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Keywords = direct oxidation to methanol

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16 pages, 4134 KiB  
Article
Effect of Oxygen-Containing Functional Groups on the Performance of Palladium/Carbon Catalysts for Electrocatalytic Oxidation of Methanol
by Hanqiao Xu, Hongwei Li, Xin An, Weiping Li, Rong Liu, Xinhong Zhao and Guixian Li
Catalysts 2025, 15(8), 704; https://doi.org/10.3390/catal15080704 - 24 Jul 2025
Viewed by 277
Abstract
The methanol oxidation reaction (MOR) of direct methanol fuel cells (DMFCs) is limited by the slow kinetic process and high reaction energy barrier, significantly restricting the commercial application of DMFCs. Therefore, developing MOR catalysts with high activity and stability is very important. In [...] Read more.
The methanol oxidation reaction (MOR) of direct methanol fuel cells (DMFCs) is limited by the slow kinetic process and high reaction energy barrier, significantly restricting the commercial application of DMFCs. Therefore, developing MOR catalysts with high activity and stability is very important. In this paper, oxygen-functionalised activated carbon (FAC) with controllable oxygen-containing functional groups was prepared by adjusting the volume ratio of H2SO3/HNO3 mixed acid, and Pd/AC and Pd/FAC catalysts were synthesised via the hydrazine hydrate reduction method. A series of characterisation techniques and electrochemical performance tests were used to study the catalyst. The results showed that when V(H2SO3):V(HNO3) = 2:3, more defects were generated on the surface of the AC, and more oxygen-containing functional groups represented by C=O and C–OH were attached to the surface of the support, which increased the anchor sites of Pd and improved the dispersion of Pd nanoparticles (Pd NPs) on the support. At the same time, the mass–specific activity of Pd/FAC for MOR was 2320 mA·mgPd, which is 1.5 times that of Pd/AC, and the stability was also improved to a certain extent. In situ infrared spectroscopy further confirmed that oxygen functionalisation treatment promoted the formation and transformation of *COOH intermediates, accelerated the transformation of COL into COB, reduced the poisoning of COads species adsorbed to the catalyst, optimised the reaction path and improved the catalytic kinetic performance. Full article
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19 pages, 2212 KiB  
Article
Impact of the Anode Serpentine Channel Depth on the Performance of a Methanol Electrolysis Cell
by Vladimir L. Meca, Elena Posada, Antonio Villalba-Herreros, Rafael d’Amore-Domenech, Teresa J. Leo and Óscar Santiago
Hydrogen 2025, 6(3), 51; https://doi.org/10.3390/hydrogen6030051 - 19 Jul 2025
Viewed by 325
Abstract
This work addresses for the first time the effect of anode serpentine channel depth on Methanol Electrolysis Cells (MECs) and Direct Methanol Fuel Cells (DMFCs) for improving performance of both devices. Anode plates with serpentine flow fields of 0.5 mm, 1.0 mm and [...] Read more.
This work addresses for the first time the effect of anode serpentine channel depth on Methanol Electrolysis Cells (MECs) and Direct Methanol Fuel Cells (DMFCs) for improving performance of both devices. Anode plates with serpentine flow fields of 0.5 mm, 1.0 mm and 1.5 mm depths are designed and tested in single-cells to compare their behaviour. Performance was evaluated through methanol crossover, polarization and power density curves. Results suggest shallower channels enhance mass transfer efficiency reducing MEC energy consumption for hydrogen production at 40 mA∙cm−2 by 4.2%, but increasing methanol crossover by 30.3%. The findings of this study indicate 1.0 mm is the best depth among those studied for a MEC with 16 cm2 of active area, while 0.5 mm is the best for a DMFC with the same area with an increase in peak power density of 14.2%. The difference in results for both devices is attributed to higher CO2 production in the MEC due to its higher current density operation. This increased CO2 production alters anode two-phase flow, partially hindering the methanol oxidation reaction with shallower channels. These findings underscore the critical role of channel depth in the efficiency of both MEC and DMFC single-cells. Full article
(This article belongs to the Topic Hydrogen Energy Technologies, 3rd Edition)
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17 pages, 2243 KiB  
Article
Phytochemical Analysis and Chymotrypsin Inhibitory Potential of Galium sp. and Solidago sp. via Effect-Directed HPTLC Bioassay
by Bartosz Rył and Izabela Jasicka-Misiak
Molecules 2025, 30(13), 2746; https://doi.org/10.3390/molecules30132746 - 26 Jun 2025
Viewed by 350
Abstract
Chymotrypsin inhibitors were initially considered mainly as anti-nutritional factors. However, the potential for their use as therapeutics has been recognized, particularly in the control of cancer, neurodegenerative diseases, and inflammatory processes. The search for new, effective, and safe chymotrypsin inhibitors has become important [...] Read more.
Chymotrypsin inhibitors were initially considered mainly as anti-nutritional factors. However, the potential for their use as therapeutics has been recognized, particularly in the control of cancer, neurodegenerative diseases, and inflammatory processes. The search for new, effective, and safe chymotrypsin inhibitors has become important not only for food and feed safety reasons, but also in the search for new compounds with potential for use in the pharmaceutical industry. Oxidative stress is also an integral etiological factor in the development of the aforementioned pathological conditions. Antioxidants supplied with food can have an impact on reducing the probability of developing these diseases. Herbaceous plants are a valuable reservoir of biologically active chemical compounds, which can show both inhibitory effects against a number of enzymatic reactions and have antioxidant activity. The compounds found within them are also often characterized by higher bioavailability and safety than their synthetic analogs. In the present study, phytochemical characterization of plant materials Galium aparine L., Galium verum L., Solidago virgaurea L. and Solidago canadensis L. was performed, in order to search for new, potential substances with chymotrypsin inhibitor and antioxidant properties. Antioxidant and inhibitory activities against chymotrypsin were determined using effect-directed HPTLC. The total content of phenolic compounds and flavonoids and antioxidant activity were also determined in UV-Vis spectrophotometric tests. Both plant species showed antioxidant and chymotrypsin inhibitory activity. Among the methanol and methanol:water extracts, the extracts from Solidago sp. showed stronger inhibitory and antioxidant activity. However, in the case of dichloromethane extracts, Galium aparine inhibited chymotrypsin activity in a stronger manner than Solidago sp. The results indicate the application potential of compounds obtained from these plants as chymotrypsin inhibitors and antioxidant agents. Full article
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25 pages, 3599 KiB  
Article
Sustainable Production of Eco-Friendly, Low-Carbon, High-Octane Gasoline Biofuels Through a Synergistic Approach for Cleaner Transportation
by Tamer M. M. Abdellatief, Ahmad Mustafa, Mohamed Koraiem M. Handawy, Muhammad Bakr Abdelghany and Xiongbo Duan
Fuels 2025, 6(3), 49; https://doi.org/10.3390/fuels6030049 - 23 Jun 2025
Viewed by 513
Abstract
This research work seeks to introduce eco-friendly, low-carbon, and high-octane biofuel gasoline production using a synergistic approach. Four types of high-octane gasoline, including SynergyFuel-92, SynergyFuel-95, SynergyFuel-98, and SynergyFuel-100, were generated, emphasizing the deliberate combination of petroleum-derived gasoline fractions using reformate, isomerate, and delayed [...] Read more.
This research work seeks to introduce eco-friendly, low-carbon, and high-octane biofuel gasoline production using a synergistic approach. Four types of high-octane gasoline, including SynergyFuel-92, SynergyFuel-95, SynergyFuel-98, and SynergyFuel-100, were generated, emphasizing the deliberate combination of petroleum-derived gasoline fractions using reformate, isomerate, and delayed coking (DC) naphtha with octane-boosting compounds—bio-methanol and bio-ethanol. A set of tests have been performed to examine the effects of antiknock properties, density, oxidation stability, distillation range characteristics, hydrocarbon composition, vapor pressure, and the volatility index on gasoline blends. The experimental results indicated that the gasoline blends made from biofuel (SynergyFuel-92, -95, -98, and 100) showed adherence to important fuel quality criteria in the USA, Europe, and China. These blends had good characteristics, such as low quantities of benzene and sulfur, regulated levels of olefins and aromatics, and good distillation qualities. By fulfilling these strict regulations, Synergy Fuel is positioned as a competitive and eco-friendly substitute for traditional gasoline. The results reported that SynergyFuel-100 demonstrated the strongest hot-fuel-handling qualities and resistance to vapor lock among all the mentioned Synergy Fuels. Finally, the emergence of eco-friendly, low-carbon, and high-octane biofuel gasoline production with synergistic benefits is a big step in the direction of sustainable transportation. Full article
(This article belongs to the Special Issue Sustainability Assessment of Renewable Fuels Production)
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20 pages, 2398 KiB  
Article
The Protective Effect of Boschnikia rossica Extract on Free Radical-Induced Oxidative Damage of Biomolecules and Establishment of a Method for Determining the Content of Oleanolic Acid
by Zhuohao Zhao, Mingjie Jia, Yuning An, Yihong Bao and Yuncai Zhao
Foods 2025, 14(10), 1658; https://doi.org/10.3390/foods14101658 - 8 May 2025
Viewed by 468
Abstract
Oxidative stress-induced damage to biomolecules such as proteins, lipids, and DNA is closely related to chronic diseases. Developing efficient, low-toxicity, and multi-target natural antioxidants has become an important research direction in food and medicine. This study established a detection method for oleanolic acid [...] Read more.
Oxidative stress-induced damage to biomolecules such as proteins, lipids, and DNA is closely related to chronic diseases. Developing efficient, low-toxicity, and multi-target natural antioxidants has become an important research direction in food and medicine. This study established a detection method for oleanolic acid (OA) content in Boschnikia rossica extract (BRE). It systematically evaluated the in vitro antioxidant activity and protective effect of Boschnikia rossica extract on oxidative damage of biomolecules. Firstly, the detection method based on RP-HPLC has improved the problem of low separation efficiency and high interference in detecting OA in Boschnikia rossica. The optimal analysis conditions were obtained by optimizing the chromatographic conditions: the chromatographic column was Agilent TC-C18 (250 mm × 4.6 mm, 5 μm); the mobile phase was methanol/0.4% phosphoric acid aqueous solution (85/15, v/v), pH 2.14; the column temperature was 20 °C; the flow rate was 1.2 mL/min; and the detection wavelength was 220 nm. Under these conditions, the linear relationship of OA was good within the concentration range of 100–800 mg/L, with a recovery rate of 98.88–101.46% and RSD less than 2%. The content of OA was 0.358 mg/g. Next, the in vitro antioxidant effect of BRE was tested, and it was found that BRE had reasonable scavenging rates against ABTS, DPPH, and hydroxyl radicals, with IC50 values of 224.32 mg/L, 58.43 mg/L, and 432.21 mg/L, respectively. In addition, BRE had significant inhibitory effects on protein oxidative degradation, carbonylation modification, lipid oxidation, and DNA oxidative damage induced by different free radicals. Finally, BRE can be a natural alternative to synthetic antioxidants and has important application value in delaying food oxidation and developing anti-aging functional foods. Full article
(This article belongs to the Section Food Nutrition)
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39 pages, 4380 KiB  
Article
Power Density and Thermochemical Properties of Hydrogen Magnetohydrodynamic (H2MHD) Generators at Different Pressures, Seed Types, Seed Levels, and Oxidizers
by Osama A. Marzouk
Hydrogen 2025, 6(2), 31; https://doi.org/10.3390/hydrogen6020031 - 2 May 2025
Cited by 3 | Viewed by 1590
Abstract
Hydrogen and some of its derivatives (such as e-methanol, e-methane, and e-ammonia) are promising energy carriers that have the potential to replace conventional fuels, thereby eliminating their harmful environmental impacts. An innovative use of hydrogen as a zero-emission fuel is forming weakly ionized [...] Read more.
Hydrogen and some of its derivatives (such as e-methanol, e-methane, and e-ammonia) are promising energy carriers that have the potential to replace conventional fuels, thereby eliminating their harmful environmental impacts. An innovative use of hydrogen as a zero-emission fuel is forming weakly ionized plasma by seeding the combustion products of hydrogen with a small amount of an alkali metal vapor (cesium or potassium). This formed plasma can be used as a working fluid in supersonic open-cycle magnetohydrodynamic (OCMHD) power generators. In these OCMHD generators, direct-current (DC) electricity is generated straightforwardly without rotary turbogenerators. In the current study, we quantitatively and qualitatively explore the levels of electric conductivity and the resultant volumetric electric output power density in a typical OCMHD supersonic channel, where thermal equilibrium plasma is accelerated at a Mach number of two (Mach 2) while being subject to a strong applied magnetic field (applied magnetic-field flux density) of five teslas (5 T), and a temperature of 2300 K (2026.85 °C). We varied the total pressure of the pre-ionization seeded gas mixture between 1/16 atm and 16 atm. We also varied the seed level between 0.0625% and 16% (pre-ionization mole fraction). We also varied the seed type between cesium and potassium. We also varied the oxidizer type between air (oxygen–nitrogen mixture, 21–79% by mole) and pure oxygen. Our results suggest that the ideal power density can reach exceptional levels beyond 1000 MW/m3 (or 1 kW/cm3) provided that the total absolute pressure can be reduced to about 0.1 atm only and cesium is used for seeding rather than potassium. Under atmospheric air–hydrogen combustion (1 atm total absolute pressure) and 1% mole fraction of seed alkali metal vapor, the theoretical volumetric power density is 410.828 MW/m3 in the case of cesium and 104.486 MW/m3 in the case of potassium. The power density can be enhanced using any of the following techniques: (1) reducing the total pressure, (2) using cesium instead of potassium for seeding, and (3) using air instead of oxygen as an oxidizer (if the temperature is unchanged). A seed level between 1% and 4% (pre-ionization mole fraction) is recommended. Much lower or much higher seed levels may harm the OCMHD performance. The seed level that maximizes the electric power is not necessarily the same seed level that maximizes the electric conductivity, and this is due to additional thermochemical changes caused by the additive seed. For example, in the case of potassium seeding and air combustion, the electric conductivity is maximized with about 6% seed mole fraction, while the output power is maximized at a lower potassium level of about 5%. We also present a comprehensive set of computed thermochemical properties of the seeded combustion gases, such as the molecular weight and the speed of sound. Full article
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20 pages, 3281 KiB  
Article
Effective and High-Performance MgFe2O4/Mg-MOF Composite for Direct Methanol Fuel Cells
by M. R. Hussein, Amna A. Kotp, E. M. Elsayed, A. M. Elseman and Mohamed Sh. Abdel-wahab
Catalysts 2025, 15(4), 394; https://doi.org/10.3390/catal15040394 - 18 Apr 2025
Cited by 1 | Viewed by 736
Abstract
The development of efficient and sustainable electrocatalysts for optimizing methanol oxidation reactions (MORs) in direct methanol fuel cells (DMFCs) is crucial for the innovation of clean electrode energy technologies. This study highlights the synthesis and characterization of magnesium ferrite (MgFe2O4 [...] Read more.
The development of efficient and sustainable electrocatalysts for optimizing methanol oxidation reactions (MORs) in direct methanol fuel cells (DMFCs) is crucial for the innovation of clean electrode energy technologies. This study highlights the synthesis and characterization of magnesium ferrite (MgFe2O4) and magnesium-based metal–organic framework (Mg-MOF) composites, utilizing cost-effective and scalable methods such as co-precipitation and ultrasound-assisted synthesis. The composite material, prepared in a 1:1 ratio, demonstrated enhanced catalytic performance due to the synergistic integration of MgFe2O4 and Mg-MOF. Comprehensive structural and morphological analyses, including X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), the Brunauer–Emmett–Teller (BET) technique, and X-ray photoelectron spectroscopy (XPS), confirmed the successful formation of the composite. Also, the modification of magnetic properties, particularly the values of coercive force (Hc), led to a significant enhancement in electrical and catalytic performance. The material exhibited mesoporous characteristics and an improved surface area. Electrochemical evaluations revealed superior MOR activity for the composite electrode, achieving a current density of 31.5 mA∙cm−2 at 1 M methanol with an onset potential of 0.34 V versus Ag/AgCl, measured at a scan rate of 100 mV/s. Remarkably, the composite electrode showed a 75% improvement in current density compared to its components. Additionally, the composite exhibited a low overpotential of 350 mV and favorable Tafel slopes of 22.54 and 4.27 mV∙dec−1 at high and low potentials, respectively, confirming rapid methanol oxidation kinetics on this electrode. It also demonstrated excellent stability, retaining 97.4% of its current density after 1 h. Electrochemical impedance spectroscopy (EIS) further revealed a reduced charge transfer resistance of 9.26 Ω, indicating enhanced conductivity and catalytic efficiency. These findings underscore the potential of MgFe2O4/Mg-MOF composites as cost-effective and high-performance anode materials for DMFCs, paving the way for sustainable energy solutions. Full article
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15 pages, 5978 KiB  
Article
Enhanced Methanol Electro-Oxidation in Hierarchical Au-Pt Dendrites Supported on Graphene-like Substrate
by Zifeng Zhu, Yiming Zhao, Yongming Ruan, Xuexiang Weng and Gesmi Milcovich
Coatings 2025, 15(4), 458; https://doi.org/10.3390/coatings15040458 - 12 Apr 2025
Cited by 1 | Viewed by 669
Abstract
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 [...] Read more.
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
(This article belongs to the Section Surface Characterization, Deposition and Modification)
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15 pages, 2726 KiB  
Article
Electrochemical Quartz Microbalance for Studying Electrodeposited Pt Catalysts for Methanol Oxidation Reaction
by Bangfeng Zong, Xiaojun Pan, Bo Wei, Lifang Zhang, Xiangxiong Feng, Chenggong Hou, Hai Yan, Wenju Xie, Guicheng Liu and Feng Ye
Inorganics 2025, 13(4), 111; https://doi.org/10.3390/inorganics13040111 - 3 Apr 2025
Viewed by 492
Abstract
Pt catalysts are investigated for methanol oxidation in direct methanol fuel cells, utilizing the electrochemical quartz microbalance method (EQCM) with exceptional resolution and sensitivity. Pt catalysts were deposited onto the gas-diffusion layer of carbon using stationary potential electrodeposition. Physical characterization and electrochemical tests [...] Read more.
Pt catalysts are investigated for methanol oxidation in direct methanol fuel cells, utilizing the electrochemical quartz microbalance method (EQCM) with exceptional resolution and sensitivity. Pt catalysts were deposited onto the gas-diffusion layer of carbon using stationary potential electrodeposition. Physical characterization and electrochemical tests were performed. SEM results showed that Pt presented dendrite crystals with nanoscale facets. Cyclic voltammetry (CV) demonstrated that the current density for the methanol oxidation reaction highly reached 1020 mA·cm−2 for the deposited Pt catalyst by EQCM. The dendrite crystal structures of deposited Pt provide much area for high catalytic activity. It found that the peak density of the Pt catalysts for the methanol oxidation reaction decreased after five cycles. Furthermore, the response frequency for the adsorption of the deposited Pt catalysts was investigated using EQCM and compared with commercial PtRu catalysts. The results showed that the response frequency of the Pt catalysts decreased more rapidly than that of the PtRu catalysts. It is possible for the adsorption of small organic molecules on Pt catalysts to occur during the methanol electro-oxidation with COad intermediates. The reaction mechanism is preliminarily discussed by the electrochemical measurement combined with EQCM. Full article
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27 pages, 3909 KiB  
Review
Styrene and Its Derivatives Used in Proton Exchange Membranes and Anion Exchange Membranes for Fuel Cell Applications: A Review
by Muhammad Rehman Asghar, Ayesha Zahid, Huaneng Su, Kumar Divya, Muhammad Tuoqeer Anwar and Qian Xu
Batteries 2025, 11(4), 134; https://doi.org/10.3390/batteries11040134 - 29 Mar 2025
Cited by 1 | Viewed by 987
Abstract
The proton exchange membrane (PEM) is a critical component of fuel cells, responsible for controlling the flow of protons while minimizing fuel crossover through its channels. The commercial membrane commonly used in fuel cells is made of Nafion, which is expensive and prone [...] Read more.
The proton exchange membrane (PEM) is a critical component of fuel cells, responsible for controlling the flow of protons while minimizing fuel crossover through its channels. The commercial membrane commonly used in fuel cells is made of Nafion, which is expensive and prone to swelling when in contact with water. To address these limitations, various polymers have been explored as alternatives to replace the costly Nafion membrane. Styrene, a versatile and cost-effective material, has emerged as a promising candidate. It can be modified into different forms to meet the requirements of a fuel cell membrane. The aromatic rings in styrene can copolymerize with hydrophilic functional groups, enhancing water (H2O) uptake, proton conductivity, and ion exchange capacity (IEC) of the membrane. Additionally, the hydrophobic nature of styrene helps maintain the structural integrity of the membrane’s channels, reducing excessive swelling and minimizing fuel crossover. The flexible aromatic chains in styrene facilitate the attachment of hydrophilic functional groups, such as sulfonic groups, further improving the membrane’s ion conductivity, IEC, thermal stability, mechanical strength, and oxidative stability. This review article explores the application of styrene and its derivatives in fuel cell membranes, with a focus on proton exchange membrane fuel cells (PEMFCs), direct methanol fuel cells (DMFCs), and anion exchange membrane fuel cells (AEMFCs). Full article
(This article belongs to the Special Issue New Polymer Electrolyte Membranes for Fuel Cells)
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23 pages, 2792 KiB  
Article
Enhanced Electrocatalytic Performance of Nickel-Cobalt-Titanium Dioxide-Embedded Carbon Nanofibers for Direct Alcohol Fuel Cells
by Wael M. Mohammed, Mahmoud A. Mohamed, Mohamed O. Abdel-Hamed and Esam E. Abdel-Hady
J. Compos. Sci. 2025, 9(3), 125; https://doi.org/10.3390/jcs9030125 - 10 Mar 2025
Cited by 1 | Viewed by 1483
Abstract
This study focuses on making non-precious electrocatalysts for improving the performance of Direct Alcohol Fuel Cells (DAFCs). Specifically, it examines the oxidation of ethanol and methanol. Conventional platinum-based catalysts are expensive and suffer from problems such as degradation and poisoning. To overcome these [...] Read more.
This study focuses on making non-precious electrocatalysts for improving the performance of Direct Alcohol Fuel Cells (DAFCs). Specifically, it examines the oxidation of ethanol and methanol. Conventional platinum-based catalysts are expensive and suffer from problems such as degradation and poisoning. To overcome these challenges, we fabricated tri-metallic catalysts composed of nickel, cobalt, and titanium dioxide (TiO2) embedded in carbon nanofibers (CNFs). The synthesis included electrospinning and subsequent carbonization as well as optimization of parameters to achieve uniform nanofiber morphology and high surface area. Electrochemical characterization revealed that the incorporation of TiO2 significantly improved electrocatalytic activity for ethanol and methanol oxidation, with current densities increasing from 57.8 mA/cm2 to 74.2 mA/cm2 for ethanol and from 38.69 mA/cm2 to 60.39 mA/cm2 for methanol as the TiO2 content increased. The catalysts showed excellent stability, with the TiO2-enriched sample (T2) showing superior performance during longer cycling tests. Chronoamperometry and electrochemical impedance spectroscopy are used to examine the stability of the catalysts and the dynamics of the charge carriers. Impedance spectroscopy indicated reduced charge transfer resistance, confirming enhanced activities. These findings suggest that the synthesized non-precious electrocatalysts can serve as effective alternatives to platinum-based materials, offering a promising pathway for the development of cost-efficient and durable fuel cells. Research highlights non-precious metal catalysts for sustainable fuel cell technologies. Full article
(This article belongs to the Section Nanocomposites)
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20 pages, 13636 KiB  
Article
Cross-Linked Self-Standing Graphene Oxide Membranes: A Pathway to Scalable Applications in Separation Technologies
by Juan A. G. Carrio, Vssl Prasad Talluri, Swamy T. Toolahalli, Sergio G. Echeverrigaray and Antonio H. Castro Neto
Membranes 2025, 15(1), 31; https://doi.org/10.3390/membranes15010031 - 15 Jan 2025
Viewed by 1714
Abstract
The large-scale implementation of 2D material-based membranes is hindered by mechanical stability and mass transport control challenges. This work describes the fabrication, characterisation, and testing of self-standing graphene oxide (GO) membranes cross-linked with oxides such as Fe2O3, Al2 [...] Read more.
The large-scale implementation of 2D material-based membranes is hindered by mechanical stability and mass transport control challenges. This work describes the fabrication, characterisation, and testing of self-standing graphene oxide (GO) membranes cross-linked with oxides such as Fe2O3, Al2O3, CaSO4, Nb2O5, and a carbide, SiC. These cross-linking agents enhance the mechanical stability of the membranes and modulate their mass transport properties. The membranes were prepared by casting aqueous suspensions of GO and SiC or oxide powders onto substrates, followed by drying and detachment to yield self-standing films. This method enabled precise control over membrane thickness and the formation of laminated microstructures with interlayer spacings ranging from 0.8 to 1.2 nm. The resulting self-standing membranes, with areas between 0.002 m2 and 0.090 m2 and thicknesses from 0.6 μm to 20 μm, exhibit excellent flexibility and retain their chemical and physical integrity during prolonged testing in direct contact with ethanol/water and methanol/water mixtures in both liquid and vapour phases, with stability demonstrated over 24 h and up to three months. Gas permeation and chemical characterisation tests evidence their suitability for gas separation applications. The interactions promoted by the oxides and carbide with the functional groups of GO confer great stability and unique mass transport properties—the Nb2O5 cross-linked membranes present distinct performance characteristics—creating the potential for scalable advancements in cross-linked 2D material membranes for separation technologies. Full article
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16 pages, 4793 KiB  
Article
Simulation of Surface Segregation in Nanoparticles of Pt-Pd Alloys
by Jose Brito Correia and Ana Isabel de Sá
Crystals 2025, 15(1), 53; https://doi.org/10.3390/cryst15010053 - 7 Jan 2025
Cited by 5 | Viewed by 1086
Abstract
Platinum (Pt) and palladium (Pd) are crucial in hydrogen energy technologies, especially in fuel cells, due to their high catalytic activity and chemical stability. Pt-Pd nanoparticles, produced through various methods, enhance catalytic performance based on their size, shape, and composition. These nanocatalysts excel [...] Read more.
Platinum (Pt) and palladium (Pd) are crucial in hydrogen energy technologies, especially in fuel cells, due to their high catalytic activity and chemical stability. Pt-Pd nanoparticles, produced through various methods, enhance catalytic performance based on their size, shape, and composition. These nanocatalysts excel in direct methanol fuel cells (DMFCs) and direct ethanol fuel cells (DEFCs) by promoting alcohol oxidation and reducing CO poisoning. Pt-Pd catalysts are also being explored for their oxygen reduction reaction (ORR) on the cathodic side of fuel cells, showing higher activity and stability than pure platinum. Molecular dynamics (MD) simulations have been conducted to understand the structural and surface energy effects of PdPt nanoparticles, revealing phase separation and chemical ordering, which are critical for optimizing these catalysts. Pd migration to the surface layer in Pt-Pd alloys minimizes the overall potential energy through the formation of Pd surface monolayers and Pt-Pd bonds, leading to a lower surface energy for intermediate compositions compared to that of the pure elements. The potential energy, calculated from MD simulations, increases with a decreasing particle size due to surface creation, indicating higher reactivity for smaller particles. A general contraction of the average distance to the nearest neighbour atoms was determined for the top surface layers within the nanoparticles. This research highlights the significant impact of Pd segregation on the structural and surface energy properties of Pt-Pd nanoparticles. The formation of Pd monolayers and the resulting core–shell structures influence the catalytic activity and stability of these nanoparticles, with smaller particles exhibiting higher surface energy and reactivity. These findings provide insights into the design and optimization of Pt-Pd nanocatalysts for various applications. Full article
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13 pages, 1934 KiB  
Article
Ceria-Catalysed Production of Dimethyl Carbonate from Methanol and CO2: Effect of Using a Dehydrating Agent Combined with a Solid Cocatalyst
by Dichao Shi, Svetlana Heyte, Mickaël Capron and Sébastien Paul
Molecules 2024, 29(23), 5663; https://doi.org/10.3390/molecules29235663 - 29 Nov 2024
Viewed by 918
Abstract
The direct synthesis of dimethyl carbonate (DMC) from CO2 and methanol over ceria-based catalysts, in the presence of a dehydrating agent shifting the thermodynamical equilibrium of the reaction, has received significant interest recently. In this work, several dehydrating agents, such as molecular [...] Read more.
The direct synthesis of dimethyl carbonate (DMC) from CO2 and methanol over ceria-based catalysts, in the presence of a dehydrating agent shifting the thermodynamical equilibrium of the reaction, has received significant interest recently. In this work, several dehydrating agents, such as molecular sieves, 2,2-dimethoxypropane (DMP), dimethoxymethane (DMM) and 1,1,1-trimethoxymethane (TMM), are combined with commercial ceria to compare their influence on the DMC yield obtained under the same set of operating conditions. TMM is found to be the most efficient; however, its conversion is not complete even after 48 h of reaction. Therefore, it is proposed for the very first time, to the best of our knowledge, to add a second solid cocatalyst in the reaction medium to accelerate the TMM hydration reaction without degrading the DMC already formed. Basic oxides and acidic zeolites with different Si/Al ratios are employed to accelerate the hydration of TMM, so as to improve the DMC yield. 13X was identified as the best option to play this role. Finally, three different commercial cerias are tested in the presence of TMM and molecular sieve 13X as the second catalyst. The most efficient combination of ceria, TMM, and molecular sieve 13X is ultimately tested in a 250 mL autoclave to start to scale up the process. A very high DMC production of 199.5 mmol DMC/gcat. is obtained. Full article
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20 pages, 4666 KiB  
Article
CuI-Zeolite Catalysis for Biaryl Synthesis via Homocoupling Reactions of Phenols or Aryl Boronic Acids
by Xiaohui Di, Tony Garnier, Arnaud Clerc, Eliott Jung, Christian Lherbet, Valérie Bénéteau, Patrick Pale and Stefan Chassaing
Molecules 2024, 29(23), 5552; https://doi.org/10.3390/molecules29235552 - 25 Nov 2024
Cited by 1 | Viewed by 1727
Abstract
Due to the importance of biaryls as natural products, drugs, agrochemicals, dyes, or organic electronic materials, a green alternative biaryl synthesis has been developed based on easy-to-prepare and cheap copper(I)-exchanged zeolite catalysts. CuI-USY proved to efficiently catalyze the direct homocoupling of [...] Read more.
Due to the importance of biaryls as natural products, drugs, agrochemicals, dyes, or organic electronic materials, a green alternative biaryl synthesis has been developed based on easy-to-prepare and cheap copper(I)-exchanged zeolite catalysts. CuI-USY proved to efficiently catalyze the direct homocoupling of either phenols or aryl boronic acids under simple and practical conditions. The CuI-USY-catalyzed oxidative homocoupling of phenols could conveniently be performed under air either in warm methanol or water with good to high yields. In methanol, a small amount of Cs2CO3 was required, while none was necessary in water. The homocoupling of aryl boronic acids was best performed also in warm methanol, without an additive. These mild conditions showed good functional-group tolerance, leading to a variety of substituted (hetero)biaryls (28 examples). The heterogeneous CuI-USY catalyst could readily be recovered and reused. Interestingly, the homocoupling of vinyl boronic acids was successfully coupled to a Diels–Alder reaction, even in a one-pot process, allowing access to highly functionalized cyclohexenes. Full article
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