Search Results (43)

Developing efficient and durable non-precious metal catalysts for oxygen electrocatalysis in fuel cells and zinc–air batteries remains an urgent issue to be addressed. Herein, a bimetallic CoCe-NC catalyst is synthesized through pyrolysis of Co/Ce co-doped metal–organic frameworks (MOFs), retaining the inherently high surface area of MOFs to maximize the exposure of Co-N and Ce-N active sites. The electronic interaction between Co and Ce atoms effectively modulates the adsorption/desorption behavior of oxygen-containing intermediates, thereby enhancing intrinsic catalytic activity. In alkaline media, the CoCe-NC catalyst exhibits E_1/2 = 0.854 V electrocatalytic capability comparable to commercial Pt/C, along with superior methanol resistance and durability. Notably, CoCe-NC demonstrates an overpotential 84 mV lower than Pt/C at 300 mA cm⁻² in a GDE half-cell. When the catalyst is employed as a cathode in zinc–air batteries, it demonstrates an open-circuit voltage of 1.47 V, a peak power density of 202 mW cm⁻², and exceptional cycling durability. Full article

The design of efficient and cost-effective electrocatalysts to replace Pt in an oxygen reduction reaction (ORR) is crucial for advancing proton exchange membrane fuel cell (PEMFC) technologies. This study synthesized Pd-Co bimetallic alloy nanoparticles supported on reduced graphene oxide (rGO) through a simple chemical-reduction method, making it suitable for low-cost, large-scale fabrication and significantly reducing the need for Pt. The nanostructures were systematically characterized using various analytical techniques, including X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), energy-dispersive X-ray spectroscopy (EDX), and cyclic voltammetry (CV). Electrochemical investigations revealed that the Pd-Co/rGO catalyst exhibits remarkable ORR performance in an alkaline environment, with an electrode-area-normalized activity rivaling that of the commercial Pt/C catalyst. Remarkably, Pd-Co/rGO demonstrated an onset potential (E_onset) of 0.944 V (vs. RHE) and a half-wave potential (E_1/2) of 0.782 V (vs. RHE), highlighting its excellent ORR activity. Furthermore, the Pd-Co/rGO catalyst displayed superior methanol-tolerant ORR activity, outperforming Pt/C and monometallic Pd/rGO and Co/rGO systems. The enhanced electrocatalytic performance is attributed to the smallest size, consistent shape, and good dispersion of the alloy structure on the RGO surface. These findings establish Pd-Co/rGO as a promising alternative to Pt-based catalysts, addressing key challenges such as methanol crossover while advancing PEMFC technology in alkaline media. Full article

Developing non-noble metal catalysts that exhibit oxygen reduction reaction (ORR) activity comparable to or exceeding that of platinum-based catalysts remains a significant challenge. This research presents the successful fabrication of novel cobalt-nitrogen (Co-N) catalysts through a straightforward one-step synthesis method. This method involves stirring a mixture of cobalt (II) nitrate, polyhexamethylene guanidine (PHMG) as a nitrogen source, and carbon spheres at ambient temperature. By varying the mass ratio of PHMG to cobalt salt, three distinct catalyst formulations were produced. The catalyst with an optimal PHMG-to-cobalt nitrate ratio of 2:1 (Co-PHMG-2@C) exhibited exceptional electrocatalytic activity for the oxygen reduction reaction (ORR) in alkaline electrolytes. This catalyst demonstrated a high onset potential of 0.97 V and a half-wave potential of 0.82 V versus the reversible hydrogen electrode (RHE), favorably comparable to those of the benchmark Pt/C catalyst (1.02 V vs. RHE). Furthermore, Co-PHMG-2@C displayed superior stability and resistance to methanol poisoning. The scalability of this synthesis technique offers a promising pathway for cost-effective and environmentally friendly production of carbon nanomaterials for applications in fuel cells and other electrochemical energy devices. Full article

Methanol is a versatile substance that can be used in combustion engines and fuel cells and as a feedstock for the production of various chemicals. However, the majority of methanol is currently produced from fossil fuels, which is not sustainable. The aim of this study was to analyze and evaluate the feasibility of methanol production from renewable sources as a bridge to a low-carbon economy and its potential as an alternative to fossil-derived chemicals. For this purpose, the process of methanol production from captured CO₂ and water as an H₂ source was simulated in Aspen Plus. For CO₂ capture, the monoethanolamine (MEA) absorption process was assumed. The H₂ required for methanol synthesis was obtained by alkaline water electrolysis using electricity from renewable sources. The captured CO₂ and the produced H₂ were then converted into methanol through the process of CO₂ hydrogenation in two ways, direct and two-step synthesis. In the direct conversion, the hydrogenation of CO₂ to methanol was carried out in a single step. In the two-step conversion, the CO₂ was first partly converted to CO by the reverse water-gas shift (RWGS) reaction, and then the mixture of CO and CO₂ was hydrogenated to methanol. The results show that direct synthesis has a higher methanol yield (0.331 kmol of methanol/kmol of H₂) compared to two-step synthesis (0.326 kmol of methanol/kmol of H₂). The direct synthesis produces 13.4 kmol of methanol/MW, while the two-step synthesis produces 11.2 kmol of methanol/MW. This difference amounts to 2.2 kmol of methanol/MW, which corresponds to a saving of 0.127 $/kmol of methanol. Besides the lesser energy requirements, the direct synthesis process also produces lower carbon emissions (22,728 kg/h) as compared to the two-step synthesis process (33,367 kg/h). Full article

A Pb-containing PtAu nanoflower electrocatalyst was deposited on the cathode via galvanic replacement reaction in a double-cabin galvanic cell (DCGC) with a Cu plate as the anode, a multiwalled carbon nanotube (MWCNT) modified glassy carbon electrode (GCE) as the cathode, 0.1 M HClO₄ aqueous solution as the anolyte, and Pb²⁺-containing Pt⁴⁺ salt and Au³⁺ salt mixed aqueous solution as the catholyte, respectively, and the electrocatalytic performance of the modified electrode toward methanol oxidation in the alkaline medium was investigated. Electrochemical studies reveal that the stripping of bulk Cu can induce underpotential deposition (UPD) of Pb on Pt during the galvanic replacement reaction, which affects the morphology and composition of Pb-containing PtAu nanoparticles. Under the optimal experimental conditions, a Pb-Pt₃Au₁/MWCNTs/GCE shows the highest activity and the best stability toward electrocatalytic oxidation of methanol in the alkaline medium, and the Pt active area-normalized specific electrocatalytic activity of Pb-Pt₃Au₁/MWCNTs/GCE is as high as 59.8 mA cm_Pt⁻². We believe that the method presented here of depositing highly active noble metal nanostructures by galvanic replacement reaction in a DCGC device is expected to be widely applied in the preparation of nanomaterials for their study in fuel cells and electrocatalysis. Full article

The application of organometallic materials as anodes in fuel cell devices has experienced a notable increase in recent years. However, the use of POCOP pincer complexes remains scarcely explored despite their great relevance in catalysis. Thus, in this work, the electrocatalytic activity to methanol in alkaline media of three Ni(II)-based POCOP pincer complexes—[NiCl{C₆H₂-4-OH-2,6-(OPiPr₂)₂}] (a1), [NiCl{C₆H₂-4-OH-2,6-(OPtBu₂)₂}] (a2), and [NiCl{C₆H₂-4-OH-2,6-(OPPh₂)₂}] (a3)—will be discussed. The complexes were use as modifiers of carbon paste electrodes that were evaluated using cyclic voltammetry considering diverse factors, such as the absence and presence of MeOH, diverse proportions (% w/w) of the complex in the electrode, scan rate, and different MeOH concentrations. Results indicated the presence of a redox pair Ni(II)/Ni(III) with a quasi-reversible behavior in all complexes, the anodic peak currents of which were proportional to the increase in MeOH concentrations (0.05–0.3 mM), and their oxidation potentials varied in the function of the P-substituent in the Ni(II)-POCOPs backbone. Complex a1 exhibited the best current density (429.5 mA cm² at 0.5 mM) compared to its analogs a2 and a3. The current intensity of all electrodes displays good stability, which remains—with slight changes—up to 100 s. Moreover, a comparison of their catalytic rate constants suggested a great activity in complex a1 (0.52 × 10⁶ cm³ mol⁻¹ s⁻¹) compared to its analogues, implying a great activity in the electro-oxidation of MeOH. Hence, this work opens new opportunities for the electrochemical application of POCOPs complexes for future DMFCs development. Full article

This study investigates the potential of using gold nanoparticles (Au NPs) synthesized from e-waste as electrocatalysts for the methanol oxidation reaction (MOR), with the aim of applying them as an anode in alkaline direct methanol fuel cells (ADMFCs). The research addresses the pressing environmental challenge of e-waste disposal and explores the recycling of e-waste to obtain valuable materials for sustainable applications. Vulcan-supported gold nanoparticles (Au_e-w/C NPs) are synthesized from gold coatings recovered from Intel Pentium 4 processor pins, demonstrating the feasibility of e-waste as electrocatalyst precursors. Comprehensive characterization techniques such as UV-Vis spectroscopy, high-resolution transmission and transmission electron microscopy (HR-TEM, TEM), selected area electron diffraction (SAED), scanning electron microscopy (SEM), and X-ray diffraction (XRD) are employed to evaluate the structural properties of the electrocatalyst. Electrochemical evaluation in 0.5 M KOH electrolyte by cyclic voltammetry reveals that the synthesized Au_e-w/C NPs exhibit electrocatalytic activity (25.5 mA·mg⁻¹_Au) comparable to their commercially synthesized counterparts (30.1 mA·mg⁻¹_Au). This study highlights the potential for sustainable approaches in the production of electrocatalysts by utilizing e-waste as a source of valuable catalyst materials. It represents a pioneering effort in harnessing e-waste as a sustainable resource, offering new avenues for sustainable energy technologies while addressing environmental concerns and technological challenges in the field of ADMFCs. Full article

Currently, the development of nonmetallic oxygen reduction reaction (ORR) catalysts based on heteroatomic-doped carbon materials is receiving increaseing attention in the field of fuel cells. Here, we used enzymolytic lignin (EL), melamine, and thiourea as carbon, nitrogen, and sulfur sources and NH₄Cl as an activator to prepare N- and S-codoped lignin-based polyporous carbon (ELC) by one-step pyrolysis. The prepared lignin-derived biocarbon material (ELC-1-900) possessed a high specific surface area (844 m² g⁻¹), abundant mesoporous structure, and a large pore volume (0.587 cm³ g⁻¹). The XPS results showed that ELC-1-900 was successfully doped with N and S. ELC-1-900 exhibited extremely high activity and stability in alkaline media for the ORR, with a half-wave potential (E_1/2 = 0.88 V) and starting potential (E_onset = 0.98 V) superior to those of Pt/C catalysts and most non-noble-metal catalysts reported in recent studies. In addition, ELC-1-900 showed better ORR stability and methanol tolerance in alkaline media than commercial Pt/C catalysts. Full article

The oxygen reduction reaction (ORR) is a key cathodic reaction in energy-converting systems, such as fuel cells (FCs). Thus, it is of utmost importance to develop cost-effective and efficient electrocatalysts (ECs) without noble metals to substitute the Pt-based ones. This study focuses on polyoxometalate (POM)-based ECs for ORR applications. A Wells–Dawson POM salt K₇ [P₂W₁₇(FeOH₂)O₆₁].·20H₂O was immobilised onto graphene flakes and multiwalled carbon nanotubes doped with nitrogen, denominated as P₂W₁₇Fe@GF_N8 and P₂W₁₇Fe@MWCNT_N8. The successful preparation of the composites was proved with various characterisation techniques, including FTIR, XPS and SEM. Both materials showed good ORR performance in an alkaline medium with similar potential onset values of ~0.84 V vs. RHE and diffusion-limiting current densities of −3.9 and −3.3 mA cm⁻² for P₂W₁₇Fe@MWCNT_N8 and P₂W₁₇Fe@GF_N8, respectively. Furthermore, both composites presented low Tafel slopes (48–58 mV dec⁻¹). Chronoamperometric tests revealed that the as-prepared nanocomposites rendered a significant improvement achieving between 90 and 94% of current retention in tolerance to methanol in comparison with Pt/C, and moderate to good long-term electrochemical stability with current retentions comprised between 68 and 88%. This work reinforces the use of POMs as important electroactive species for the preparation of alternative ORR electrocatalysts, exhibiting good activity, stability and selectivity towards the ORR in the presence of methanol. Full article

The electrocatalyst of oxygen reduction reactions is one of the basic components of a fuel cell. In addition to costly Pt/C benchmark catalysts, cost-effective carbon-based catalysts have received the most attention. Enormous efforts have been dedicated to trade off the catalyst performance against the economic benefit. Optimizing composition and/or structure is a universal strategy for improving performance, but it is typically limited by tedious synthesis steps. Herein, we have found that directly introducing CNT into MOF-derived carbonaceous nanopolyhedra, i.e., introduced carbon nanotubes (CNTs) penetrated porous nitrogen-doped carbon polyhedra (NCP) dotted with cobalt nanoparticles (denoted as CNTs-Co@NCP), can optimize the catalytic activity, stability, and methanol tolerance. The hierarchical architecture combines the 0D/1D/3D Co/CNT/NCP interfaces and 1D/3D CNT/NCP junctions with the frameworks with a greatly exposed active surface, strengthened mass transport kinetics, stereoscopic electrical conductivity networks and structural robustness. The sterical self-consistency of MOF-self-assembly triggered by introduced CNTs demonstrates tactful ORR electrocatalytic activity regulation. Eventually, the CNTs-Co@NCP showed a half-wave potential (E_1/2) of 0.86 V and a diffusion-limited current density (J_L) of 5.94 mA/cm² in alkaline electrolyte. The CNTs-Co@NCP was integrated into the cathode of a direct methanol fuel cell (DMFC) with an anion-exchange membrane, and an open-circuit voltage (OCV) of 0.93 V and a high power density of 46.6 mW cm⁻² were achieved. This work successfully developed a catalyst with competitive ORR performance through plain parameter fine-tuning without complex material design. Full article

The design and fabrication of low-cost catalysts for highly efficient oxygen reduction are of paramount importance for various renewable energy-related technologies, such as fuel cells and metal–air batteries. Herein, we report the synthesis of Fe₃N nanoparticle-encapsulated N-doped carbon nanotubes on the surface of a flexible biomass-derived carbon cloth (Fe₃N@CNTs/CC) via a simple one-step carbonization process. Taking advantage of its unique structure, Fe₃N@CNTs/CC was employed as a self-standing electrocatalyst for oxygen reduction reaction (ORR) and possessed high activity as well as excellent long-term stability and methanol resistance in alkaline media. Remarkably, Fe₃N@CNT/CC can directly play the role of both a gas diffusion layer and an electrocatalytic cathode in a zinc–air battery without additional means of catalyst loading, and it displays higher open-circuit voltage, power density, and specific capacity in comparison with a commercial Pt/C catalyst. This work is anticipated to inspire the design of cost-effective, easily prepared, and high-performance air electrodes for advanced electrochemical applications. Full article

In this study, hierarchical NiCo₂S₄ nanostructures have been successfully prepared on Ni foam support using a simple and economical two-step hydrothermal process. The hierarchical NiCo₂S₄ nanostructure comprises rod-like NiCo₂S₄ cores enveloped by a thin nanoribbon shell. When the NiCo₂S₄/Ni foam was employed as an electrode for methanol electrooxidation directly, a current density of 194 mA mg⁻¹ was achieved at 0.60 V. The prepared NiCo₂S₄/Ni foam demonstrates high electrocatalytic activity and durability in alkaline environments for the methanol oxidation reaction. After 1000 cyclic voltammetry cycles in the alkaline electrolyte, the current density of the hierarchical NiCo₂S₄ decreased to 72.2% of its initial value, with the loss of catalytic activity during the cycling test attributed to their surface oxidation. These findings suggest the NiCo₂S₄ sample as a non-noble metal electrocatalyst holds great potential for direct methanol fuel cells. Full article

Membrane-less fuel cells are a promising power source for portable applications that enable the solving of membrane-related issues, such as water management and high cost, in conventional fuel cells. Apparently, research on this system uses a single electrolyte. This study focused on enhancing the performance of membrane-less fuel cells by introducing multiple reactants that are dual electrolytes with hydrogen peroxide (H₂O₂) and oxygen as oxidants in membrane-less direct methanol fuel cells (DMFC). The conditions tested for the system are (a) acidic, (b) alkaline, (c) dual medium with oxygen as an oxidant, and (d) dual medium and dual oxygen and hydrogen peroxide as an oxidant. Additionally, the effect of fuel utilization on different electrolyte and fuel concentrations was also studied. It was found that the fuel utilization decreases dramatically with the increasing of the fuel concentration, but it improved with the increasing of the electrolyte concentration until 2M. The performance of the dual oxidants in dual-electrolyte membrane-less DMFCs was 15.5 mW cm⁻² of the power density achieved before optimization. Later, the system was optimized, and the power density increased to 30 mW cm⁻². Finally, this work presented the stability of the cell using the suggested parameters from the optimization process. This study indicated that the performance of the membrane-less DMFC increased for dual electrolytes with mixed oxygen and hydrogen peroxide as oxidants compared to a single electrolyte. Full article

This paper describes the use of a commercial Fumasep^® FAA3-50 membrane as an anion exchange membrane (AEM) in alkaline direct methanol fuel cells (ADMFCs). The membrane, supplied in bromide form, is first exchanged in chloride and successively in the hydroxide form. Anionic conductivity measurements are carried out in both a KOH aqueous solution and in a KOH/methanol mixture. AEM-DMFC tests are performed by feeding 1 M methanol, with or without 1 M KOH as a supporting electrolyte. A maximum power density of 5.2 mW cm⁻² at 60 °C and 33.2 mW cm⁻² at 80 °C is reached in KOH-free feeding and in the alkaline mixture, respectively. These values are in good agreement with some results in the literature obtained with similar experimental conditions but with different anion exchange membranes (AEMs). Finally, methanol crossover is investigated and corresponds to a maximum value of 1.45 × 10⁻⁸ mol s⁻¹ cm⁻² at 50 °C in a 1 M KOH methanol solution, thus indicating that the Fumasep^® FAA3-50 membrane in OH form is a good candidate for ADMFC application. Full article

Advancements in inexpensive, efficient, and durable oxygen reduction catalysts is important for maintaining the sustainable development of fuel cells. Although doping carbon materials with transition metals or heteroatomic doping is inexpensive and enhances the electrocatalytic performance of the catalyst, because the charge distribution on its surface is adjusted, the development of a simple method for the synthesis of doped carbon materials remains challenging. Here, a non-precious-metal tris (Fe/N/F)-doped particulate porous carbon material (2₁P₂-Fe₁-850) was synthesized by employing a one-step process, using 2-methylimidazole, polytetrafluoroethylene, and FeCl₃ as raw materials. The synthesized catalyst exhibited a good oxygen reduction reaction performance with a half-wave potential of 0.85 V in an alkaline medium (compared with 0.84 V of commercial Pt/C). Moreover, it had better stability and methanol resistance than Pt/C. This was mainly attributed to the effect of the tris (Fe/N/F)-doped carbon material on the morphology and chemical composition of the catalyst, thereby enhancing the catalyst’s oxygen reduction reaction properties. This work provides a versatile method for the gentle and rapid synthesis of highly electronegative heteroatoms and transition metal co-doped carbon materials. Full article