrowinning. The surface morphology, chemical composition, and hydrophilicity of the as-prepared electrodes were characterized using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and contact angle. An electrochemical measurement and an accelerated lifetime experiment were also conducted to investigate the electrocatalytic performance and stability of the electrodes. The results show that the Bi3+ modification electrode has an important effect on the coating morphology, the crystal structure, the surface hydrophilicity, the electrocatalytic activity, and the stability. The electrode prepared from the solution containing 2 mmol·L-1 Bi(NO3)3 (marked as the Ti/Sb-SnO2/2Bi-PbO2 electrode) exhibits the best hydrophilicity performance (θ = 21.6°) and the longest service life (1196 h). During the electrochemical characterization analysis, the Ti/Sb-SnO2/2Bi-PbO2 electrode showed the highest oxygen evolution activity, which can be attributed to it having the highest electroactive surface (qT* = 21.20 C·cm-2) and the best charge-transfer efficiency. The DFT calculation demonstrated that the doping of Bi3+ leads to a decrease in the OER reaction barrier and an increase in the DOS of the electrode, which further enhances the catalytic activity and the conductivity of the electrode. Moreover, the simulated zinc electrowinning experiment demonstrated that the Ti/Sb-SnO2/2Bi-PbO2 electrode consumes less energy than other electrodes. Therefore, it is expected that the Bi3+ modified electrode will become a very promising electrode material for zinc electrowinning in the future.

Beyond S and Se: Electrocatalytic Hydrogen Production by Tellurolate-Bridged Co(III)-Mn(I) Heterodinuclear Complexes.

In the pursuit of efficient electrocatalysts for the hydrogen evolution reaction (HER), a series of manganese and cobalt heterodinuclear complexes have been synthesized and characterized that have a stark resemblance with the [NiFe]-hydrogenase active site structure. Irradiation of [Mn2(CO)10] in the presence of 1.5 eq of [NaEPh] [E = S, Se, Te] followed by reaction with [Cp*CoCl]2 led to the formation of half-sandwiched trichalcogenate-bridged heterodinuclear complexes [{Mn(CO)3}(μ-EPh)3(CoCp*)] [E = S (C1); Se (C2) and Te (C3)]. The reaction of these heterodinuclear trichalcogenate-bridged complexes with [LiBH4·THF] yielded the corresponding dichalcogenate hydride-bridged heterobimetallic complexes [(CO)3Mn(μ-EPh)2(μ-H)(CoCp*)] [E = S (C5); Se (C6) and Te (C7)], which closely imitate the Ni-R intermediate of [NiFe]-hydrogenase. The resultant complexes (C5-C7) displayed impressive H2 production in DMF in the presence of HBF4, whereas the Te-based complex (C7) showcased the highest TON (184 h-1) with an impressive Faradaic efficiency of >98%. The DFT investigations revealed a unique role of bridging chalcogens in catalysis, wherein, depending on the identity of the chalcogen (S, Se, or Te), protonation could occur via two distinct routes. This study represents a rare example of the full trio of S/Se/Te-based heterodinuclear complexes whose electrocatalytic HER activity has been probed under analogous conditions.

Nitrogen-doped iron-manganese porous carbon particle electrodes for electrocatalytic degradation of tetracycline: Interfacial reaction mechanisms

In this study, nitrogen-doped porous carbon-supported iron-manganese microspheres (FeMn@NC-700) were successfully synthesized and employed as three-dimensional particle electrodes (3DPE) for electro-oxidative of tetracycline (TCH) in water. FeMn@NC-700 exhibited stable catalytic activity and effective TCH removal capabilities under complex water quality conditions and varying pH levels. Under optimized conditions, the 3D/FeMn@NC-700 system reduced the TCH concentration from an initial 20 mg/L to 0.96 mg/L within 60 min, achieving a 95.23 %removal efficiency with an energy consumption of only 10.05 kWh/m3. The outstanding electrocatalytic activity of the 3D/FeMn@NC-700 system was attributed to the dynamic redox cycling between the Fe and Mn species on the 3DPE surface. Radical quenching experiments and electron paramagnetic resonance (EPR) analysis identified the predominant role of singlet oxygen (1O2), effectively removing TCH with the assistance of hydroxyl radicals (·OH) and superoxide anions (O2·-). The degradation pathways of major intermediate products of TCH were proposed, along with a toxicity assessment. In conclusion, the 3D/FeMn@NC-700 system represents a reliable and cost-effective technology for TCH wastewater treatment.

Universal and large-scale transform engineering from commercial metals to micron/nanoporous metals via an induced oxidation-reduction reaction

Three-dimensional (3D) nanoporous metals are being increasingly utilized in various fields such as catalysis, energy storage, and sensing. However, the conventional fabrication approaches for 3D nanoporous metals, such as dealloying and template methods, require additional sacrificial materials and multiple fabrication steps and generate chemical waste. Herein, we propose a novel gaseous (O2 and H2) oxidation-reduction (GOR) method to directly transform various transition metals/alloys into 3D micron/nanoporous materials by utilizing the spontaneous reconstruction of metallic atoms. This method eliminates the need for sacrificial materials and acidic/alkaline solutions, making it facile, cost-effective, and environmentally friendly. The resulting micron/nanoporous Ni/Ni alloy exhibits excellent mechanical properties, atomic hydrogen adsorption capability, and hydrophilicity, leading to outstanding electrocatalytic activity and durability for hydrogen evolution reaction.

Incorporation of Ag in Co9S8-Ni3S2 for Predominantly Enhanced Electrocatalytic Activities for Oxygen Evolution Reaction: A Combined Experimental and DFT Study.

Electrodeposition of abundant metals to fabricate efficient and durable electrodes indicate a viable role in advancing renewable electrochemical energy tools. Herein, we deposit Co9S8-Ag-Ni3S2@NF on nickel foam (NF) to produce Co9S8-Ag-Ni3S2@NF as a exceedingly proficient electrode for oxygen evolution reaction (OER). The electrochemical investigation verifies that the Co9S8-Ag-Ni3S2@NF electrode reveals better electrocatalytic activity to OER because of its nanoflowers' open-pore morphology, reduced overpotential (η10=125 mV), smaller charge transfer resistance, long-term stability, and a synergistic effect between various components, which allows the reactants to be more easily absorbed and subsequently converted into gaseous products during the water electrolysis route. Density functional theory (DFT) calculation as well reveals the introduction of Ag (222) surface into the Co9S8 (440)-Ni3S2 (120) structure increases the electronic density of states (DOS) per unit cell of a system and increases the electrocatalytic activity of OER by considerably lowering the energy barriers of its intermediates. This study provides the innovation of employing trimetallic nanomaterials immobilized on a conductive, continuous porous three-dimensional network formed on a nickel foam (NF) substrate as a highly proficient catalyst for OER.

Simple construction of efficient graphite supported NiCoCu functional catalysts for methanol oxidation reaction using mechanical milling

A low-energy methodology has been proposed to synthesized Ni-based binary and ternary compounds from M-acetylacetonates (M = Ni, Co and Cu) and mechanical milling (MM) to be used as electrocatalysts for the methanol oxidation reaction in alkaline medium (1 M KOH). The strategies used in this study expand the possibilities of obtaining materials with efficient electrocatalytic activities from noble metal-free catalysts, while reducing the production cost. The prepared electrodes were characterized to evaluate changes in the thermal decomposition, as well as chemical, structural, morphological and microstructural changes with the composition. Electrochemical performance was evaluated by conventional methods such as cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The series of Ni-based catalysts demonstrated that after MM the composites integrate with oxides of the individual metallic materials without the formation of solid solutions. The electrocatalytic mass activities of the as-obtained composites were found in the following order: Ni0.80Co0.10Cu0.10/C (1181.14 A/g) ≅ Ni0.8Cu0.2/C (1124.45 A/g) > Ni0.80Co0.05Cu0.15/C (254.50 A/g) > Ni0.80Co0.15Cu0.05/C (209.34 A/g) > Ni0.8Co0.2/C (136.64 A/g). Among them, Ni0.80Co0.10Cu0.10/C showed the greatest stability and the leastwest charge transfer resistance that ranges between 0.28 and 0.80 Ω depending on the methanol concentration, and also presented activities higher than those of the commercial Pt/C catalysts. The results demonstrate that with this simple method, it is possible to modulate the electronic structure reducing CO poisoning on the surface of the catalysts and act as an alternative to replace high-cost noble metals during energy conversion from methanol.

Suppressing Surface Oxidation of Pyrite FeS2 by Cobalt Doping in Lithium Sulfur Batteries.

Lithium-sulfur batteries have emerged as a promising energy storage device due to ultra-high theoretical capacity, but the slow kinetics of sulfur and polysulfide shuttle hinder the batteries' further development. Here, the 10% cobalt-doped pyrite iron disulfide electrocatalyst deposited on acetylene black as a separator coating in lithium-sulfur batteries is reported. The adsorption rate to the intermediate Li2S6 is significantly improved while surface oxidation of FeS2 is inhibited: iron oxide and sulfate, thus avoiding FeS2 electrocatalyst deactivation. The electrocatalytic activity has been evaluated in terms of electronic resistivity, lithium-ion diffusion, liquid-liquid, and liquid-solid conversion kinetics. The coin batteries exhibit ultra-long cycle life at 1C with an initial capacity of 854.7 mAh g-1 and maintained at 440.8 mAh g-1 after 920 cycles. Furthermore, the separator is applied to a laminated pouch battery with a sulfur mass of 326 mg (3.7 mg cm-2) and retained the capacity of 590 mAh g-1 at 0.1 C after 50 cycles. This work demonstrates that FeS2 electrocatalytic activity can be improved when Co-doped FeS2 suppresses surface oxidation and provides a reference for low-cost separator coating design in pouch batteries.

Electrospun carbon nanofibers loaded with sulfur vacancy CoS2 as separator coating to accelerate sulfur conversion in Lithium-Sulfur batteries

Lithium–sulfur batteries (LSBs) have been sought after by researchers owing to their high energy density; however, the inevitable capacity decay and slow reaction kinetics have hindered their advancement. Here, we prepare a Prussian blue analog, Co3[Co(CN)6]2 and synthesize carbon nanofibers/S vacancy CoS2−x (CNFs/CoS2−x) as electrocatalysts for separator coating via electrospinning, carbonization, sulfurization, and hydrogen reduction. CNFs/CoS2−x exhibits excellent electrocatalytic activity, wherein S vacancies induce the partial oxidation of Co2+ to Co3+ in CoS2 and CNFs provide long-range electron transport pathways. Various electrochemical tests, such as Tafel, ion diffusion coefficient, Li2S precipitation, and Li2S6 symmetric cells, further confirm the enhanced electrocatalytic activity. The LSBs with CNFs/CoS2−x modified separator delivers an initial discharge capacity of 1056.7 mAh g−1 at 0.2C, maintaining 840.8 mAh g−1 after 100 cycles at 0.2C. When S loading is increased to 4.42 mg cm−2, the battery retains a discharge capacity of 687.9 mAh g−1 (3.04 mAh cm−2) after 70 cycles at 0.1C. Our work can provide a reference for synthesizing anion-vacancy materials and designing anion-vacancy electrocatalytic composites for LSBs.

Improving the electrocatalytic activity of the copper (II) metal-organic framework by functionalized imidazolate linker and functionalized carbon nanoparticles for detection of acyclovir

With the aim of expansion of nanocomposite materials in electrochemical sensors, the use of nanostructures as the electrode modifier has been shown to improves the kinetics of the electron transfer reactions and consequently increases the sensitivity of the sensors. So, in this study, a new electrochemical sensor was fabricated by using the nanocomposite of copper (II) metal–organic framework with functionalized imidazolate linker [Cu3(BTC)2-2-MIM] and cationic functionalized carbon nanoparticles (CFCNPs) at the glassy carbon electrode (GCE); Cu3(BTC)2-2-MIM/CFCNPs/GCE. The as prepared nanocomposite; Cu3(BTC)2-2-MIM/CFCNPs was characterized using various instrumental techniques. To identify the capabilities and electrocatalytic activity of the synthesized nanocomposite in analytical chemistry, it was used as an electrochemical modifier along with suitable electrochemical techniques. In this regard, the prepared modified electrode; Cu3(BTC)2-2-MIM/CFCNPs/GCE was utilized to the electrooxidation and determination of the acyclovir (ACR) in NaOH solution. Under optimal experimental conditions, the Cu3(BTC)2-2-MIM/CFCNPs/GCE showed low detection limit (0.24 µM) over the concentration ranges of 2.49–84.28 μM of ACR. On the other hand, the present sensor has robust stability, good reproducibility, high selectivity and sensitivity (5.907 µAµM−1 cm−2) in electrodetermination of ACR. Also, the diffusion coefficient of ACR (DACR = 9.25 × 10−6 cm2 s−1), the transfer coefficient (α = 0.34) and catalytic rate constant (kcat = 10.1 × 105 cm3 mol−1 s−1) of ACR electrooxidation reaction were estimated at the surface of modified electrode in NaOH solution. Finally, the Cu3(BTC)2-2-MIM/CFCNPs/GCE was applied as a promising and low-cost sensor for determination of the ACR in actual pharmaceutical formulations and biological samples.

Elevating Oxygen Evolution using Iron Phthalocyanine Infused Vanillic acid Electrocatalyst.

Oxygen evolution reaction (OER) is the bottle neck step in water splitting reaction towards the realization of hydrogen based clean energy production and storage. Metal air batteries and polymer electrolyte membrane fuel cells (PEMFC) are the alternative green energy systems that utilise O2 and H2 in the production of continuous and high energy output without the utilization of carbon based fuels which are the major sources of pollution. Transition metal based N4 organics are explored extensively as oxygen electrocatalysts i. e., OER and oxygen reduction reaction (ORR) catalysts because of their ease of synthesis, tuneable properties, low cost and high performance with long term stability. Here, vanillic acid functionalized iron phthalocyanine (FeVAPc) was synthesised and characterised by various spectroscopic techniques. The novel FeVAPc exhibited good thermal stability and was coated on Ni foam for OER studies. The scanning electron microscopy images showed net-work like surface morphology and the X-ray photoelectron spectroscopy indicated the presence of Fe in +3 oxidation state. The Ni/FeVAPc demonstrated excellent electrocatalytic activity for OER with overpotential of 312 mV at 10 mA.cm-2 current density in 1.0 M KOH electrolyte. The designed organic based catalyst exhibited lesser Tafel slope value which is nearer to the benchmark catalyst, IrO2. The proposed catalyst exhibited good stability as phthalocyanines are highly stable and do not undergo decomposition even in strong acidic and basic corrosive media. Integration of FeVAPc onto the Ni foam resulted in higher mass activity, lower charge transfer resistance, high active surface area leading to enhanced conductivity and activity. The fabricated Ni/FeVAPc is an appropriate cost-effective, efficient and stable catalyst for OER towards industrial applications.