Electrocatalyst For Oxidation Research Articles

A self-reactivated PdCu catalyst for aldehyde electro-oxidation with anodic hydrogen production.

The low-potential aldehyde oxidation reaction can occur at low potential (~0 VRHE) and release H2 at the anode, enabling hydrogen production with less than one-tenth of the energy consumption required for water splitting. Nevertheless, the activity and stability of Cu catalysts remain inadequate due to the oxidative deactivation of Cu-based materials. Herein, we elucidate the deactivation and reactivation cycle of Cu electrocatalyst and develop a self-reactivating PdCu catalyst that exhibits significantly enhanced stability. Initially, in-situ Raman spectroscopy confirm the cycle involved in electrochemical oxidation and non-electrochemical reduction. Subsequently, in-situ Raman spectroscopy and X-ray absorption fine structure reveal that the Pd component accelerates the rate of the non-electrochemical reduction, thereby enhancing the stability of the Cu-based electrocatalyst. Finally, a bipolar hydrogen production device is assembled utilizing the PdCu electrocatalyst, which can deliver a current of 400 mA cm-2 at 0.42 V and operate continuously for 120 h. This work offers guidance to enhance the stability of the Cu-based electrocatalyst in a bipolar hydrogen production system.

Non-Noble Metal Catalysts for Electrooxidation of 5-Hydroxymethylfurfural.

2,5-Furandicarboxylic acid (FDCA) is a class of valuable biomass-based platform compounds. The creation of FDCA involves the catalytic oxidation of 5-hydroxymethylfurfural (HMF). As a novel catalytic method, electrocatalysis has been utilized in the 5-hydroxymethylfurfural oxidation reaction (HMFOR). Common noble metal catalysts show catalytic activity, which is limited by price and reaction conditions. Non-noble metal catalyst is known for its environmental friendliness, affordability and high efficiency. The development of energy efficient non-noble metal catalysts plays a crucial role in enhancing the HMFOR process. It can greatly upgrade the demand of industrial production, and has important research significance for electrocatalytic oxidation of HMF. In this paper, the reaction mechanism of HMF undergoes electrocatalytic oxidation to produce FDCA are elaborately summarized. There are two reaction pathways and two oxidation mechanisms of HMFOR discussed deeply. In addition, the speculation on the response of the electrode potential to HMFOR is presented in this paper. The main non-noble metal electrocatalysts currently used are classified and summarized by targeting metal element species. Finally, the paper focus on the mechanistic effects of non-noble metal catalysts in the reaction, and provide the present prospects and challenges in the electrocatalytic oxidation reaction of HMF.

Fabrication and electrochemical investigations of nanostructured PtSn-NiTiO3 heterostructured electrocatalysts for direct methanol oxidation

The methanol oxidation reaction of a PtSn nanoparticle decorated NiTiO3 nanostructured material system is reported in this paper. NiTiO3 and PtSn nanoparticles were formed in rhombohedral and cubic phases, respectively. The crystallite size of the PtSn nanoparticles was calculated to be 2.8 nm from the XRD peak parameters and TEM studies. The surface plasmon resonance peak observed at 308 nm indicates the decoration of PtSn-NiTiO3 nanostructures with Pt nanoparticles on the surface. The chemical oxidation states investigated by XPS showed a metallic state of Pt and Sn with a small amount of surface oxidization. From the electrochemical analysis, the Pt0.5Sn0.5-NiTiO3 nanostructures showed superior electrocatalytic performance with higher electrochemical surface area (252 m2/g), high current density (196 mA/cm2), lower Tafel value (161.31 mV/dec) and small charge transfer resistance. This work demonstrated that the Pt0.5Sn0.5 −NiTiO3 nanostructure would be a suitable electrocatalyst for oxidation for methanol in DMFC.

Boosting multi-carbon products selectivity of carbon dioxide reduction via bifunctional cyclodextrin-modification on copper/copper(I) oxide electrocatalysts

Electrochemical carbon dioxide reduction to multi-carbon (C2+) products presents a significant opportunity for converting greenhouse gases into valuable fuels and feedstocks. The development of highly active and stable catalysts remains a critical challenge. In this study, we report the design and synthesis of cyclodextrin-modified Cu/Cu2O electrocatalysts, which exhibit remarkable efficiency in driving the CO2 electroreduction process towards C2+ products. Our optimized catalyst achieves a C2+ Faradaic efficiency exceeding 50 % at a high current density of over 200 mA cm−2. Experimental findings, supported by density functional theory (DFT) calculations, reveal that cyclodextrin plays a dual role in stabilizing Cu+ and increasing the surface density of hydroxyl radicals. This dual function greatly benefits for enhancing *CO intermediate adsorption and promotes *CHO formation, thereby facilitating the crucial dimerization step for the formation of C2+ products. This work provides valuable insights into the development of highly active and selective electrocatalysts by carefully tuning the local catalytic environment, potentially opening new avenues for functionalizing electrocatalysts for future research in this area.

A Comparative Study on the Electrocatalytic Efficiency of Coupled (CuO-Co3O4) vs. Mixed (CuCo2O4) Metal Oxides: Probed by Hydrazine Oxidation and Sensitive Determination

This work reports the synthesis of copper- and cobalt-based coupled and mixed metal oxides (CuO-Co3O4 and CuCo2O4, respectively) utilizing a simple hydrothermal and calcination approach. CuO-Co3O4, CuCo2O4, and the control samples were characterized by powder X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray, and X-ray photoelectron spectroscopy. TEM and FE-SEM analyses of CuO-Co3O4 reveal the presence of two distinct morphologies: rod- and sphere-shaped particles (CuO and Co3O4, respectively). Further, CuO-Co3O4 was efficiently utilized as an electrocatalyst for the selective oxidation of hydrazine (Hyz). CuO-Co3O4 shows a high redox response compared to CuO, Co3O4, CuCo2O4, and the physical mixture of CuO and Co3O4 (CuO/Co3O4). This enhanced performance is attributed to the synergistic interaction between the metal ions caused by their close proximity and the increased exposure of surface active sites. CuO-Co3O4 shows a broad linear range (1-3500 µM), a low detection limit (0.29 µM), and high sensitivity (0.5756 µA µM-1 cm-2) for the Hyz determination. Kinetic parameters, for instance the diffusion coefficient and catalytic rate constant for Hyz oxidation were obtained using chronoamperometry. Additionally, CuO-Co3O4 was effectively utilized to analyze Hyz in real samples with acceptable recovery rates.

Molybdenum-doping to enhance the deprotonation ability of nickel-based hydroxide electrocatalysts for ethanol oxidation

With technological advancements, the practical application of ethanol oxidation reaction (EOR) is becoming increasingly promising, yet the need for higher ethanol concentrations highlights the growing importance of the deprotonation ability (Ni2+ to Ni3+) of the catalyst. The deprotonation ability is the key step for nickel-based catalysts in EOR, as it is essential for Ni2+ to continuously undergo deprotonation to transform into Ni3+ in order to maintain the continuous EOR. Herein, we developed Mo-doped Ni(OH)2 nanosheets by a hydrothermal method. The Mo-doped Ni(OH)2 nanosheets show excellent EOR performance due to the high valence doping of Mo, the onset potential of the oxidation peak (Ni2+ to Ni3+) appears at a position with a small overpotential,. The in-situ Raman spectroscopy technique further characterized the increase in NiOOH in the process of EOR. The Mo-doped Ni(OH)2 nanocomposite catalyst facilitates the oxidation of Ni2+ into Ni3+. Based on the above theoretical guidance, Mo-doped Fe/Ni(OH)2 nanosheets was designed and synthesized. The outstanding EOR performance of the Mo-Fe/Ni(OH)2-3 showed a potential of 1.352 V at 10 mA cm−2. The catalyst was used to design three-electrode reversible zinc-ethanol-air battery (T-RZEAB), which effectively overcomes the opposing kinetic and thermodynamic requirements for EOR and oxygen reduction reaction (ORR) catalysts in the oxygen electrode. The charging voltage of T-RZEAB with Mo-Fe/Ni(OH)2-3 is 240 mV lower than that of a traditional zinc-air battery at 25 mA cm−2.

Synergy strategy of multi-metals confined in heteroatom framework toward constructing high-performance water oxidation electrocatalysts

The development of a low-cost, highly active, and non-precious metal catalyst for oxygen evolution reaction (OER) is of great significance. Multi-metallic catalysts containing Fe, Co, and Ni exhibit remarkable OER activity, while the specific contributions of each component and the synergistic effects in the ternary metal catalyst has remained elusive. In this work, we synthesized a series of S and N-doped mono-metallic, bi-metallic, and tri-metallic hollow carbon sphere electrocatalysts (M−SNC) with the goal of enhancing the catalysts OER activity and shedding light on the unique roles and synergistic effects of the various metals in the FeCoNi ternary metal catalyst. Our systematic analyses demonstrated the introduction of Fe effectively reduces the overpotential, Co accelerates the kinetics of OER, and the addition of Ni further improves the OER performance. Benefiting from the synergistic effects, the FeCoNi-SNC exhibits a low overpotential of 270 mV, with no morphological or structural changes after reaction, maintaining high activity for 72 h at 10 mA cm−2. Moreover, the assembled FeCoNi-SNC || Pt/C water electrolysis device operates for 65,000 s with minimal degradation, demonstrating its potential for practical application. This work presents a synergy strategy for the preparation of low-cost and highly efficient OER catalysts and further provides insights into the rational design and preparation of multicomponent catalysts.

Additive-free Electrodeposition of SnCoNi Trimetallic Catalysts for Ethanol Electrooxidation

SnCoNi catalysts were synthesized via electrodeposition, with and without citric acid, to assess their ethanol electrooxidation performance. The additive-free catalyst exhibited superior properties, including lower charge transfer resistance and a smaller Tafel slope compared to the citric acid-modified catalyst. Chronoamperometry testing further revealed better electrochemical stability for the additive-free catalyst, with less current loss over time. Cyclic voltammetry confirmed the enhanced ethanol oxidation activity with a relatively high current density. The improved performance is attributed to better mass transport, active site exposure, and the synergistic effects of Sn, Co, and Ni in the additive-free catalyst, making it more efficient for ethanol electrooxidation. These findings suggest that the additive-free catalyst exhibits more favorable properties for ethanol electrooxidation compared to its citric acid-modified counterpart.

Poly(3-thiophenemalonic acid) Modified NiFe Layered Double Hydroxide Electrocatalyst for Stable Seawater Oxidation at an Ampere-Scale Current Density

Poly(3-thiophenemalonic acid) Modified NiFe Layered Double Hydroxide Electrocatalyst for Stable Seawater Oxidation at an Ampere-Scale Current Density

One-Pot Fast Electrochemical Synthesis of Ternary Ni-Cu-Fe Particles for Improved Urea Oxidation

The climate crisis has become the most serious concern of human beings and environments worldwide in the 21st century. Global concerns about cancer epidemiology mainly originate from anthropogenic activities, particularly fossil-based operations. A key solution to this problem is the use of fuel cells—devices—capable of the direct conversion of fuel chemical energies like urea into electricity. To make their commercialization reasonable, one of the problems that needs to be solved is the development of anodic materials. The majority of investigations on urea oxidation are based on nickel, but its inadequate activity limits the efficiency of these devices. In this work, we propose and synthesize a Ni-Cu-Fe ternary electrocatalyst for urea oxidation through a fast and facile electrodeposition method. The properties of the synthesized material are examined by Scanning Electron Microscopy (SEM) conjugated with Energy Dispersive X-ray Spectroscopy (EDS), Transmission Electron Microscopy (TEM), and X-ray Diffraction (XRD). Its electrochemical properties were also examined in a 1 M KOH solution with and without 0.15 M urea. We found that the prepared powder is active in the electro-oxidation of urea, with 1.65 Vvs RHE required for a current density of 10 mA cm−2 and a stable potential of 2.38 Vvs RHE required for 3 h of polarization at 10 mA cm−2.

Nanoflower-like NiCoFe layered hydroxide by in-situ electrochemical corrosion as highly efficient electrocatalyst for water oxidation

Layered double hydroxides have been widely applied for oxygen evolution reaction (OER) in the alkaline water electrolysis. However, the issues of poor connection between the catalyst and nickel foam and the specific mechanisms for active sites has not been fully documented. In this study, the in-situ nickel foam etching in a mixed solution of ferric chloride and cobalt nitrate at low temperatures was adopted for NiCoFe layered ternary hydroxides (NiCoFe LTHs) synthesis with a better tight integration. Physicochemical characterization indicated that the NiCoFe LTHs could grow directly through corroding nickel foam with a nano-flower-like morphology and structures. That is favorable for electron transfer from the catalytic layer to the conductive substrate. With the transition metal ions interaction and the tight integration construction, NiCo1Fe4-LTH-T60/NF presented an enhanced electrolysis performance with the overpotential of 234 mV (1.464 V vs. RHE) at current density of 100 mA cm−2 in 1 M KOH electrolyte. The Tafel slope for NiCo1Fe4-LTH-T60/NF electrode was 36.19 mV dec−1 for an enhanced OER kinetics. Besides, it demonstrated faster interfacial charge transfer process, better intrinsic electrochemical activity and stability in large current stability testing. It was revealed that the synergistic effect of the transition metal ions interaction enhancement and the mechanism of oxygen evolution elementary reaction for NiCo1Fe4-LTH-T60/NF during the water electrolysis by the electrochemical and theoretical calculation. This work provides theoretical basis and experimental support for the design and synthesis of future OER catalyst and substrate, which is significant for hydrogen and oxygen generation from water electrolysis.

Homojunction-Incorporated Oxygen Vacancy Functionalized Spherical TiO2 Nanocrystals for the Electrochemical Detection of Chemical Oxygen Demand.

Chemical oxygen demand (COD) is a critical criterion for the analytical assessment of the degree of organic contaminants in an aqueous system. Typically, toxic and expensive reagents are employed in standardized COD analysis methods, leading to secondary pollution. In this work, we developed a rapid electrochemical method for COD detection based on the oxidation of hydroxyl radicals for organics in water by using oxygen vacancy doped anatase/rutile-TiO2 nanoparticles as electrooxidation catalysts. Homojunction interface generated increasing oxygen vacancies for enhancing electron-transfer rate and accelerating H2O oxidation to substantially improve ·OH yield. Oxygen vacancy further increased the oxygen evolution potential of the material. Initially, glucose was chosen as a standard analyte to evaluate electrochemical responses, and water from urban wastewater treatment plants was assessed as real samples subsequently. Excellent analytical characteristics were achieved with the A/R-TiO2 sensor under the optimal conditions, exhibiting a linear range from 1 to 300 mg L-1 and detection limit of 0.1 mg L-1 COD. The estimated COD values obtained from the samples were highly consistent with those determined using the conventional standard dichromate method. We have presented a fast, cost-effective, and ecologically sustainable method that outperforms the standard COD analysis method and holds great potential for the accurate determination of COD and boasts high detection sensitivity and a broad linear range.

Deciphering Doping Effects in a V-Doped Ni Catalyst for Hydrogen Electrooxidation.

The improved performance of soluble metal-doped Ni catalysts is perplexed by the evolvable surface structures in the alkaline electrolytes for hydrogen oxidation reaction (HOR). Herein, V-doped Ni nanoparticles, as a proof of concept, were carefully evaluated to explore the intrinsic function of the enthetic V-species in assisting the HOR kinetic improvement. As expected, it exhibits a mass-normalized kinetic current density of 50.34 mA mgNi-1, more than 12 times that of the Ni counterpart without the introduction of V. Systematic investigations prove that the surface V-species, including the V-oxides and the doped V atoms at the outmost layer, would be dissolved into the electrolytes during the alkaline HOR process. The remaining V-dopants inside the nanoparticles would rationally weaken the hydroxyl binding energy (OHBE) of the Ni-based surfaces, thereby accelerating the formation of water molecules. We also uncover that Ni is located at the overstrong branch of the OHBE-described volcano plot through theoretical calculations and alkali-metal cation probe experiments, and weakening the OHBE by internal V-doping can leave the activity to the volcanic apex.

Transforming Prussian Blue Analogues: The Future-Centric Pathway to Rise of Thin Layered Double Hydroxides for Superior Water Oxidation: An Overview

Prussian blue analogues (PBAs)[1–5] have exhibited great performance towards electrochemical water oxidation because of their high activity and stability. However, there were some challenges because of their limited surface area and less accessible active sites. Herein this work, we have explored the synthesis of a Prussian blue analogue-based thin layered double hydroxide (PBA-TLDH)[6–9] through a reconstruction method. The (PBA-TLDH) possessed high surface area and a large number of active sites for enhanced electrochemical water oxidation. These PBA-LDH materials were well characterized by X-ray diffraction, Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), and electrochemical techniques[1,7,10–12]. The PBA-TLDH materials had a well-defined thin layered structure with the PBAs uniformly distributed in the interlayer spaces of the LDHs. The PBA-LDH catalyst showed enhanced electrocatalytic activity towards water oxidation, with a very low overpotentials up to 240 mV and current density of 10 mA cm-2,[9,13–16] have been achieved which is significantly lower than that of the pristine PBAs. Moreover, these thin layered double hydroxides material showed excellent stability over large electrochemical cycle. This work provides a new strategy for the design and synthesis of highly active and stable electrocatalysts for water oxidation.

Dynamic Fe-O-Cu induced electronic structure modulation on CuOx electrode for selective electrocatalytic oxidation of glycerol

Electrocatalytic glycerol oxidation reaction to produce high-value organic chemicals has research significance for managing the overproduction of glycerol and handling the energy crisis. Herein, a copper-based self-supporting catalytic electrode with a dynamic Fe-O-Cu optimized coordination (Fe-CuOx/CF) was prepared. The oxygen-bridged asymmetric coordination structure (Fe-O-Cu) optimized the electronic configuration and promoted the formation of the crucial intermediate species. After Fe was embedded in the lattice of copper oxides, a remarkable enhancement in the adsorption capacity of OH- and glycerol was confirmed. As a result, Fe-CuOx/CF exhibited an excellent production capacity of formate, with high faradaic efficiency and selectivity values of 93.65 % and 95.10 %. Concurrent production of formate and high purity hydrogen was achieved in the double-electrode flow electrolyzer. This work provides guiding significance for the optimization of the catalytic coordination and the design of high-efficiency transition metal-based catalysts for electrooxidation of biomass platform molecules.

Unveiling the Electrocatalytic Activity of Bifunctional Iron‐Niobium Double Perovskites for Overall Water Splitting: A‐Site Cation Influence

AbstractCapitalizing on the electrochemical conversion of water into hydrogen stands as a pivotal strategy in the global transition toward sustainable energy sources. This study investigates the influence of the A‐site cation type within A2FeNbO6 double perovskites (where A = Ca, Sr, or Ba) on their bifunctional electrocatalytic activities. The electrocatalytic performance is scrutinized in relation to charge transfer resistance, oxygen vacancy concentration, and metal‐oxygen covalency. Among the variants, Sr2FeNbO6 is distinguished as the optimal catalyst, achieving a current density of 10 mA cm⁻2 at overpotentials of 260 mV for the oxygen evolution reaction (OER) and 176 mV for the hydrogen evolution reaction (HER), thus matching the performance of leading metal oxide electrocatalysts. The study reveals pH‐dependent kinetics for Sr2FeNbO6, indicative of a lattice oxygen evolution mechanism for OER. An electrolyzer employing Sr2FeNbO6 electrodes for both the anode and cathode delivers a current density of 10 mA cm⁻2 at an efficient cell voltage of 1.76 V for complete alkaline water splitting, while also demonstrating exceptional stability. These insights advance the understanding of material optimization for electrocatalysis and position Sr2FeNbO6 as a viable catalyst for the sustainable production of hydrogen.

Bifunctional MoNi4/nickel foam electro-catalyst for ultra-efficient oxidation of high-concentration 5-hydroxymethylfurfural and HER.

The electro-catalytic oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) provides an attractive route to produce 2, 5-furandicarboxylic acid (FDCA) as a substitute for terephthalic acid used in the plastics industry. Herein, we prepared MoNi4 alloy on nickel foam (NF) using a simple hydrothermal method followed by hydrogen reduction. Applied MoNi4/NF as the bifunctional electrodes for the electro-catalytic HMF oxidation reaction (HMFOR) and HER, 98.7% FDCA yield and 97.3% Faraday efficiency (FE) can be achieved even with HMF concentration as high as 200 mM. Notably, no obvious deactivation was observed after ten consecutive cycles. In-situ Raman, XANES and EXAFS results show that the nickel species of MoNi4/NF is first oxidized to Ni3+ species under the applied voltage, and after undergoing the electro-catalytic HMFOR, then reduced to Ni2-δ state (with a valence between 0 and +2) due to the electron-donating effect from Mo. MoNi4/NF with more than one electron transfer between Ni3+ and Ni2-δ during the HMFOR enables it to have excellent electro-catalytic oxidation ability toward HMFOR.

Palladium nanocrystals immobilized on boron and nitrogen codoped mesoporous carbon spheres as efficient methanol oxidation electrocatalysts

The development of cost-effective and high-performance electrocatalysts is crucial for the widespread application of direct methanol fuel cell. Herein, a convenient and robust method is developed to the controllable fabrication of Pd nanocrystals in situ immobilized on boron and nitrogen codoped mesoporous carbon spheres (Pd/BNMCS) as anode catalysts for the methanol oxidation reaction. The as-derived Pd/BNMCS hybrids are equipped with a series of useful structural features, such as large specific surface area, abundant mesoporous channels, presence of plentiful B and N atoms, well-dispersive Pd nanoparticles, and good electrical conductivity. As a consequence, the optimized Pd/BNMCS catalyst demonstrates superior electrocatalytic methanol oxidation properties in terms of a large electrochemically active surface area, high mass/specific activities, and reliable long-term stability, which are significantly better than those of traditional carbon black and undoped mesoporous carbon sphere supported Pd catalysts. This study highlights the potential of heteroatom codoped mesoporous carbon matrixes in the construction of advanced noble metal electrocatalysts for practical fuel cell applications.

Mo-Doped α-MnO2 for Enhanced Electrocatalytic Water Oxidation.

Manganese is a key metal involved in the catalysis of natural photosynthesis. Thus, the investigation of Mn-based electrocatalysts for water oxidation is of high importance. This work reports the doping of Mo into α-MnO2 nanorods to improve the water oxidation performance. The doping of Mo can transform the microstructure of α-MnO2 from nanorods into nanosphere superstructures. As a dopant, Mo expands the α-MnO2 lattice to result in a decrease in the average oxidation state of Mn and the generation of oxygen vacancies, which are beneficial to water oxidation catalysis. Under optimized doping, the overpotential of 2.34 wt.% Mo/α-MnO2 is reduced by 80 mV (at 10 mA/cm2) compared with pure α-MnO2.

Single-Atom Copper-Bearing Cerium Oxide Electrocatalysts Embedded in an Integrated System Enable Sustainable Nitrogen Recycling from Natural Water Bodies

Single-Atom Copper-Bearing Cerium Oxide Electrocatalysts Embedded in an Integrated System Enable Sustainable Nitrogen Recycling from Natural Water Bodies