Search Results (168)

This review surveys recent advances and emerging prospects in phase-transfer catalysis (PTC) for fuel desulfurization. In response to increasingly stringent environmental regulations, the removal of sulfur from transportation fuels has become imperative for curbing SO_x emissions. Conventional hydrodesulfurization (HDS) operates under severe temperature–pressure conditions and displays limited efficacy toward sterically hindered thiophenic compounds, motivating the exploration of non-hydrogen routes such as oxidative desulfurization (ODS). Within ODS, PTC offers distinctive benefits by shuttling reactants across immiscible phases, thereby enhancing reaction rates and selectivity. In particular, PTC enables efficient migration of organosulfur substrates from the hydrocarbon matrix into an aqueous phase where they are oxidized and subsequently extracted. The review first summarizes the deployment of classic PTC systems—quaternary ammonium salts, crown ethers, and related agents—in ODS operations and then delineates the underlying phase-transfer mechanisms, encompassing reaction-controlled, thermally triggered, photo-responsive, and pH-sensitive cycles. Attention is next directed to a new generation of catalysts, including quaternary-ammonium polyoxometalates, imidazolium-substituted polyoxometalates, and ionic-liquid-based hybrids. Their tailored architectures, catalytic performance, and mechanistic attributes are analyzed comprehensively. By incorporating multifunctional supports or rational structural modifications, these systems deliver superior desulfurization efficiency, product selectivity, and recyclability. Despite such progress, commercial deployment is hindered by the following outstanding issues: long-term catalyst durability, continuous-flow reactor design, and full life-cycle cost optimization. Future research should, therefore, focus on elucidating structure–performance relationships, translating batch protocols into robust continuous processes, and performing rigorous environmental and techno-economic assessments to accelerate the industrial adoption of PTC-enabled desulfurization. Full article

The cobalt crystalline islands (Co_cryst) were electrochemically deposited onto a glassy carbon (GC) support and then modified by a facile spontaneous deposition of platinum. The electrocatalytic activity of the resulting Co_cryst-Pt core-shell catalyst was evaluated for the oxygen reduction reaction (ORR) in an alkaline medium. The XRD characterization of the Co_cryst-Pt islands revealed that the cobalt core had a hexagonal close-packed (hcp) crystalline structure, and that the platinum shell exhibited a crystalline structure with a preferential (111) orientation. SEM images showed that the average lateral size of the Co_cryst islands was 1.17 μm, which increased to 1.32 μm after adding platinum. The XPS analysis indicated that the outer layer of the bulk metallic Co_cryst islands was fully oxidized. During the spontaneous deposition of platinum, the outer Co(OH)₂ layer was dissolved, leaving the cobalt core in a metallic state, while the platinum shell remained only partially oxidized. The high electrochemically active surface area of the Co_cryst-Pt/GC electrode, along with a suitable crystalline structure of the Co_cryst-Pt islands, contributes to enhancing its ORR activity by providing a greater number of surface active sites for oxygen adsorption and subsequent reduction. The ORR on the Co_cryst-Pt catalyst occurs via a four-electron reaction pathway, with onset and half-wave potentials of 1.07 V and 0.87 V, respectively, which exceed those of polycrystalline platinum and a commercial benchmark Pt/C. Full article

This study presents a straightforward hydrothermal synthesis approach to fabricate uniform and highly dispersed nanoscale Fe₃O₄ electrocatalysts for the oxygen reduction reaction (ORR). FeSO₄·7H₂O is used as the precursor, and sodium dodecyl sulfate (SDS) is incorporated as a dispersing agent to optimize particle size and dispersion. The SDS concentration plays a crucial role in controlling the particle size and distribution, with higher SDS concentrations resulting in smaller, well-dispersed particles (30–40 nm), compared to the agglomerated particles formed without SDS. The Fe₃O₄ catalyst demonstrates significant enhancement in ORR performance, with a half-wave potential of 0.091 V vs. Hg/HgO and a limiting diffusion current density of −5.50 mA cm², surpassing the performance of agglomerated Fe₃O₄ and approaching that of state-of-the-art 20% Pt/C catalysts. Additionally, the Fe₃O₄ catalyst exhibits superior stability and resistance to methanol and CO poisoning, presenting a promising alternative to platinum-based catalysts for ORR applications. This work introduces an efficient approach for the synthesis of high-performance and evenly distributed Fe₃O₄ electrocatalysts, offering a new pathway for the development of metal oxide-based ORR catalysts with enhanced activity and durability. Full article

This study presents an easy and rapid two-step electrodeposition method for the synthesis of a novel hierarchical dendritic AuPt bimetallic nanocomposite electrode. Ascorbic acid served as both a reducing and directing agent, while a roughened carbon substrate facilitated the formation of the unique dendritic nanostructure. The structural and compositional properties of the synthesized material were comprehensively characterized using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), selected area electron diffraction (SAED), and transmission electron microscopy (TEM). The resulting nanocomposite exhibited a significantly enhanced specific surface area of 6.97 m² g⁻¹, compared to commercial Pt/C. Electrochemical investigations demonstrated superior electrocatalytic activity and durability for methanol oxidation in the prepared AuPt nanocomposite electrode, suggesting its promising potential for fuel cell applications. Full article

Protein phosphatases are crucial enzymes that regulate key cellular processes such as the cell cycle, gene transcription, and translation in eukaryotes. Seven PP2C protein phosphatases have been identified in Magnaporthe oryzae. However, their synergistic roles in the pathology and physiology of M. oryzae remain poorly investigated. By qRT-PCR analysis, we found that PTC1 and PTC2 are significantly upregulated in the PTC5 deletion mutant. The double deletion of the MoPTC5/MoPTC1 and MoPTC5/MoPTC2 genes significantly reduced hyphal growth, conidiophore formation, sporulation, and virulence in M. oryzae. In addition, the double-knockout mutants were increasingly sensitive to different osmotic, oxidative, and cell wall stresses. Western blot analysis revealed that MoPtc5 plays a synergistic function with MoPtc1 and MoPtc2 in the regulation of MoMps1 and MoOsm1 phosphorylation levels. Lastly, appressorium formation and turgor generation were remarkably affected in the ΔMoptc5ΔMoptc1 and ΔMoptc5ΔMoptc2 double-deletion mutants. These findings demonstrate the overlapping roles of PP2c protein phosphatase in the fungal development and pathogenesis of M. oryzae. Full article

The electrocatalytic reduction of nitric oxide and nitrogen dioxide (NOx) remains a significant challenge due to the need for stable, efficient, and cost-effective materials. This study presents a novel support system for NOx reduction in alkaline media, composed of ZrO₂-WO₃-C (ZWC), synthesized via coprecipitation. Platinum nanoparticles (10 wt.%) were loaded onto ZWC and Vulcan carbon support, using similar methods for comparison. Comprehensive physicochemical and electrochemical analyses (N₂ physisorption, XRD, XPS, SEM, TEM, and cyclic and linear voltammetry) revealed that PtZWC outperformed PtC and commercial PtEtek in NOx electrocatalysis. Notably, PtZWC exhibited the highest total electric charge for NOx reduction. At the same time, the hydrogen evolution reaction (HER) was shifted to more negative cathodic potentials, indicating reduced hydrogen coverage and a modified dissociative Tafel mechanism on platinum. Additionally, the combination of WO₃ and ZrO₂ in ZWC enhanced electron transfer and suppressed HER by reducing NO and hydrogen atom adsorption competition. While the incorporation of WO₃ and ZrO₂ lowered the surface area to 96 m²/g, it significantly improved pore properties, facilitating better Pt nanoparticle dispersion (3.06 ± 0.85 nm, as confirmed by SEM and TEM). XRD analysis identified graphite and Pt phases, with monoclinic WO₃ broadening PtZWC peaks (20–25°). At the same time, XPS confirmed oxidation states of Pt, W, and Zr and tungsten-related oxygen vacancies, ensuring chemical stability and enhanced catalytic activity. Full article

Sn-doped TiO₂–carbon composites were identified as promising multifunctional supports for Pt electrocatalysts, in which the oxide component enhances resistance against corrosion and strong metal–support interactions at the Pt-oxide boundary ensure high stability for the Pt nanoparticles. This work is devoted to the study of the influence of preliminary functionalization of the carbon on the properties of Pt/Ti_0.9Sn_0.1O₂–C catalysts. The structural, compositional and morphological differences between the samples prepared using functionalized or unmodified carbon, as well as the effect of carbon pre-modification on the electrocatalytic behavior of the synthesized Pt catalysts, were investigated using TEM, XRD, XPS, nitrogen adsorption and electrochemical measurements. The presence of oxygen-containing functional groups on carbon treated with HNO₃ and glucose leads to the formation of a homogeneous coating of the carbon with dispersed crystallites of mixed oxide. Elemental mapping revealed the proximity of Sn species with highly dispersed (2–3 nm) Pt particles. Notably, the electrochemical results indicated enhanced activity in CO electrooxidation for both functionalized and unmodified carbon-containing catalysts. An improvement in the 10,000-cycle long-term stability of the catalyst prepared using functionalized carbon was evident compared to the catalyst with untreated carbon or reference Pt/C. 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

Non-noble metal electrocatalysts for the hydrogen oxidation reaction (HOR) that are both highly active and low-cost are essential for the widespread use of fuel cells. Herein, a simple two-step method for creating an in-plane heterostructure of Ni₃N/MoSe₂ loaded on N-doped reduced graphene oxide (Ni₃N/MoSe₂@N-rGO) as an effective electrocatalyst for the HOR is described. The process involves hydrothermal treatment of the Ni and Mo precursors with N-doped reduced graphene oxide, followed by the annealing with urea. The Ni₃N/MoSe₂@N-rGO catalyst exhibits high activities for the HOR, with current densities of 2.15 and 3.06 mA cm⁻² at 0.5 V vs. the reversible hydrogen electrode (RHE) in H₂-saturated 0.1 M KOH and 0.1 M HClO₄ electrolytes, respectively, which is comparable to a commercial 20% Pt/C catalyst under similar experimental conditions. Furthermore, the catalyst demonstrates excellent durability, maintaining its performance during accelerated degradation tests for 5000 cycles. This work offers a practical framework for the designing and preparing of non-precious metal electrocatalysts for the HOR in fuel cells. Full article

This study explores the development of core–shell electrocatalysts for efficient glycerol oxidation in alkaline media. Carbon-supported M@Pt/C (M = Co, Ni, Sn) catalysts with a 1:1 atomic ratio of metal (M) to platinum (Pt) were synthesized using a facile sodium borohydride reduction method. The analysis confirmed the formation of the desired core–shell structure, with Pt dominating the surface as evidenced by energy-dispersive X-ray spectroscopy (EDS). X-ray diffraction (XRD) revealed the presence of a face-centered cubic (fcc) Pt structure for Co@Pt/C and Ni@Pt/C. Interestingly, Sn@Pt/C displayed a PtSn alloy formation indicated by shifted Pt peaks and the presence of minor Sn oxide peaks. Notably, no diffraction peaks were observed for the core metals, suggesting their amorphous nature. Electrocatalytic evaluation through cyclic voltammetry (CV) revealed superior glycerol oxidation activity for Co@Pt/C compared to all other catalysts. The maximum current density followed the order Co@Pt/C > Ni@Pt/C > Sn@Pt/C > Pt/C. This highlights the effectiveness of the core–shell design in enhancing activity. Furthermore, Sn@Pt/C displayed remarkable poisoning tolerance attributed to a combined effect: a bifunctional mechanism driven by Sn oxides and an electronic effect within the PtSn alloy. These findings demonstrate the significant potential of core–shell M@Pt/C structures for designing highly active and poisoning-resistant electrocatalysts for glycerol oxidation. The presented approach paves the way for further development of optimized catalysts with enhanced performance and stability aiming at future applications in direct glycerol fuel cells. Full article

The supported RuO₂ catalysts are known for their synergistic and interfacial effects, which significantly enhance both catalytic activity and stability. However, polymer-supported RuO₂ catalysts have received limited attention due to challenges associated with poor conductivity. In this study, we successfully synthesized the RuO₂-polytetrafluoroethylene (PTFE) catalyst via a facile annealing process. The optimized nucleation and growth strategies enable the formation of RuO₂ particles (~13.4 nm) encapsulating PTFE, establishing a conductive network that effectively addresses the conductivity issue. Additionally, PTFE induces the generation of oxygen vacancies and the formation of stable RuO₂/PTFE interfaces, which further enhance the acidic OER activity and the stability of RuO₂. As a result, the RuO₂-PTFE catalyst exhibits a low overpotential of 219 mV at 10 mA cm⁻² in the three-electrode system, and the voltage of the RuO₂-PTFE||commercial Pt/C system can keep 1.50 V for 800 h at 10 mA cm⁻². This work underscores the versatility of PTFE as a substrate for fine-tuning the catalyst morphology, the crystal defect, and the stable interface outerwear. This work not only broadens the application scope of PTFE in catalyst synthesis but also provides a novel approach to the design of high-performance metallic oxide catalysts with tailored oxygen vacancy concentration and stable polymer outerwear. Full article

The hydrogen economy, as an emerging paradigm for sustainable energy, relies on efficient hydrogen oxidation (HOR) and hydrogen evolution reactions (HER). These reactions require effective catalysts to enhance reaction kinetics and reduce costs. Platinum (Pt) is widely used but faces issues such as high cost and CO poisoning. Non-precious metal catalysts, particularly Ni-based alloys, are being explored as viable alternatives. This study introduces a ternary MoWNi alloy catalyst synthesized via microwave-assisted methods and annealing. The MoWNi alloy catalyst achieves a current density of 3.5 mA·cm⁻² at an overpotential of 100 mV in HOR and requires only 25 mV overpotential to reach a current density of 10 mA·cm⁻² in HER, making it comparable to commercial 20% Pt/C catalysts. Notably, the catalyst also exhibits superior stability and resistance to CO toxicity. These findings underscore the potential of MoWNi alloy catalysts in advancing hydrogen-based energy systems. Full article

Pt on carbon black (Pt/C) has been widely used as a catalyst for both ORR and hydrogen oxidation reaction (HOR), but its stability is compromised due to carbon corrosion and catalyst poisoning, leading to low Pt utilization. To address this issue, this study suggests replacing carbon black with graphene in the catalyst layer. The importance of this work lies in the detailed examination of novel electrocatalysts with high electrocatalytic activity for large-scale power generation. In this paper, we discuss the use of regulatory techniques like structure tuning and composition optimization to construct nanocatalysts impregnated with noble and non-noble metals on graphene supports. Finally, it highlights the limitations and advantages of these nanocatalysts along with some future perspectives. Our objective is that this summary will help in the research and rational design of graphene-based nanostructures for efficient ORR electrocatalysis. The results of this study showed that the performances of graphene-based catalysts show high electrochemical active surface areas for Pt-Fe/GNPs and Pt-Ni/GNPs catalysts (132 and 136 m² g⁻¹, respectively) at 100 operating cycles. Also, high current densities and power densities were observed for Pt₃-Ni/G and Pt-Co/G catalysts used at the cathode. The values for current density were 1.590 and 1.779 A cm⁻², respectively, while the corresponding values for power density were 0.57 and 0.785 W cm⁻². Full article

In this paper, platinum nanoparticles with a size of less than 50 nm were rapidly and successfully synthesized in low-temperature molten salt using a microwave method. The morphology and structure of the product were characterized by SEM, TEM, EDX, XRD, etc. The TEM and SEM results showed that the prepared product was a nanostructure with concave and uniform size. The EDX result indicated that the product was pure Pt, and the XRD pattern showed that the diffraction peaks of the product were consistent with the standard spectrum of platinum. The obtained Pt/C nanoparticles exhibited remarkable electrochemical performance in a formic acid catalytic oxidation reaction (FAOR), with a peak mass current density of 502.00 mA·mg⁻¹_Pt and primarily following the direct catalytic oxidation pathway. In addition, in the chronoamperometry test, after 24 h, the mass-specific activity value of the Pt concave NPs/C catalyst (10.91 mA·mg⁻¹_Pt) was approximately 4.5 times that of Pt/C (JM) (2.35 mA·mg⁻¹_Pt). The Pt/C NPs exhibited much higher formic acid catalytic activity and stability than commercial Pt/C. The microwave method can be extended to the preparation of platinum-based alloys as well as other catalysts. Full article

Anode catalysts are important for direct methanol fuel cells (DMFCs) of energy conversion. Herein, we report a novel strategy by ethylene glycol-based deep eutectic solvents (EG-DESs) for the fabrication of a multi-walled carbon nanotubes (MWCNTs)-supported Pt nanoparticles catalyst (referred to as Pt/CNTs-EG-DES). The Pt/CNTs-EG-DES catalyst provides an increased electrochemically active surface area (ECSA) and shows remarkably improved electrocatalytic performance towards methanol oxidation reaction compared to Pt/CNTs-W (fabricated in water) and commercial Pt/C catalysts. The improved performance is attributed to the generation of more Pt–O bonds which change the electronic states of the Pt atoms and the special node structure that obtains more active sites for a high CO resistance. This study suggests an effective synthesis strategy for Pt-based electrocatalysts with high performance for DMFC applications. Full article