Direct Electro-oxidation Research Articles

Cascading Water Activation and Interfacial Lattice Oxygen over Nanocluster CuOx-Modified MnO2 for Electrocatalytic Propylene Oxidation.

Direct electrooxidation of propylene using water-oxidation intermediates represents a promising route for propylene glycol production. Unfortunately, this economic and environmentally friendly process suffers from low yield and poor Faradaic efficiency resulting from the mismatched oxidative capacity of reactive oxygen species and pronounced side reactions. Herein, we developed an earth-abundant metal-based nanocluster CuOx-modified MnO2 catalyst for the efficient electrooxidation of propylene into propylene glycol, achieving a remarkable production rate of 63.0 g/m2/h and 95 % Faradaic efficiency at 1.3 V vs. Ag/AgCl. Mechanistic studies revealed that the oxygen vacancy-mediated water activation on CuOx-MnO2 in synergy with the activated interfacial lattice oxygen drove the propylene oxidation to a novel *OOH pathway rather than the traditional *OH route. Additionally, the interfacial interactions intensified the propylene adsorption and polarization for its activation. This work offers new insights into the mechanism of electrocatalytic propylene oxidation and presents great opportunities for the synthesis of commercial chemicals based on earth-abundant metal catalysts and renewable electricity-driven route.

Cascading Water Activation and Interfacial Lattice Oxygen over Nanocluster CuOx‐modified MnO2 for Electrocatalytic Propylene Oxidation

Direct electrooxidation of propylene using water‐oxidation intermediates represents a promising route for propylene glycol production. Unfortunately, this economic and environmentally friendly process suffers from low yield and poor Faradaic efficiency resulting from the mismatched oxidative capacity of reactive oxygen species and pronounced side reactions. Herein, we developed an earth‐abundant metal‐based nanocluster CuOx‐modified MnO2 catalyst for the efficient electrooxidation of propylene into propylene glycol, achieving a remarkable production rate of 63.0 g/m2/h and 95% Faradaic efficiency at 1.3 V vs. Ag/AgCl. Mechanistic studies revealed that the oxygen vacancy‐mediated water activation on CuOx‐MnO2 in synergy with the activated interfacial lattice oxygen drove the propylene oxidation to a novel *OOH pathway rather than the traditional *OH route. Additionally, the interfacial interactions intensified the propylene adsorption and polarization for its activation. This work offers new insights into the mechanism of electrocatalytic propylene oxidation and presents great opportunities for the synthesis of commercial chemicals based on earth‐abundant metal catalysts and renewable electricity‐driven route.

Efficient CO and Acrolein Coproduction via Paired Electrolysis

Interest has grown recently in paired electrolysis: the combining of a productive cathodic reaction, such as CO2electroreduction (CO2RR), with selective oxidation on the anode. Unfortunately, direct electro-oxidation reactions typically exhibit limited Faradaic efficiencies (FEs) towards a single product. Here we pursued paired electrolysis and focused on acidic CO2RR and the model organic oxidation reaction of allyl alcohol oxidation reaction (AOR) to acrolein. We report a system having (96 ± 1)% FE of CO2 to CO on the cathode; and (85 ± 1)% FE of allyl alcohol to acrolein on the anode. We thereby lower, as a result of this pairing with organic oxidation on the anode, the full-cell voltage of the system by 0.7 V compared to the best previously-reported full-cell acidic CO2-to-CO studies at the same 100 mA cm-2 current density. The acidic cathode avoids carbonate formation, enabling us to document a single-pass utilization of CO2 of 84% on the cathode, fully a 6× improvement in the atom-efficiency of CO2 utilization relative to the best prior CO2-to-CO reports undertaken above 100 mA cm-2. Energy consumption analysis suggests that, when producing the same amount of CO, this CO2RR-AOR system reduces energy consumption by an estimated 1.6× compared to the most energy-efficient prior acidic CO2-to-CO ambient-temperature electrolysis systems. Figure 1

Electrochemical Synthesis of Nitrite and Nitrate via Cathodic Oxygen Activation in Liquefied Ammonia.

The electrochemical oxidation of ammonia (NH3) enables decentralized small-scale synthesis of nitrate (NO3-) and nitrite (NO2-) under ambient conditions by directly utilizing renewable energy. Yet, their electrosynthesis has been restricted to aqueous media and low ammonia concentrations. For the first time, we demonstrate here a strategy enabling the direct electrooxidation of liquefied NH3 to NO3- and NO2- by using molecular oxygen, achieving combined Faraday efficiencies above 40%.

Cold plasma-activated Ni-Co tandem catalysts with CN vacancies for enhancing CH4 electrocatalytic to methyl formate

The direct electrooxidation of methane (CH4OR) into high value-added liquid products has been considered an effective method to efficient and clean utilization of methane. However, this process is mainly limited by CH4 activation and subsequent intermediate regulation. Here, we report the first successful achieve methyl formate from CH4OR on Ni-Co tandem catalysts with CN vacancies prepared by H2 cold plasma. The faradaic efficiency of CH4OR into methyl formate reaches 56.7 % at 2.0 V vs. RHE with remained stability for 160 h. In situ ATR-SEIRAS and DFT calculations suggest that the CN vacancies can shift the d-band center of the active Ni sites upwards to enhance the chemisorption of CH4 over Ni atom near CN vacancy, generating the key intermediates of *CH3 and *CH2. *CH2 further overflows onto the Co atom around the same CN vacancy, providing favorable conditions for esterification reaction to obtain methyl formate. This work opens a new avenue for the development of efficient electrocatalytic systems for the clean utilization of methane and the electrosynthesis of methyl formate under ambient conditions.

Pt–Ni–Co trimetallic nanoparticles anchored on graphene oxide: An effective catalyst for ammonia-borane hydrolysis and direct electrooxidation of ammonia-borane in alkaline solution

In this study, graphene oxide supported platin, nickel and cobalt trimetallic nanoparticles (PtNiCo@GO) were prepared by the impregnation/reduction method. The catalytic performances of PtNiCo@GO catalysts prepared with different atomic ratios were investigated for hydrogen production and electro-oxidation of ammonia-borane (AB). For hydrolysis of ammonia-borane, Pt0.8Ni0.1Co0.1@GO catalyst exhibited higher catalytic activity than Pt0.6Ni0.2Co0.2@GO, Pt0.4Ni0.3Co0.3@GO, and Pt0.2Ni0.4Co0.4@GO. The hydrogen generation rate and turnover frequency values were found to be 540 mL min−1g−1 and 42.8 min−1, respectively, in the experiment conducted at 35 °C, 0.5 mmol AB, and 50 mg Pt0.8Ni0.1Co0.1@GO catalyst. The activation parameters (Ea, ΔH#, and ΔS#) in the catalytic hydrolysis of AB were obtained at 42.22 kJ/mol, 31.95 kJ/mol and −114.82 J/(mol × K), respectively. The effects of the PtNiCo@GO catalyst on AB electro-oxidation were made at a scanning rate of 100 mV/s in the potential range of - 1V/+1V against Ag/AgCl, and chronoamperometry measurements were made at constant potentials of - 0.2V, 0.1V and 0.4V. For cyclic voltammetry and chronoamperometry measurements, 5 mM [Fe(CN)6]3/4 (1 M KCl) redox probe and 1 M NaOH + 50 mM AB solution were used.

High-Performance Methanol Oxidation via Ni12-Metal8/CNF Catalyst for Fuel Cell Applications

In this work, non-precious electrocatalysts were synthesized using the electrospinning technique. Ni12M8/CNF (M = Cd, Co, and Cu) catalysts were successfully prepared in a fixed ratio to withstand the optimum transition metal co-catalyst in addition to the role of CNFs as support in ion-charge movement through the catalyst surface. The prepared catalysts were physically studied by XRD, SEM, and TEM. The electrochemical activity was verified using different fuel concentrations, different sweeping scan rates, and electrochemical impedance. Ni12Cu8/CNFs showed the highest electrochemical activity reaching 152 mA/cm2 through different methanol concentrations. The outstanding performance is attributed to the large active surface area provided by carbon nanofibrous that eases the charge carrier transfer through the untrapped surface of the catalyst. The electrochemical tests suggest that Ni12Cu8/CNFs have the lowest ohmic impedance resistance ensuring the highest efficiency of the designed catalyst. The obtained results serve as an efficient catalyst for direct methanol electrooxidation reactions and suggest a possible application of a low-cost, easily accessible, and large surface area established via the preparing method.

Online FTIR and Mass Spectrometry Study of Direct Methyl Formate Electro-oxidation for Fuel-Cells Application

Online FTIR and Mass Spectrometry Study of Direct Methyl Formate Electro-oxidation for Fuel-Cells Application

Layer-by-layer Fabrication of Gold Nanoparticles/Polyaniline Modified Gold Electrodes for Direct Non-enzymatic Oxidation of Glucose

Background: Non-enzymatic direct glucose biofuel cell is a promising technology to harness sustainable renewable energy. Furthermore, monitoring glucose levels is essential for human lives with age. Thus, there is an increasing need to develop highly efficient and stable modified electrodes. Methods: This study reported the manufacture of gold nanoparticles/polyaniline/modified gold electrodes (Au NPs/PANI/Au electrode) based on the electrochemical polymerization method followed by the deposition of gold nanoparticles. The shapes and chemical constitution of the electrodes were examined by using different techniques including SEM, FTIR, XRD, EDS, and Raman spectroscopy techniques. The electrocatalytic efficiency of the present electrodes toward direct glucose oxidation was evaluated by applying cyclic voltammetry, linear sweep voltammetry, and square wave voltammetry techniques. Results: The results exhibited high electrocatalytic performance for direct glucose electrooxidation in alkaline media. The modified electrodes show the ability to electrooxidation of various glucose concentrations (1 μM ̶ 100 μM) with a limit of detection and limit of quantitation of 140 nM and 424 nM, respectively. Furthermore, the Au NPs/PANI/Au electrode showed higher durability, sensitivity, and selectivity toward glucose oxidation than the Au NPs/ Au electrode, which confirmed the role of the PANI layer in enhancing the stability of the modified electrode. Conclusion: Moreover, the molar fraction of glucose to KOH has a crucial role in the output current. Hence, the modified electrodes are great candidates for direct glucose biofuel cell application.

Impacts of chloride ions on the electrochemical decomplexation and degradation of Cr(III)-EDTA: Reaction mechanisms of HO• and RCS

The removal of Cr(III)-organic complexes, encompassing both decomplexation and ligand degradation, presents significant challenges in industrial wastewater treatment. As one of the most common anions in wastewater, Cl− significantly improves the efficiency of electrochemically removing Cr(III)-organic complexes through generated reactive chlorine species (RCS). In the electrochemical chlorine (EC/Cl2) process, extensive experimentation revealed that ClO• plays a dominant role in the degradation of Cr(III)-EDTA, surpassing the effects of free chlorine, direct electrooxidation, HO•, and other RCS. Density functional theory calculations indicated that RCS, primarily Cl• and ClO•, preferentially oxidize the ligand in Cr(III)-EDTA via H-abstraction, whereas HO• trends to attack the Cr atom through electron transfer. The influential factors on the degradation efficiency of Cr(III)-EDTA, Cr(VI) yield, and total organic carbon removal in EC/Cl2 were also assessed, including Cl− concentration, current density, and pH. Real industrial wastewater was employed as a reaction matrix to evaluate the application of the EC/Cl2 process for treating Cr(III)-EDTA, accompanied by energy efficiency calculations. Additionally, a two-chamber reactor was established to simultaneously oxidize Cr(III)-EDTA at the anode and reduce Cr(VI) at the cathode. This study provided insight into developing RCS-dominated AOPs to effectively decomplex and decompose organic Cr(III)-complexes in Cl−-containing industrial wastewater.

Mechanistic Insights on Direct Ammonia Solid Fuel Cell Using Ni-YSZ Anode: Experimental and Density Functional Theory Studies

While Ni-Yttria-stabilized zirconia (Ni-YSZ) cermet exhibits a great potential to realize high-efficiency ammonia to power using direct ammonia solid oxide fuel cell (DA-SOFC), the mechanisms of NH3 cracking and H2 oxidation reactions as well as direct electro-oxidation of ammonia are still unclear. In this context, with the motivation, the DA-SOFC performance of fuel electrode (Ni-YSZ) using conventional anode-supported cell (Ni-YSZ|YSZ|GDC-LSCF) is studied through microscale observation coupled with density functional theory (DFT) calculations to unravel the reaction mechanisms on Ni-YSZ(111) anode. The performance of DA-SOFC is examined using NH3, H2 and N2/H2 mixture as fuel at the temperature range of 700-800℃. In addition to XRD and SEM-EDX characterizations, the electrochemical characterization is performed using the impedance spectroscopy (EIS) measurements at three different temperatures of 700, 750 and 800 °C. Interestingly, the experimentally observed trend in Open-circuit voltage (OCV) implies that direct electro-oxidation of ammonia is the dominant reaction mechanism. Notably, polarization resistance is primarily contributed by ammonia anodic reaction and secondarily by the gas diffusion impedance. DFT results revealed that ammonia adsorbs favorably on the Ni cluster, and hydrogen follows a dissociative mode of adsorption on the Ni cluster. The activation barriers of elementary steps involved in the proposed mechanisms for fuel cracking and oxidation reactions are computed. This work is anticipated to provide valuable insights into the rational design of Ni-YSZ-based fuel electrodes. Keywords: ammonia, hydrogen, SOFC, fuel cells, DFT, reaction mechanism

Monte Carlo Simulation, Artificial Intelligence and Machine Learning-based Modelling and Optimization of Three-dimensional Electrochemical Treatment of Xenobiotic Dye Wastewater

The present study investigates the synergistic performance of the three-dimensional electrochemical process to decolourise methyl orange (MO) dye pollutant from xenobiotic textile wastewater. The textile dye was treated using electrochemical technique with strong oxidizing potential, and additional adsorption technology was employed to effectively remove dye pollutants from wastewater. Approximately 98% of MO removal efficiency was achieved using 15 mA/cm2 of current density, 3.62 kWh/kg of energy consumption and 79.53% of current efficiency. The 50 mg/L MO pollutant was rapidly mineralized with a half-life of 4.66 min at a current density of 15 mA/cm2. Additionally, graphite intercalation compound (GIC) was electrically polarized in the three-dimensional electrochemical reactor to enhance the direct electrooxidation and.OH generation, thereby improving synergistic treatment efficiency. Decolourisation of MO-polluted wastewater was optimized by artificial intelligence (AI) and machine learning (ML) techniques such as Artificial Neural Networks (ANN), Support Vector Machine (SVM), and random forest (RF) algorithms. Statistical metrics indicated the superiority of the model followed this order: ANN > RF > SVM > Multiple regression. The optimization results of the process parameters by artificial neural network (ANN) and random forest (RF) approaches showed that a current density of 15 mA/cm2, electrolysis time of 30 min and initial MO concentration of 50 mg/L were the best operating parameters to maintain current and energy efficiencies of the electrochemical reactor. Finally, Monte Carlo simulations and sensitivity analysis showed that ANN yielded the best prediction efficiency with the lowest uncertainty and variability level, whereas the predictive outcome of random forest was slightly better.Highlights• In-depth analysis of various artificial intelligence optimization techniques.• Prediction efficiency of artificial intelligence and machine learning algorithms.• 98% dye removal and 100% regeneration of graphite intercalation compound.• Advanced statistical analysis of targeted responses and data fitting techniques.• Analysis of uncertainties and variability using Monte Carlo simulation.

Direct Electrooxidation of Ammonia-Enriched Wastewater Using a Bipolar Membrane-Integrated Electrolytic Cell

The treatment of reject water containing concentrated ammonia and non-biodegradable organics is a challenging task in wastewater treatment plants. To address this problem, we propose a novel process consisting of a selective ammonium-exchange resin and an ammonia electrooxidation reaction (AmER-AOR). Because an alkaline condition is essential for direct ammonia oxidation, the use of a bipolar membrane (BPM) was helpful. Nonetheless, an initial pH of 13 and KOH addition were required to maintain a high alkalinity for the complete elimination of ammonia. The linear sweep voltammogram elucidated the high pH requirement and ammonia oxidation promotion. When the current density varied from 30 to 80 mA cm−2, 60 mA cm−2 showed the highest current efficiency (30.39%) and the lowest specific energy demand (95.3 kWh/kg-N), indicating the most energy-effective condition. Increasing the initial concentration of ammonia from 0.1 M to 0.5 M improved the current efficiency (51.57%), demonstrating an additional energy-effective strategy for the AmER-AOR. The energy efficiency of pure H2 production in the cathodic chamber was 30%. To estimate the viability for practical applications, reject water collected from a local wastewater treatment plant was applied in the AmER-AOR. Notably, no significant difference in the ammonia removal rate was observed with synthetic wastewater. To the best of our knowledge, this is the first study that employs a BPM as a separator and OH− supplier for direct ammonia oxidation. Our findings reveal that the AmER-AOR with a BPM has promising practical applicability in the treatment of reject water and energy production.

Electrochemical Oxidative Cross-Coupling for the Construction of C(sp3)–C(sp3) Bonds

AbstractA highly effective oxidation cross-coupling method involving para-cresol derivatives and malononitrile derivatives has been developed utilizing undivided electrolytic conditions. This electrochemical approach offers a robust route for synthesizing diverse malononitrile derivatives featuring quaternary carbon centers and incorporating para-phenol groups. Notably, the direct electrooxidation of the C(sp3)–H bond in the para-cresol derivative plays a crucial role in this process under electrolytic conditions. Various para-cresol derivatives and malononitrile derivatives with different substituents are readily compatible with this electrochemical transformation, affording coupling compounds in up to 99% yield.

Cobalt(II) mediated electro-oxidation of toluene and its derivatives

The oxidation of toluene and its derivatives is crucial for the chemical industry. Traditional liquid-phase oxidation technologies require high-temperature and high-pressure conditions, which causes high safety risks and urgently requires alternatives. This article reports an electrochemical oxidation method using cobalt acetate as a mediator, which successfully realizes the mild oxidation of toluene. The method turns toluene into highly active radicals by the electrochemically generated Co(III) from cobalt acetate, which significantly reduces the anodic potential in contrast to the direct electro-oxidation and the other reported mediated oxidation processes. The target products, benzaldehyde and benzoic acid, exhibit high yields at 85 °C as the ratio of AcO- to Co(II) is close to 2 in the homogeneous anhydrous electrolyte. A benzyl radical-centered mechanism for the Co(II) mediated electro-oxidation of toluene is proposed based on the cyclic voltammetry tests and a radical inhibiting experiment. The method has also been successfully applied to the derivatives of toluene.

Tuning Cu2O morphologies of Cu2O/Ni foam electrodes for the control of reactivity and nitrogen selectivity in direct ammonia electrooxidation reaction

Direct electrochemical oxidation of ammonia (AEO) using non-precious metal catalysts is an energy-efficient and low-carbon-footprint method for ammonia removal from wastewater. In this work, Cu2O with three types of morphologies, including flower, particle, and sheet, were electrodeposited on Ni foam substrates (Cu2O/NF) for direct AEO. The Cu2O flower-deposited NF electrode showed the largest electrochemical surface area (19.6 cm2) and the smallest Cu2O size (200–600 nm) among all Cu2O/NF electrodes. In the ammonia solution, the peak current densities of direct AEO from cyclic voltammograms (CVs) at 10 mVs−1 on the Cu2O flower, Cu2O particle, and Cu2O sheet-deposited NF electrodes reached 4.6, 3.1, and 2.2 mAcm−2, respectively. The result showed that, at an initial pH of 11 and an applied potential of 0.95 V vs. Hg/HgO, the order of three types of Cu2O morphologies with respect to ammonia removal efficiency and rate is: Cu2O flower (52%, 4.1×10−3 min−1) > Cu2O particle (38%, 2.6×10−3 min−1) > Cu2O sheet (30%, 1.8×10−3 min−1). Interestingly, ammonia oxidation to N2 on the Cu2O sheet-deposited NF electrode exhibited the highest selectivity (SN2: 60%), which was much higher than the Cu2O flower-deposited NF electrode (SN2: 31%). The high SN2 of Cu2O sheets was ascribed to the presence of the stable Cu(I) sheet structure during direct AEO, confirmed by X-ray photoelectron spectroscopy analysis. On the other hand, the Cu(II)-rich flower structure facilitated the formation of NO3-. Our findings demonstrate that the surface morphologies of Cu2O deposited on the NF electrode show significant stability difference of Cu(I), which determines reactivity and N selectivity during direct AEO.

Electrochemical-Induced C-N Bond Formation: A New Method to Synthesis (Z)-Quinazolinone Oximes Using Primary Amines and Quinazolin-4(3H)-one.

A novel and highly selective electrochemical method for the synthesis of diverse quinazolinone oximes via direct electrooxidation of primary amines/C(sp2)-H functionalization of oximes has been developed. The reaction is conducted in an undivided cell under constant current conditions and is oxidant-free, open-air, and eco-friendly. Notably, the protocol shows good functional group tolerance, providing versatile quinazolinone oximes in good yields. Moreover, the mechanism is investigated through control experiments and cyclic voltammogram (CV) experiments.

Nickel and cobalt-based tungstate nanocomposites as promising electrocatalysts in alkaline direct methanol fuel cells.

In this work, a non-precious group metal (non-PGM) electrocatalyst based on transition metals is introduced as a promising solution for enhancing the efficiency of direct methanol fuel cell (DMFC). Nickel-cobalt mixed tungstate was prepared using a simple co-precipitation method with different molar ratios of Ni, Co and W. The prepared materials were tested and validated using different characterization techniques. It was observed using SEM that the materials are agglomerated amorphous random circular nanocomposite structures. The electrochemical performance of the prepared electrocatalysts revealed that the best nanocomposite was the one with the Ni : Co : W ratio of 1 : 1 : 1.5 (W1.5). This composite showed a higher current density of 229 mA cm-2 towards methanol oxidation at a scan rate of 50 mV s-1 in 1 M methanol at 0.6 V, with the lowest onset potential of 0.33 V. The obtained results present a new strong non-PGM material for direct methanol electro-oxidation reactions and open new doors for economic and earth-abundant electrocatalysts as an alternative to expensive commercially available catalysts.

Electrochemical Investigations of Protein Denaturating Agents Dithiobutylamine and Dithiothreitol and of the Antineoplastic Alemtuzumab at Glassy Carbon Electrode

A study to establish redox and thermodynamic properties of the protein denaturing agents dithiobutylamine (DTBA) and dithiothreitol (DTT) and of the monoclonal antibody alemtuzumab (ATZ), in aqueous electrolytes, with different pH values, under different experimental conditions, was carried out on a glassy carbon electrode (GCE), using cyclic voltammetry (CV), differential pulse voltammetry (DPV) and square wave voltammetry (SWV). The voltammetric study demonstrated that DTBA, as well as DTT, were both susceptible to direct electro-oxidation on the electrode surface. The study established that the oxidation of DTBA and DTT took place in three subsequent steps, the first two occurring in the thiol groups forming a cyclic intermediate. The oxidation mechanisms of DTBA and DTT were postulated and proposed. The results using DPV and SWV clearly demonstrated the spontaneous adsorption of ATZ on the hydrophobic GCE surface and that it undergoes electro-oxidation in amino acid residues of tyrosine and tryptophan, exposed superficially on the three-dimensional structure of the protein and on the electrode. An oxidation mechanism of ATZ was also proposed.

Bromine-mediated strategy endows efficient electrochemical oxidation of amine to nitrile.

Conventional methods for nitrile synthesis bring inherent environmental risks due to their reliance on oxidants and harsh reaction conditions. Meanwhile, direct electrooxidation of amines to nitriles suffers from low current density. In this study, we propose an innovative indirect electrooxidation strategy for nitrile formation, mediated by Br-/Br2, utilizing a highly efficient CoS2/CoS@Graphite Felt (GF) electrode. Notably, the anodic nitrile generation can be synergistically coupled with the cathodic hydrogen evolution reaction (HER). Through meticulous optimization of reaction parameters, we achieve an impressive 98% selectivity for octanenitrile at a current density of 60 mA cm-2 with a remarkable faradaic efficiency (FE) of 87%. Furthermore, our approach demonstrates excellent versatility, as we successfully evaluate both aliphatic and aromatic primary amines, highlighting its promising potential for practical applications in the field.