Cyclic Voltammetry Research Articles

Incorporation of Pd Catalyst into Highly Effective Borophene Nanosheet Co-Catalyst for Electrokinetics and Electrochemical Oxygen Reduction Reactions

AbstractTo improve the performance of the system, it is of great importance to develop efficient catalysts for ethanol (EtOH) electro-oxidation. Pd/B electrocatalyst was synthesized using a sonochemical method. Structural and electrochemical properties of the prepared nanomaterial were investigated using electrochemical and physical techniques such as Raman spectroscopy, electrochemical impedance spectroscopy (EIS), x-ray diffraction (XRD), zetersizer, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM) and energy-dispersive x-ray spectroscopy (EDS) and cyclic voltammetry (CV). FTIR confirmed all the functional groups of carbon black, Pd/C, borophene, and Pd/B, and the crystallinity was investigated using XRD. EIS showed that Pd/B has a faster charge transfer and, through investigation using CV, Pd/B showed a more negative onset potential and higher current (−0.76 V vs. Ag|AgCl; 0.07 mA) than Pd/C (−0.65 V vs. Ag|AgCl; 0.05 mA), indicating a more catalytic behavior and tolerance of Pd/B. The active sites could be attributed to the addition of borophene. During the anodic sweeping direction of Pd/B electrocatalyst, it was observed that the ratio of backward peak current (Ibwd) to forward peak current (Ifwd), (Ibwd/Ifwd) of in a 2 M of NaOH + 2 M of EtOH is almost equal to (Ibwd/Ifwd) 1 which shows excellent tolerance of Pd/B to poisoning by ethanol intermediate species. The electron transfer rate (Ks) values for Pd/B at 0.1 M, 0.5 M, 1 M, 1.5 M, and 2 M were estimated to be 4.50 × 10−13 s−1, 1.08 × 10−12 s−1, 4.28 × 10−13 s−1, 5.25 × 10−14 s−1 and 9.35 × 10-14 s−1. At 2 M there is a faster electron transfer than at other concentrations which is also evidenced by the obtained diffusion values (D) of the system which were found to be 2.92 × 10−7 cm2 s−1, 4.72 × 10−8 cm2 s−1, 4.82 × 10−8 cm2 s−1, 1.22 × 10−7 cm2 s−1, and 9.12 × 10−8 cm2 s−1. The electrochemically active surface area (ECSA) is strongly related to intrinsic activity, Pd/B (1.85 cm2/mg × 10−5 cm2/mg) denotes the highest Pd-O stripping charge than Pd/C (1.13 cm2/mg × 10−5 cm2/mg).

Synthesize electrode material based on rGO/Polyacrylic acid prepared by a combination of direct ink writing technique and UV irradiation

In this work, the rGO/polyacrylic acid (rGO/PAA) composite film was synthesized using the 3D direct ink writing technique with GO/acrylic acid (GO/AA) ink and UV irradiation. Results show that after a UV irradiation time of 3.6 seconds, GO was reduced into rGO, and AA was polymerized into PAA. The prepared material was characterized by using Fourier Transform Infrared Spectroscopy (FT-IR), Energy-dispersive X-ray spectroscopy (EDX), cyclic voltammetry (CV), and galvanostatic charge/discharge technique (GCD). The obtained composite film is applied as an electrode for the supercapacitor. The electrode has a specific capacity of 321 F/g at a current density of 1 A/g and retains 82% of its initial capacity after 5,000 charge/discharge cycles at a current density of 5 A/g.

Synthesis, characterisation and voltammetric study of dimethylammonium lead iodide perovskite

In the last decade, the most investigated perovskite materials are the hybrid organic-inorganic perovskites (HOIPs) due to their optoelectronic properties and possible application in the production of photovoltaics. This interest has led to an ongoing search for new HOIP variants, alongside thorough investigations of the properties of existing HOIPs. That is why our research in the field of organic-inorganic perovskites is aimed at the synthesis, characterization, and investigation of the electrochemical properties of dimethylammonium lead iodide (DMAPbI3) using voltammetric studies. A modified synthesis of DMAPbI3, differing slightly from the one described in the literature, was performed by combining stoichiometric amounts of lead iodide (PbI2) and dimethylammonium iodide (DMAI) dissolved in acetonitrile. After conducting controlled evaporation, a yellow crystalline powder of DMAPbI3 was obtained. The identity and purity of the obtained compound were confirmed by powder X-ray diffraction (PXRD), infrared (IR) and Raman spectroscopy, and scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDX). Investigations on the electrochemical properties of DMAPbI3 by cyclic voltammetry were performed with dichloromethane (DCM) and tetrabutylammonium chloride (TBAC) as the electrolyte. A paraffin-impregnated graphite electrode (PIGE) was used as a working electrode, on which the perovskite microparticles were immobilized. The electrochemical activity of DMAPbI3 is recognized through an intense, broad, and irreversible anodic peak attributed to the oxidation of the constituents to different possible products and the decomposition of the perovskite structure.

Tube-Like Copper Cobalt Oxide Anchored with Multiwalled Carbon Nanotube Nanocomposites Based on a Glassy Carbon Electrode for the Electrochemical Detection of Nilutamide

Abstract Developing a precise and effective method to detect Nilutamide (NIL) is essential due to its contamination of the environment, which poses significant risks to human health and the biosphere. In this study, we employed a simple hydrothermal technique to create a nanocomposite of CuCo2O4 (copper cobalt oxide) and multi-walled carbon nanotube (MWCNT), which was then anchored onto a glassy carbon electrode for NIL detection. Various spectroscopic techniques were employed to confirm the structure of the nanomaterial, and its electrochemical properties were examined using cyclic voltammetry, differential pulse voltammetry, and electrochemical impedance spectroscopy. The CuCo2O4/MWCNT nanocomposite-modified electrode exhibited a wide linear detection range from 0.01 to 170 µM, a high sensitivity of 1.50 μA μM−1 cm−2, a low detection limit of 0.01 μM, outstanding stability, repeatability, and practical applicability for NIL detection.

Influence of electrophoretic deposition of micro- or nanosized silica particles on the microstructure of carbon fibers and their bond behavior with cementitious matrices

The application of carbon fiber (CF) reinforced cementitious composites is often restricted by the poor load transfer between the components. In this study, two reactive coating materials—nano-silica and micro-silica—are utilized to modify the CF surfaces via an electrophoretic deposition approach. These negatively charged particles are able to be electrosorbed onto the fiber surfaces under a constant electrical field according to the zeta and cyclic voltammetry measurements. After surface treatment, XRD analysis of CFs showed an increase in graphite crystallite thickness and decrement in interlayer spacing d002\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${d}_{002}$$\\end{document}, significantly affecting the fiber diameters. Additionally, the lengths of crystallites were reduced, which can impair the fiber strength and their temperature stability. Single fiber pullout tests exhibited that the interfacial bonding can be clearly enhanced by both reactive coatings. Microscopic observation revealed that C–S–H gel and calcite structures can be formed near the fiber surfaces after immersion in cement pore solution owing to pozzolanic reaction and nucleation effect, tremendously heightening both chemical and mechanical interaction between fiber and cement. Finally, based on a detailed micromechanical analysis, the reinforcing mechanisms between the differently modified fibers and the cementitious matrix were elaborated and discussed.Graphical abstract

Establishing a new efficiency descriptor for methanol oxidation reaction and its validation with commercially available Pt‐based catalysts

AbstractDirect methanol fuel cells (DMFCs) have received a lot of attention in recent years as promising technology for generating clean and efficient energy. In DMFC, the anode catalyst is a vital component because it is involved in the oxidation of methanol, which produces electrons that can be used as an energy source. Cyclic voltammetry (CV) is commonly used to test the characteristics of the electrode materials before they are employed in the actual fuel cell. Interestingly in the case of DMFCs CV also is a useful technique to obtain vital information about the performance and expected efficiency of the electrodes. In general, the CV of methanol electrooxidation for Pt‐based catalysts has two peaks, If in the forward scan (anodic scan) and Ib in the backward scan (cathodic scan). The ratio of these two peaks (If/Ib) is the most commonly used criterion for investigating CO poisoning in catalysts. However, there is a great deal of ambiguity surrounding this criterion, owing to the genesis of Ib. Addressing this we present here a new criterion to evaluate the efficiency of the catalyst using the same CV technique. We validate this newly proposed criterion with commercial Pt/C (comm. Pt/C) and other commercially available alloy catalysts.

Tailoring Spinel with Perovskite: Sr Substitution in the Perovskite Phase of CoFe2O4–LaCoO3 Nanocomposite for Oxygen Evolution and Methanol Oxidation in Alkaline Medium

CoFe2O4–La1−xSrxCoO3 (x = 0.2, 0.6, 0.8) composites have been synthesized using a two‐step, low‐temperature wet chemical approach that combines coprecipitation and sol–gel techniques. The composite materials have been physicochemically analyzed using Fourier‐transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscope. The electrocatalytic properties of the composite materials have been assessed in terms of their performance in oxygen evolution reaction (OER) and methanol oxidation reaction (MOR) in alkaline medium. Cyclic voltammetry has been used for analyzing the redox behavior of the materials in 1 M KOH solution. The electrocatalytic activity of the materials has been assessed using anodic polarization curves on Ni substrate and the CoFe2O4–La0.2Sr0.8CoO3 film electrode demonstrates excellent activity, with current densities of 11.1 mA cm−2 for OER and 47.4 mA cm−2 for MOR at 650 mV. Also, the CoFe2O4–La0.2Sr0.8CoO3 film electrode has the maximum specific activity of 1.1 × 103 mA cm−2 g−1 at 650 mV toward OER. The electrodes’ stability has been assessed through chronoamperometric experiments and additional insight into the enhancement of electrocatalytic activity gained through the electrochemical surface area estimations using electrochemical impedance spectroscopy. From chronoamperometric experiment, it has been observed that the CoFe2O4–La0.2Sr0.8CoO3 film electrode attains stability within 114 s with a current density of 108.7 mA cm−2. Furthermore, the thermodynamic parameters, including the standard enthalpy of activation (ΔH°#), standard entropy of activation (ΔS°#), and standard electrochemical energy of activation (), have been estimated by anodic polarization curve recorded in KOH as well as KOH with CH3OH solutions at various temperatures.

ZnO/TiO2 heterojunction nanorod array for efficient photoelectrochemical water splitting

This study presents a novel approach utilizing a simple, stable, reproducible CV (Cyclic Voltammetry) electrodeposition method to deposit varying amounts of ZnO onto ordered TiO2 (Rutile) nanorod arrays. Comprehensive investigations were conducted on the morphology, semiconductor band-gap structure of different ZnO/Rutile composites, and their performance in photocatalytic (PC) and photoelectrochemical (PEC) hydrogen production. Results demonstrate that the ZnO/TiO2 photoanodes fabricated in this manner exhibit outstanding PC/PEC hydrogen production capabilities. Particularly noteworthy is the Z/R-15 photoanode, showcasing superior PEC performance with a photocurrent density 3.5 times higher than that of the pristine TiO2 photoanode under equivalent conditions. Furthermore, it was observed that depositing ZnO onto highly crystalline, annealed TiO2 nanorods yields optimal photoelectrical properties. Incorporating oxygen-rich vacancies in ZnO significantly enhances the photoelectrocatalytic performance of TiO2 photoanodes. The CV electrodeposition method offers valuable insights for developing efficient photocatalytic hydrogen production catalysts.

Selective and sensitive MIP-Based electrochemical Sensor for the analytical determination of Lanreotide

Lanreotide (LAN) is an analog of somatostatin used to treat acromegaly and neuroendocrine tumors. Considering drug toxicity and the lack of sensitive techniques in drug analysis, the development of sensitive analytical methods is of great importance. During this research, a molecular imprinted polymer (MIP) based film [P(HEMA-MAGA)@MIP/GCE] was prepared by photopolymerization technique for electrochemical determination of LAN for the first time. N-methacryloyl-L-glutamic acid (MAGA) and hydroxyethyl methacrylate (HEMA) were used as functional and basic monomers, respectively. The surface alterations were investigated using scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) and the chemical composition of the MIP-based sensor. Theelectrochemical characterization of the modifiedelectrodes was assessed using electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). Using differential pulse voltammetry (DPV) in standard solution and spiked serum sample of LAN, the linear response range for LAN was obtained as 1.0x10 − 14 M – 1.0x10 − 13 M. The limit of detection (LOD) values were 1.76x10 − 15 M and 1.82x10 − 15 M in water and commercial human serum, respectively. The limit of quantitation(LOQ) values for these were 5.85x10 − 15 M and 6.07x10 − 15 M, respectively. The P(HEMA-MAGA)@MIP/GCE sensor also showed excellent recovery in pharmaceutical preparation and commercial human serum form with of 99.37 % and 99.27 %, respectively, with a good RSD value (0.51–0.73), confirming the accuracy and precision of the sensor. As a control, the non-imprinted polymer (NIP) was also prepared to serve in the same way but without the template. The selectivity experiments were conducted using somatostatin (SOM) and octreotide (OC) as potential competitors to demonstrate the selectivity of the proposed sensor against LAN molecules.

Revolutionising pesticide detection: a high-sensitivity electrochemical sensor with CdS/g-C3N4/MWCNTs for paraquat monitoring

ABSTRACT Over a decade, the Malaysia National Poison Centre found that 40% of pesticide poisoning cases may be linked to excessive paraquat (PQ) in water, soil, or food, underscoring the widespread impact on public health and emphasising the importance of detecting even trace amounts of PQ residues in the environment. Thus, this study presents a novel electrochemical sensor based on multiwalled carbon nanotubes (MWCNTs) reinforced cadmium sulphide co-anchoring on graphitic carbon nitride (CdS/g-C3N4) nanocomposites for PQ detection. The CdS/g-C3N4 nanocomposite was successfully synthesised and characterised through FTIR, XRD, EDX, FESEM and TEM analysis. The modified electrode (CdS/g-C3N4/MWCNTs PE) exhibited improved electrocatalytic activity, as demonstrated by cyclic voltammetry (CV) and impedance spectroscopy. The CdS/g-C3N4/MWCNTs PE displayed a high CV peak and low Rct value which corresponded to a higher electron transfer rate, reduced charge transfer resistance and enhanced mass transport properties. The electrochemical sensor’s performance was evaluated for the detection of PQ, and it demonstrated a linear response in a range of 1.0 µM to 0.1 mM with a limit of detection of 0.14 μM. Furthermore, the sensor exhibited selectivity with a less than 16% potential interference from various organic chemicals and inorganic ions. The sensor’s applicability was tested by quantifying PQ in real water samples, showing excellent recovery percentages ranging from 98.9% to 102.0%. The developed electrochemical sensor provides a practical solution for the rapid and accurate monitoring of PQ levels in the environment. This work establishes the foundation for the development of a selective electrochemical sensor for pesticide analysis, addressing both public health and environmental concerns.

High-efficient electrooxidation of ethylene glycol and ethanol on PdSn alloy loaded by versatile poly(3,4-ethylenedioxythiophene)

Developing a novel catalyst with lower noble-metal loading and higher catalytic efficiency is significant for promoting the widespread application of direct alcohol fuel cells (DAFCs). In this work, poly(3,4-ethylenedioxythiophene) (PEDOT) supported the PdSn alloy (PdSn/PEDOT) were simply synthesized and their electrocatalytic performance toward the oxidation of ethylene glycol and ethanol (EGOR and EOR) were investigated in alkaline media, respectively. In comparison with other control catalysts, the optimized Pd4Sn6/PEDOT catalyst exhibits the highest mass activity (7125/4166 mA mgPd−1) and specific activity (26/15 mA cm−2) towards EGOR/EOR. The mass activity of Pd4Sn6/PEDOT for EGOR and EOR are 11.9 and 10.9 times higher than commercial Pd/C, respectively. Moreover, chronoamperometry (CA) and successive cyclic voltammetry (CV) tests show that the CO resistance ability and durability of the Pd4Sn6/PEDOT catalyst were superior to Pd4Sn6, Pd/PEDOT and commercial Pd/C catalysts, which can be attributed to the d-band center of Pd can be effectively downshifted and the interface strain effect between electrons caused by the conjugated structure between PEDOT groups. This work provides an effective strategy for the development of highly efficient anode catalysts of DAFCs.

Regulating effect of the halogen atoms on the cofacial dinuclear Schiff base complexes: Synthesis, spectroscopy, electrochemistry, and DFT calculations

The present study reports the synthesis and characterization of two new halogenated Schiff base copper (II) derivatives, namely [CuII2(3‐Cl‐Salmphen)2] (Cu‐Cl‐Salmphen) and [CuII2(3‐Br‐Salmphen)2] (Cu‐Br‐Salmphen), which were characterized by UV–Vis, FT‐IR, 1H‐NMR, and 13C‐NMR spectroscopy. Single crystal structural analysis revealed that each complex contains two crystallography independent, distorted copper centers, where each Cu center exhibits the same coordination environment with N2O2 donor atoms from two different ligands. To investigate the substitution effect of halogen atoms on the properties of the complexes, the non‐halogenated isomer [CuII2(H‐Salmphen)2] (Cu‐H‐Salmphen) was introduced for comparison. The differences between the halogenated and the non‐halogenated analogues were compared through spectroscopic, electrochemical, DFT, and TD‐DFT theoretical calculations. The optical experimental results indicated that the introduction of halogen atoms decreased the energy gap between the ground and excited states, leading to enhanced optical absorption capabilities of the compounds. Electrochemical tests showed that the halogenated analogues exhibited better electrochemical performance, and with the increase in an atomic number of the halogen atoms, the compounds displayed a gradual increase in cyclic voltammetry peak areas, diffusion coefficients, and conductivities. Theoretical calculations revealed that the introduction of halogen atoms simultaneously expanded the conjugated area of the molecules, decreased the HOMO‐LUMO energy levels of the complexes, and strengthened the intramolecular interactions. Furthermore, the potential mechanism of the tuning effect of halogen atoms on the charge transfer process was proposed.

Electrocatalytic Transfer Hydrogenation of 1‐Octene with [(tBuPCP)Ir(H)(Cl)] and Water

Electrocatalytic hydrogenation of 1‐octene as non‐activated model substrate with neutral water as H‐donor is reported, using [(tBuPCP)Ir(H)(Cl)] (1) as the catalyst, to form octane with high faradaic efficiency (FE) of 96% and a kobs of 87 s–1. Cyclic voltammetry with 1 revealed that two subsequent reductions trigger the elimination of Cl– and afford the highly reactive anionic Ir(I) hydride complex [(tBuPCP)Ir(H)]– (2), a previously merely proposed intermediate for which we now report first experimental data by mass spectrometry. In absence of alkene, the stoichiometric electrolysis of 1 in THF with water selectively affords the Ir(III) dihydride complex [(tBuPCP)Ir(H)2] (3) in 88% FE from the reaction of 2 with H2O. Complex 3 then hydrogenates the alkene in classical fashion. The presented electro‐hydrogenation works with extremely high FE, because the iridium hydrides are water stable, which prevents H2 formation. Even in strongly alkaline conditions (Bu4NOH added), the electro‐hydrogenation of 1‐octene with 1 also proceeds cleanly (89% FE), suggesting a highly robust process that may rely on H2O activation, reminiscent to transfer hydrogenation pathways, instead of classical H+ reduction. DFT calculations confirmed oxidative addition of H2O as a key step in this context.

An ultrasensitive electrochemical sensor based on boron-doped porous graphene for efficient detection of nitrite in food

Boron (B) doping plays a critical role in adjusting the electronic properties of carbon materials. In this work, B-doped porous graphene (B-PG) was successfully prepared by a simple strategy and used as an advanced electrode material for the detection of nitrite (NO-2) in food. The scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were employed to characterize this B-PG. Due to the ideal doping of boron atoms, the material has good conductivity and exhibits excellent electrochemical catalytic performance. NO-2 was used as the representative analytes to demonstrate the sensing performance of B-PG. It is found that the B-PG modified GCE exhibited a linear response over the concentration range from 3 μM – 3 mM and 3 mM – 15 mM, with a detection limit of 1.1 μM. The designed electrochemical sensor has good analytical performance, such as high sensitivity, good reproducibility and acceptable accuracy, and can be successfully applied to the accurate and precise detection of residual NO-2 in food.

Gallium Nitride Electrodeposition at Indium Tin Oxide and Fluorine Tin Oxide Electrodes in Ammonium Nitrate and Gallium Nitrate Aqueous Solution

Gallium nitride thin films in semiconductor technology have garnered interest. This study aims to develop an effective GaN electrodeposition technique applicable where needed. To determine the optimal conditions, cyclic voltammetry (CV) was done on a boron-doped diamond electrode at 0.01 mV/s potential scan rate and at 0.8 V vs. Ag/AgCl (Saturated KCl) constant applied potential. In the CV study, a well-defined peak formed at -1.75 V vs. Ag/Ag/Cl (Saturated KCl). To start examining thin film features on Indium Tin Oxide (ITO) and Fluorine Tin Oxide (FTO) electrodes, chronoamperometry (CA) measurements were done at time scales ranging from 3600s to 14,000s and at a constant applied potential of -1.7 V vs. Ag/AgCl (Saturated KCl). The characterization methods used to examine the samples included SEM and EDS. The optimal weight electrodeposition percentages of Ga and N on ITO were 10.3% and 27.2% and 47.3% and 12.7% on FTO respectively.

Synthesis, Photophysical and Electronic Properties of a D-π-A Julolidine-like Pyrenyl-o-Carborane.

We synthesized 2-(1-1,2-dicarbadodecaboranyl(12))-6,6,12,12-tetramethyl-7,8,11,12-tetrahydro-6H,10H-phenaleno[1,9-fg]pyrido[3,2,1-ij]quinoline (4) a julolidine-like pyrenyl-o-carborane, with pyrene substituted at the 2,7-positions on the HOMO/LUMO nodal plane. Using solid state molecular structures, photophysical data, cyclic voltammetry, DFT and LR-TDDFT calculations, we compare o-carborane and B(mes)2 (mes = 2,4,6-Me3C6H2) as acceptor groups. Whereas the π-acceptor strength of B(mes)2 is sufficient to drop the pyrene LUMO+1 below the LUMO, the carborane does not do this. We confirm the π-donor strength of the julolidine-like moiety, however, which raises the pyrene HOMO-1 above the HOMO. In contrast to the analogous pyrene-2-yl-o-carborane, 2-(1-1,2-dicarbadodecaboranyl(12))-pyrene VI, which exhibits dual fluorescence, because the rate of internal conversion between locally-excited (LE) and charge transfer (CT) (from the pyrene to the carborane) states is faster than the radiative decay rate, leading to a thermodynamic equilibrium between the 2 states, 4 shows only single fluorescence, as the CT state involving the carborane as the acceptor moiety in not kinetically accessible, so a more localized CT emission involving the julolidine-like pyrene moiety is observed.

Electrocatalytic Transfer Hydrogenation of 1-Octene with [(tBuPCP)Ir(H)(Cl)] and Water.

Electrocatalytic hydrogenation of 1-octene as non-activated model substrate with neutral water as H-donor is reported, using [(tBuPCP)Ir(H)(Cl)] (1) as the catalyst, to form octane with high faradaic efficiency (FE) of 96% and a kobs of 87 s-1. Cyclic voltammetry with 1 revealed that two subsequent reductions trigger the elimination of Cl- and afford the highly reactive anionic Ir(I) hydride complex [(tBuPCP)Ir(H)]- (2), a previously merely proposed intermediate for which we now report first experimental data by mass spectrometry. In absence of alkene, the stoichiometric electrolysis of 1 in THF with water selectively affords the Ir(III) dihydride complex [(tBuPCP)Ir(H)2] (3) in 88% FE from the reaction of 2 with H2O. Complex 3 then hydrogenates the alkene in classical fashion. The presented electro-hydrogenation works with extremely high FE, because the iridium hydrides are water stable, which prevents H2 formation. Even in strongly alkaline conditions (Bu4NOH added), the electro-hydrogenation of 1-octene with 1 also proceeds cleanly (89% FE), suggesting a highly robust process that may rely on H2O activation, reminiscent to transfer hydrogenation pathways, instead of classical H+ reduction. DFT calculations confirmed oxidative addition of H2O as a key step in this context.

Effect of sandblasting and acid surface pretreatment on the specific capacitance of CuO nanostructures grown by hot water treatment for supercapacitor electrode applications.

Crystalline copper oxide (CuO) nanostructures with micro, nano, and micro-nano surface roughness were grown on Cu sheet substrates by a facile, scalable, low-cost, and low-temperature hot water treatment (HWT) method that simply involved immersing Cu sheet in DI water at 75 °C for 24 hours without any chemical additives. Various morphological features and sizes of CuO nanostructures were tuned by using different surface pretreatment techniques including acid treatment, sandblasting, or a combination of those two. The surface morphology of the prepared samples was analyzed by scanning electron microscopy (SEM). The crystal structure of the CuO nanostructures was investigated by X-ray diffraction (XRD) and Raman spectroscopy. To study the pseudocapacitive behavior, their potential supercapacitor performance, and equivalent series resistance, electrochemical analysis was done by cyclic voltammetry (CV) and electrochemical impedance spectroscopy for all the CuO/Cu samples in 1 M of Na2SO4 electrolyte. Among all, the best supercapacitive performance was achieved for CuO/Cu samples pretreated with Sandblasting followed by Acid treatment resulting in a specific capacitance of about 104 F/g. The electrode with the Sandblasted + Acid pretreated sample showed a maximum of ~ 69% capacitive retention after 2000 consecutive cycles. Our results indicate that CuO nanostructures on Cu substrates prepared with different surface pretreatment conditions and grown by HWT can be promising electrodes for supercapacitor device applications.

Enhancing Stability and Activity of Transition Metal Chalcogenides: Development of Carbon-Based Hydrochar Supported Nickel-Cobalt Selenide Electrocatalyst for Oxygen Evolution Reaction

Transition metal chalcogenides (TMCs) have been utilized as cost-effective alternatives for noble metal electrocatalysts, exhibiting comparable activity in the oxygen evolution reaction (OER). Nickel-cobalt selenide (NiCoSe) is a TMC exhibiting significant potential in reducing the overpotential of the oxygen evolution reaction (OER). A carbon-based hydrochar support is used as a scaffold for depositing NiCoSe, ensuring the dispersion and stability of the synthesized electrocatalyst. This work develops a NiCoSe/hydrochar electrocatalyst to enhance the stability and activity of the TMC towards OER. Various compositions of nickel-cobalt selenide (NiCoSe2, Ni0.85Co0.85Se, and Ni0.6Co0.4Se2) with a chitin-based hydrochar support are synthesized. The electrocatalytic activity is determined using cyclic voltammetry (CV) and linear sweep voltammetry using a three-electrode set-up. NiCoSe2 has the lowest overpotential at 179.3 mV and a Tafel slope of 163.4 mV-dec-1. This highlights the enhanced performance of NiCoSe2 compared to other compositions.

Reductive Dynamic and Static Excited State Quenching of a Homoleptic Ruthenium Complex Bearing Aldehyde Groups.

A new homoleptic Ru polypyridyl complex bearing two aldehyde groups on each bipyridine ligand, [Ru(dab)3](PF6)2, where dab is 4,4'-dicarbaldehyde-2,2'-bipyridine, was synthesized, characterized, and utilized for iodide photo-oxidation studies. In acetonitrile (CH3CN) solution, the complex displayed an intense metal-to-ligand charge transfer (MLCT) absorbance maximum at 475 nm (ε = 22,000 M-1 cm-1) and an infrared (IR) band at 1712 cm-1 assigned to the pendent aldehyde groups. Visible light excitation in air-saturated solution resulted in room temperature photoluminescence (PL) with a maximum at 675 nm, a quantum yield, ϕPL = 0.048, and an excited state lifetime, το = 440 ns, from which radiative and nonradiative relaxation rate constants were extracted, kr = 9.1 × 104 s-1 and knr = 1.8 × 106 s-1. Pulsed visible light excitation yielded transient UV-vis and IR absorption spectra consistent with an MLCT excited state; relaxation occurred with the maintenance of two isosbestic points in the visible region, and a lifetime that agreed with that measured by time-resolved PL. Cyclic voltammetry studies in a CH3CN solution with 0.1 M TBAPF6 electrolyte revealed a quasi-reversible oxidation, E°(RuIII/II) = +1.25 V vs. Fc+/0, and three sequential one-electron reductions at -1.10, -1.25, and -1.54 V vs. Fc+/0. An excited state reduction potential of E°(Ru*2+/+) = +0.89 V vs. Fc+/0 was estimated with the Rehm-Weller expression. Titration of tetrabutylammonium iodide, TBAI, into a CD3CN solution of [Ru(dab)3](PF6)2 resulted in significant shifts in the aldehyde H atom and 3,3'-biypridyl resonances that were analyzed with a 1:1 equilibrium model, from which Keq = 460 M-1 was extracted, increasing to 5800 M-1 when the solvent was changed to acetone-d6. Iodide titrations resulted in a significant quenching of the [Ru(dab)3]*2+ lifetime and quantum yield in both CH3CN and acetone solvents. In CH3CN, the quenching was mainly dynamic and well described by the Stern-Volmer model, from which a quenching rate constant, kq, of 4.5 × 1010 M-1 s-1 and an equilibrium constant, Keq, of 8.3 × 103 M-1 were obtained. In acetone, the static quenching pathway by iodide was greatly enhanced, with a Keq of 1.2 × 104 M-1 and a higher kq of 9.2 × 1010 M-1 s-1.