Electrocatalyst For Oxidation Research Articles

N-doped hollow carbon nanospheres embedded in N-doped graphene loaded with palladium nanoparticles as an efficient electrocatalyst for formic acid oxidation

N-doped hollow carbon nanospheres embedded in N-doped graphene loaded with palladium nanoparticles as an efficient electrocatalyst for formic acid oxidation

Controllable Synthesis of Fe2O3/Nickel Cobaltite Electrocatalyst to Enhance Oxidation of Small Molecules

Nickel-based catalysts have been widely recognized as highly promising electrocatalysts for oxidation. Herein, we designed a catalyst surface based on iron oxide electrodeposited on NiCo2O4 spinel oxide. Nickel foam was used as a support for the prepared catalysts. The modified surface was characterized by different techniques like electron microscopy and X-ray photon spectroscopy. The activity of the modified surface was investigated through the electrochemical oxidation of different organic molecules such as urea, ethanol, and ethylene glycol. Therefore, the modified Fe@ NiCo2O4/NF current in 1.0 M NaOH and 1.0 M fuel concentrations reached 31.4, 27.1, and 17.8 mA cm−2 for urea, ethanol, and ethylene glycol, respectively. Moreover, a range of kinetic characteristics parameters were computed, such as the diffusion coefficient, Tafel slope, and transfer coefficient. Chronoamperometry was employed to assess the electrode’s resistance to long-term oxidation. Consequently, the electrode’s activity exhibited a reduction ranging from 17% to 30% over a continuous oxidation period of 300 min.

The Enhanced Performance of NiCuOOH/NiCu(OH)2 Electrode Using Pre-Conversion Treatment for the Electrochemical Oxidation of Ammonia.

Electrochemical oxidation of ammonia is an attractive process for wastewater treatment, hydrogen production, and ammonia fuel cells. However, the sluggish kinetics of the anode reaction has limited its applications, leading to a high demand for novel electrocatalysts. Herein, the electrode with the in situ growth of NiCu(OH)2 was partially transformed into the NiCuOOH phase by a pre-treatment using highly oxidative solutions. As revealed by SEM, XPS, and electrochemical analysis, such a strategy maintained the 3D structure, while inducing more active sites before the in situ generation of oxyhydroxide sites during the electrochemical reaction. The optimized NiCuOOH-1 sample exhibited the current density of 6.06 mA cm-2 at 0.5 V, which is 1.67 times higher than that of NiCu(OH)2 (3.63 mA cm-2). Moreover, the sample with a higher crystalline degree of the NiCuOOH phase exhibited lower performance, demonstrating the importance of a moderate treatment condition. In addition, the NiCuOOH-1 sample presented low selectivity (<20%) towards NO2- and stable activity during the long-term operation. The findings of this study would provide valuable insights into the development of transition metal electrocatalysts for ammonia oxidation.

Insights into the role of Co3O4/Ti3C2 MXene hybrid material in photoelectrochemical water oxidation over BiVO4 photoanode

Developing efficient hole transport layers and water oxidation electrocatalysts is vital for improving the performance of photoelectrochemical (PEC) devices for water-splitting. In this work, we synthesized Co3O4 nanoparticles/Ti3C2-MXene hybrid material and utilized it as a dual-function material to transport the photogenerated holes and catalyze the water oxidation reaction. It was found that the modification of BiVO4 with Co3O4/Ti3C2-MXene prolonged the lifetime of the photogenerated holes by 13.7-fold (i.e. from 0.26 s for BiVO4 to 3.56 s for Co3O4/Ti3C2/BiVO4) and significantly reduced the charge transfer resistance. The modification of BiVO4 with only Ti3C2-MXene resulted in significant surface recombination more likely due to the high concentration of the accumulated holes in the Mxene layer because of its low electrocatalytic activity toward water oxidation reaction. Employing the Co3O4/Ti3C2-MXene hybrid material significantly reduced the rate constant of surface recombination and dramatically enhanced the charge transfer efficiency (i.e. from 0.17% for BiVO4 to 14.0% for Co3O4/Ti3C2/BiVO4 at 0.65 VRHE). Under optimized conditions, the Co3O4/Ti3C2/BiVO4 photoanode was able to deliver 5.05 mA cm−2 at 1.23 VRHE and outperforms Ti3C2/BiVO4 and Co3O4/BiVO4 photoanodes. Moreover, it showed high stability for over 50 hours and reached a Faradaic efficiency of 90%. An applied bias photo-to-current efficiency (ABPE) value of 1.71% at 0.62 VPt was obtained for the overall water splitting. This work provides a facile method to reduce surface recombination and enhance the stability and PEC efficiency of BiVO4 photoanodes via the modification with dual-function oxygen evolution catalyst/hole transport layer hybrid material.

Oxygen Isotopologues Resolved from Water Oxidation Electrocatalysis by Electron Paramagnetic Resonance Spectroscopy.

Electrocatalytic water oxidation is a key transformation in many strategies designed to harness solar energy and store it as chemical fuels. Understanding the mechanism(s) of the best electrocatalysts for water oxidation has been a fundamental chemical challenge for decades. Here, we quantitate evolved dioxygen isotopologue composition via gas-phase EPR spectroscopy to elucidate the mechanisms of water oxidation on metal oxide electrocatalysts with high precision. Isotope fractionation is paired with computational and kinetic modeling, showing that this technique is sensitive enough to differentiate O-O bond-forming steps. Strong agreement between experiment and theory indicates that for the nickel-iron layered double hydroxide─one of the best earth-abundant electrocatalysts to be studied─water oxidation proceeds via a dioxo coupling mechanism to form a side-bound peroxide rather than a hydroxide attack to form an end-bound peroxide.

Bioinspired Tetranuclear Manganese Cubane Complex as an Efficient Molecular Electrocatalyst for Two-electron Water Oxidation Towards Hydrogen Peroxide.

Stable homogenous two-electron water oxidation electrocatalysts are highly demanded to understand the precise mechanism and reaction intermediates of electrochemical H2O2 production.Here we report a tetranuclear manganese complex with a cubane structure which can electrocatalyze water oxidation to hydrogen peroxide under alkaline and neutral conditions. Such a complex demonstrates an optimal Faradaic efficiency (FE) of 87%, which is the highest FE(H2O2) among reported homogeneous and heterogeneous electrocatalysts. In addition, active species were identified and co-catalysts were excluded through ESI-MS characterization. Furthermore, we identified water binding sites and isolated one-electron oxidation intermediate by chemical oxidation of the catalyst in the presence of water substrates. It is evident that efficient proton-accepting electrolytes avoid rapid proton building-up at electrode and substantially improve reaction rate and selectivity. Accordingly, we propose a two-electron catalytic cycle model for water oxidation to hydrogen peroxide with the bioinspired molecular electrocatalyst. The present work is expected to provide an ideal platform to elucidate the two-electron WOR mechanism at the atomic level.

Bioinspired Tetranuclear Manganese Cubane Complex as an Efficient Molecular Electrocatalyst for Two‐electron Water Oxidation Towards Hydrogen Peroxide

Stable homogenous two‐electron water oxidation electrocatalysts are highly demanded to understand the precise mechanism and reaction intermediates of electrochemical H2O2 production.Here we report a tetranuclear manganese complex with a cubane structure which can electrocatalyze water oxidation to hydrogen peroxide under alkaline and neutral conditions. Such a complex demonstrates an optimal Faradaic efficiency (FE) of 87%, which is the highest FE(H2O2) among reported homogeneous and heterogeneous electrocatalysts. In addition, active species were identified and co‐catalysts were excluded through ESI‐MS characterization. Furthermore, we identified water binding sites and isolated one‐electron oxidation intermediate by chemical oxidation of the catalyst in the presence of water substrates. It is evident that efficient proton‐accepting electrolytes avoid rapid proton building‐up at electrode and substantially improve reaction rate and selectivity. Accordingly, we propose a two‐electron catalytic cycle model for water oxidation to hydrogen peroxide with the bioinspired molecular electrocatalyst. The present work is expected to provide an ideal platform to elucidate the two‐electron WOR mechanism at the atomic level.

SnO2/CoTeO3 heterojunction for smartly conducting hydrogen evolution linking to organics electrocatalytic oxidation

As a sustainable energy form, hydrogen can be most practically obtained from electrocatalytic water splitting. The familiar organics can be oxidized to more useful intermediates in chemical industries. Herein, a SnO2/(CoTeO3)2 heterojunction is designed as an electrocatalyst for hydrogen evolution reaction (HER) and organic electrocatalytic oxidation. The heterojunction has good electrocatalytic performances with overpotentials of 281 mV at 10 mA cm−2 in 1 M KOH+0.1 M glycerol, 358 mV at 10 mA cm−2 in 1 M KOH +0.33 M urea, 203 mV in 1 M KOH+0.1 M glucose, and 111 mV for HER in 1 M KOH. The glucose is electrocatalytically oxidized to gluconic acid and formic acid. Density functional theory computation shows the formation of the SnO2/(CoTeO3)2 heterojunction makes the total densities of states of SnO2 move to the Fermi level, which is beneficial for adsorption in the electrocatalysis. This work propagandizes a new avenue for heterojunction electrocatalyst is applied for organics oxidation linking to hydrogen production.

Production of H2 and Glucaric Acid Using Electrocatalyst Glucose Oxidation by the Ta NiFe LDH Electrode.

The slow anodic oxygen evolution reaction (OER) significantly limits electrocatalytic water splitting for hydrogen production. We proposed the electrocatalyst for glucose oxidation by Ta-doping NiFe LDH nanosheets to simultaneously obtain glucaric acid (GRA) and hydrogen gas as a useful byproduct. Superior glucose oxidation reaction (GOR) activity is demonstrated by the optimized Ta-NiFe LDH, which has a low overpotential of 192 mV, allowing for a small Tafel slope of 70 mV dec-1 and a current density of 50 mA cm-2. The Ta NiFe LDH-oxidized glucose to GRA with a 72.94% yield and 64.3% Faradaic efficiency at 1.45 VRHE. Herein, we report the Ta NiFe LDH/NF electrode for the GOR&hydrogen evolution reaction (HER), which exhibits a cell voltage of 1.62 V to reach a current density of 10 mA cm-2, which is 250 mV lower compared to OER&HER (1.87 V). This study reveals that GOR is an energy-efficient and cost-effective method for producing H2 and valorizing biomass.

New type nanocomposite based on metal-organic frameworks decorated with nickel nanoparticles as a potent electrocatalyst for methanol oxidation in alkaline media

Methanol oxidation reaction (MOR) is used to provide electrical energy via direct methanol fuel cell (DMFC), which requires a practical design of electrocatalysts to accelerate the sluggish MOR. In this study, we successfully fabricated the carbon black nanoparticles/graphite ceramic electrode (CBNPs/GCE) supported metal-organic frameworks (MOFs) and decorated with nickel nanoparticles (NiNPs) as a new type nanocomposite modified electrode (NiNPs/MOFs/CBNPs/GCE) via a chemical and an electrochemical process, respectively. The surface morphology and structure of the synthesized nanocomposite materials and modified electrodes were characterized using field emission scanning electron microscopy, energy dispersive X-ray analysis, Fourier transform infrared spectroscopy, X-ray diffraction and thermogravimetric analysis. Then, the NiNPs/MOFs/CBNPs/GCE was used as a non-platinum electrocatalyst for electrocatalytic oxidation of methanol in alkaline media. The obtained results show the efficient electrocatalytic activity of the NiNPs/MOFs/CBNPs/GCE toward the MOR with high anodic peak current density (Jpa = 34.8 mA cm−2) compared with the other prepared electrocatalysts; MOFs/CCE, NiNPs/CCE, MOFs/CBNPs/GCE, NiNPs/CBNPs/GCE, and NiNPs/MOFs/CCE, due to the synergistic effect of nanocomposite components; NiNPs, MOFs and CBNPs. The prepared electrocatalyst; NiNPs/MOFs/CBNPs/GCE, not only shows a high electrochemically active surface area (ECSA = 2.15 cm2) but also has long-term durability in MOR. In general, it can be said the NiNPs/MOFs/CBNPs/GCE is a promising candidate for application in DMFC.

Three-dimensional ordered FeTe-SmCoO3 nanocomposite: As efficient electrocatalyst for water oxidation

In this work, FeTe-SmCoO3 is fabricated through a hydrothermal method and then coated on a stainless steel (SS) substrate to enhance the electrocatalytic performance. The crystal structure, surface chemical state, and morphological features of pure (FeTe and SmCoO3) and heterogeneous catalysts (FeTe-SmCoO3) are determined via XRD, XPS, and TEM/EDX techniques. The fabricated FeTe-SmCoO3 electrocatalyst is attributed to the particular morphological design resulting from the synergistic effect of FeTe and SmCoO3 phases. The as-developed high exposure level of active sites with structural transformation greatly promoted the oxidation property with an overpotential only of 199 mV to derive a current density of 10 mA/cm2, also observed a small Tafel slope of 72 mVdec−1 with extraordinary stability of 90 h. The modified heterogeneous catalyst provides outstanding catalytic behavior toward OER in the alkaline solution, due to flexibility and multiple accessible oxidation states of samarium, cobalt, and iron ions. The catalyst not only acquires additional reaction sites and opens up new channels through the dispersion of the metal centers, but also achieves quick electron transfer in FeTe-SmCoO3 nanocomposite through the interconnection between two phases.

Self-Ordered Anodic Porous Oxide Layers as a High Performance Electrocatalyst for Water Oxidation

Self-Ordered Anodic Porous Oxide Layers as a High Performance Electrocatalyst for Water Oxidation

Multiwall carbon nanotubes supported rhenium doped Co3O4 as an efficient electrocatalyst for water oxidation in alkaline medium

The recent trends for the development of efficient and low cost transition metal (TMs) based anode catalysts for water splitting is crucial and important. Even though, research is continuously progressing in different directions to design catalyst; however, catalytic OER (oxygen evolution reaction) activity has remained insufficient. Till now, various transition metal oxides (TMOs) have been used as efficient and cost-effective electrocatalyst for the oxygen evolution reaction. The catalytic performance of TMOs could be enhanced by doping with the metal, which increases the catalyst's charge transfer and electronic conductivity. Decoration of TMOs with the multi-wall carbon nanotube (MWCNT) further improves catalytic activity by providing numerous active sites. Here, Co3O4/MWCNT and Rhenium (Re) doped Co3O4/MWCNT composite were prepared by simple hydrothermal process and used as electrocatalyst for OER in alkaline medium. Different concentrations of Re (0.05 mmol, 0.1 mmol, 0.2 mmol, 0.3 mmol) were doped and it was observed that the electrochemical results of the 0.2 mmol Re doped Co3O4/ MWCNT (R0.2CO) was most efficient electrocatalyst which offers the OER overpotential of 298 mV/dec to attain the 10 mA cm−2 current density, lower Tafel slope (70 mV/dec), higher value of turn over frequency (0.95), lower value of the charge transfer resistance (3.10Ω) and good stability, demonstrating the better OER catalytic activity as compared to un-doped Co3O4/MWCNT (R0.0CO) catalyst. The investigated catalyst R0.2CO is more efficient catalyst than most of the reported similar type of catalysts and offers comparable electrocatalytic activity with benchmark electrocatalyst RuO2.

Controlled Synthesis of Bead‐like Pt as an Efficient Electrocatalyst for Electrocatalytic Ammonia Oxidation

AbstractPromoting electrocatalytic ammonia oxidation reaction (AOR) holds the key to develop efficient direct ammonia fuel cells (DAFCs) and ammonia‐mediated hydrogen production (AMHP). Recent investigations indicated that Pt with the exposure of (100) facet has a moderate *N intermediate bonding strength, resulting in the highest AOR electrocatalytic activity among others. Therefore, maximizing the exposure of (100) planes with high active surface area is highly desired for efficient electrocatalysts. In this paper, Pt catalyst composed of directional alignment of nanoparticles around 50 nm (Pt‐100/C) were synthesized by hydrothermal method in the presence of KOH. The KOH concentration was found to modulate the one‐dimensional alignment of nanoparticles. The electrocatalyst showed the largest electrochemically active areas and the highest peak current density (3.14 mA cm−2), and the catalyst exhibited high stability after 500 cycles. A series of electrochemical tests and structural characterizations show that unique bead‐structured Pt combines the excellent activity of nanoparticles with the structural stability of nanowires. A scheme for “exchanging electrodes” has been proposed to solve the problem of catalyst poisoning caused by AOR in AMHP.

Surface nitrided CuBi2O4 electrocatalysts with excellent selectivity for CO2 reduction to methanol

Developing a high-performance electrocatalyst for converting CO2 into methanol is of utmost importance. However, poor selectivity, and unavoidable competitive hydrogenolysis reaction (HER) are still challenges to be solved. In this study, a surface nitrided strategy was designed to synthesize a series N-copper-bismuth bimetallic oxide electrocatalysts (NCBO-t, t = 1, 2, 4 h) for CO2RR. The electrocatalyst NCBO-2 demonstrated a selectivity for methanol reaching 86.43 %, along with an impressive long-term stability lasting for 11 h, all achieved at a relatively low potential of −0.9 V. Experimental results and density functional theory (DFT) calculations indicated the introduction of nitrogen facilitates methanol production by optimizing binding of the reaction intermediate *OCH while promotes Faradaic efficiency of methanol products by suppressing the competitive HER, resulting in high Faradaic efficiency, current density, and stability of CO2RR at low overpotentials. This study offers a feasible idea for synthesis of high-performance CO2 methanol by electroreduction.

A customized Sn3O4 interface to stabilize *CO2 intermediate for efficient electrocatalytic CO2 reduction

Interfacial regulation strategy is considered as an effective approach to enhance the electrocatalytic performance. Herein, we demonstrate an appropriate carbon nanotubes-modified Sn3O4 electrocatalysts with maximum carbonaceous Faradaic efficiency of 91 % at −0.79 V vs. RHE, and over 86 % at −0.69 to −1.09 V vs. RHE. The carbonaceous Faradaic efficiency of 20 %CNT/Sn3O4 catalyst remains above 90 % at −0.79 V over 10 h. The chemical interfacial interaction of carbon nanotubes-modified Sn3O4 catalysts facilitates the adsorption and activation of CO2. The in situ Raman results confirm the formation of key formate intermediates and the stabilization of catalyst structure. More importantly, CO2 reduction coupling ethylene glycol (EG) oxidation reduces energy consumption and coproduces value-added formate in a two-electrode system. This work provides a reference for constructing interface-modulated metal oxide electrocatalysts and coproducing formate for co-electrolysis systems.

Superhydrophilic NiFe-LDH@Co9S8-Ni3S2/NF heterostructures for high-current-density freshwater/seawater oxidation electrocatalysts

Designing oxygen evolution reaction (OER) electrocatalysts with high efficiency and stability at large current densities is paramount for achieving hydrogen production through water splitting. In this study, a heterostructured NiFe-LDH coating Co9S8-Ni3S2 grown on nickel foam (NiFe-LDH@Co9S8-Ni3S2/NF) was successfully synthesized. The distinctive hierarchical structures featuring abundant heterointerfaces can effectively expose abundant active sites. The synergistic effect and strong electronic interaction between Co9S8-Ni3S2 and NiFe-LDH can enhance the intrinsic OER activity. Furthermore, the superhydrophilic characteristic of NiFe-LDH@Co9S8-Ni3S2/NF favors close contact between the electrode and electrolyte. Due to these advantages, NiFe-LDH@Co9S8-Ni3S2/NF can provide distinguished OER activity with low overpotentials of 274 mV in alkaline freshwater and 298 mV in alkaline seawater at 1000 mA cm−2, along with outstanding stability at high current density of 500 mA cm−2 over 200 h in both solutions. This study offers a valuable insight into fabricating high-performance OER electrocatalysts for seawater electrolysis in industrial applications.

MoO3/WO3/rGO as electrode material for supercapacitor and catalyst for methanol and ethanol electrooxidation.

The potential of metal oxides in electrochemical energy storage encouraged our research team to synthesize molybdenum oxide/tungsten oxide nanocomposites (MoO3/WO3) and their hybrid with reduced graphene oxide (rGO), in the form of MoO3/WO3/rGO as a substrate with relatively good electrical conductivity and suitable electrochemical active surface. In this context, we presented the electrochemical behavior of these nanocomposites as an electrode for supercapacitors and as a catalyst in the oxidation process of methanol/ethanol. Our engineered samples were characterized by X-ray diffraction pattern and scanning electron microscopy. As a result, MoO3/WO3 and MoO3/WO3/rGO indicated specific capacitances of 452 and 583 F/g and stability of 88.9% and 92.6% after 2000 consecutive GCD cycles, respectively. Also, MoO3/WO3 and MoO3/WO3/rGO nanocatalysts showed oxidation current densities of 117 and 170 mA/cm2 at scan rate of 50 mV/s, and stability of 71 and 89%, respectively in chronoamperometry analysis, in the MOR process. Interestingly, in the ethanol oxidation process, corresponding oxidation current densities of 42 and 106 mA/cm2 and stability values of 70 and 82% were achieved. MoO3/WO3 and MoO3/WO3/rGO can be attractive options paving the way for prospective alcohol-based fuel cells.

Repurposing Co-Fe LDH and Co-Fe LDH/Cellulose micro-adsorbents for sustainable energy generation in direct methanol fuel cells

Spent adsorbents need to be recycled as well as valorized to obtain long-term benefits from the adsorption of contaminants from wastewater. Co-Fe LDH and Co-Fe LDH/cellulose-layered double hydroxide (LDH) were prepared for crystal violet (CV) adsorption. FT-IR, XRD, SEM, TEM, and, zeta potential analyses confirmed the micro-composites. The parameters examined in this study were the initial pH, initial concentration, adsorbent dose, contact time, adsorption isotherm, and adsorption kinetics. The removal percent was 97.5 % and 88 % for Co-Fe LDH and Co-Fe LDH/cellulose, respectively. A maximum adsorption capacity was 69.4 and 50.0 mg g−1 for Co-Fe LDH and Co-Fe LDH/cellulose, respectively, at pH = 9. The Langmuir-Freundlich model can adequately explain the isotherm processes of LDH and LDH/cellulose; R2 was 0.96 and 0.95, respectively. The spent adsorbents (Co-Fe LDH/CV and Co-Fe LDH/Cellulose/CV) were applied once again as catalysts for electro-oxidation in direct-methanol fuel cells. Due to its high stability in the basic medium (NaOH), the waste material was exploited as an active catalyst to support methanol oxidation. It displayed a better efficiency of 74.75 % and a current density of 76 mA/cm2 at 50 mV/s in 1 M methanol for Co-Fe LDH/CV. The suggested technique opens up a completely new channel for reusing waste into high-value materials for application in electrocatalytic energy generation.

Design of highly effective organic catalyst for hydrazine electrooxidation: Iodobenzo[b]furan derivatives

In this study, we investigate the electrochemical characteristics of 2-aryl/alkyl-3-iodobenzo[b]furans as anode catalysts for hydrazine (N2H4) fuel cells. Cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) techniques are employed to investigate the performance of these heteroaromatic compounds. The results demonstrate the promising potential of the 2-aryl/alkyl-3-iodobenzo[b]furans in fuel cell technology. Among the tested organic catalysts (2a, 2b, 2c, 2d, and 2e), 2a exhibited the highest electrocatalytic activity, giving a total current density of 26.62 mA/cm2 within the potential range of −0.4 to −0.8 V. 2-aryl/alkyl-3-iodobenzo[b]furans were synthesized by using palladium/copper-catalyzed Sonogashira cross-coupling reactions, followed by electrophilic cyclization with iodine (I2). All products were characterized using 1H and 13C NMR spectroscopy, confirming their structures and providing insights into their chemical properties.