Search Results (314)

This study investigates reduced graphene oxide (rGO)-supported bimetallic M–Pt (M = Co, Ni, Cu) alloy nanoparticles as electrocatalysts for the hydrogen evolution reaction (HER) in alkaline media. Monometallic Pt and bimetallic M–Pt nanoparticles were synthesized and uniformly dispersed on rGO, followed by structural and compositional characterization using transmission electron microscopy and inductively coupled plasma mass spectrometry. Their electrocatalytic performance toward HER was systematically evaluated at different temperatures. All electrocatalysts exhibited enhanced activity at higher temperatures, with current densities increasing by approximately 1.68–2.65 times at 338 K compared with 298 K. Among the investigated materials, CoPt/rGO delivered the highest cathodic current densities and a Tafel slope of 75 mV dec⁻¹, indicating favorable reaction kinetics. This performance is associated with a higher electroactive surface area, as determined by cyclic voltammetry, and reduced charge-transfer resistance, as revealed by electrochemical impedance spectroscopy. Notably, the CoPt/rGO electrocatalyst demonstrated excellent short-term operational stability at a constant potential of −0.28 V vs. RHE. These results highlight the potential of rGO-supported CoPt bimetallic alloys as efficient electrocatalysts for alkaline water electrolysis. Full article

This article reports on how the length of the alkyl chain influences the morphological properties of thiol-stabilized silver nanoparticles (Ag NPs) and their subsequent effects on the performance and durability of proton exchange membrane fuel cells (PEMFCs). We synthesized thiol-stabilized Ag NPs by varying the alkyl chain length: 1-hexane thiol (C6), 1-octanethiol (C8), 1-decanethiol (C10), 1-dodecanethiol (C12), and 1-tetradecanethiol (C14), which we achieved using the two–phase Brust–Schiffrin method. X-ray Diffraction (XRD) patterns confirm the formation of crystalline Ag NPs. A morphological study conducted using a Transmission Electron Microscope (TEM) demonstrated that smaller alkyl chain length thiols (C6, C8, and C10) tend to coalesce, while C12 shows better uniformity with no agglomeration. C14 produces larger nanoparticles. A distinct pressure-area isotherm was observed when Ag NPs were spread at the water/air interface of a Langmuir–Blodgett (LB) trough. After obtaining the monolayer formation pressure range, we coated the Nafion 117 membrane of a polymer electrolyte membrane fuel cell with these nanoparticles to form monolayers of different Ag NPs (C6, C8, C12, C14) at various surface pressures (2 mN/m, 6 mN/m and 10 mN/m). Maximum power output enhancement was observed for C12, while other nanoparticles (C6, C8, C10, C14) did not exhibit noticeable power enhancement for PEMFCs. C12 Ag NPs deposited at surface pressure 6 mN/m give maximum power density increase (26.5%) at the fuel cell test station. In addition, we examined the carbon monoxide (CO) resistance test by mixing 0.1% CO with hydrogen (H2), and C12 Ag NPs showed the highest resistance to CO poisoning. However, no enhancement in power or CO tolerance was observed when C12 Ag NPs were coated by spray coating. These outcomes showcase that alkyl chain length plays a critical role in controlling the size and distribution of thiol-stabilized nanoparticles, which eventually has a direct impact on the performance and CO resistance of PEMFCs when applied to polymer electrolyte (Nafion 117). In addition, surface pressure during monolayer formation controls the distribution of Ag NPs (the distance between nanoparticles at the membrane interface), which is necessary to achieve catalytic activity for power improvement and to prevent platinum (Pt) poisoning by CO oxidation at ambient conditions. Full article

Pt-rare earth metal (Pt-RE) alloys are considered to be one of the most promising electrocatalysts for producing oxygen reduction reactions (ORRs) due to their compressively strained Pt overlayer and their exceptional negative-alloy formation energies, which result in excellent activity and stability. However, there are still great challenges in the chemical synthesis of Pt-RE nanoalloys. Herein, we report a simple method employing the nanopores of porous carbon as nanoreactors to synthesize a Pt₅La nanoalloy. The Pt₅La alloy nanoparticles are embedded in porous carbon (Pt₅La@C) with a particle size of around 1–3 nm and also exhibit a very narrow size distribution because of the confined-space effect. The as-prepared Pt₅La@C nanoalloy exhibits highly efficient ORR performance with a half-wave potential of 0.912 V in 0.1 M HClO₄, which is 56 mV higher than that of a commercial Pt/C catalyst. Moreover, it achieves an improved intrinsic activity of 0.69 mA cm⁻² and, a mass activity of 0.42 A mg_Pt⁻¹ at 0.90 V. In addition, it also delivers a very stable lifespan performance, with negligible decay in half-wave potential after accelerated stress testing for 10,000 cycles. This work also provides a new method for the development of promising Pt-RE nanoalloys with ultrasmall nanoparticles with a very narrow size distribution for various efficient energy-conversion devices. Full article

The purpose of this research is to examine how the electro-optical behavior of platinum (Pt) nanoparticles prepared via the gamma radiolysis process is related to both the radiation dose and to the Pt precursor concentration. The Pt precursor used in these experiments has been radiolytically degraded using a ⁶⁰Co gamma source at dosages ranging from 80 kGy to 120 kGy. As well, varying the concentration of the Pt precursor from 5.0 × 10⁻⁴ M to 20.0 × 10⁻⁴ M was carried out as a systematic investigation. Spectrophotometric analysis utilizing UV–Visible spectroscopy and TEM provided the optical data and particle size information for the nanoparticles. The results indicate that increasing the radiation dosage results in smaller Pt nanoparticle sizes due to an increased rate of nucleation and that increasing the Pt precursor concentration leads to larger Pt nanoparticles due to an increase in ion recombination. Both the dose and concentration dependency of the optical absorption spectrum indicate a significant relationship between size and plasmon behavior. Also, the conduction band energy level, which was determined from the maximum of the UV–Visible absorption peak, is dependent on the particle size and shows a pronounced quantum confinement effect, with the conduction band energy increasing as the particle size decreases. Thus, these studies provide a definitive correlation of structure–property in Pt nanoparticles and confirm the capability of the gamma radiolytic synthesis process to be used for controlling the specific electronic and optical properties of Pt nanoparticles. Full article

Developing efficient and durable oxygen reduction reaction (ORR) catalysts is crucial for advancing fuel cell technology and sustainable energy conversion. In this study, a scalable strategy was employed to synthesize ZIF-derived nitrogen-sulfur co-doped carbon nanosheets embedded with in situ generated ZnS and Co₉S₈ nanoparticles. The synergistic effect of heteroatom doping and metal sulfide modification effectively modulated the electronic structure, optimized charge transfer pathways, and enhanced structural stability. The optimized catalyst exhibited a half-wave potential of 0.83 V vs. RHE, close to that of commercial 20 wt% Pt/C (0.85 V), excellent 4e⁻ ORR selectivity, and exceptional stability, with only a ~15 mV degradation after 10,000 cycles. These results demonstrate that the combination of nitrogen sulfur co-doping and in situ metal sulfide addition pro-vides an effective approach for designing highly active and durable non-precious metal catalysts for the ORR. This synthetic concept provides practical guidance for the scalable preparation of multifunctional nanomaterial-based catalysts for electrochemical energy applications. Full article

To improve the electrocatalytic methanol oxidation (MOR) performance of platinum (Pt)-based catalysts in direct methanol fuel cells (DMFCs), this study uses phosphorus-doped carbon nanotubes (P-CNTs) as a support material. Through a hydrothermal method, different proportions of potassium bromide (KBr) are introduced as a structural directing agent to prepare a series of Pt/P-CNTs-M catalysts (where M represents the molar ratio of KBr to Pt). The study systematically investigates the mechanism by which KBr regulates the crystal plane of Pt nanoparticles and its structure–activity relationship. Physical characterization revealed that KBr selectively regulates Pt crystal plane growth through Br⁻ adsorption. When M = 30, Pt/P-CNTs-30 exhibited the highest proportion of exposed Pt(111) crystal planes (27.21%), with Pt⁰ content reaching 51.64%, and featured moderate particle size (2.22 nm) and uniform dispersion. Electrochemical testing indicates that the MOR mass-specific activity of this catalyst reaches 3559.85 mA·mg⁻¹_Pt, which is 1.17 times that of Pt/P-CNTs-0; it exhibits the lowest charge transfer impedance, with a current density of 488.25 mA·mg⁻¹_Pt still maintained after 3600 s of chronoamperometry testing, and a more negative CO oxidation onset potential, demonstrating optimal resistance to poisoning. The study indicates that an appropriate KBr ratio can synergistically optimize Pt crystal plane structure and electronic states, providing a theoretical basis for the design of high-efficiency fuel cell catalysts. Full article

Platinum is known as the most efficient catalyst for oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). However, Pt catalysts still encounter high loading demands, poor atom utilization, and uncontrolled nanoparticle aggregation, which severely restrict their practical use. To address these issues, we designed a Pt-W_1.33C hybrid catalyst with strong interfacial coupling between Pt nanoparticles and the vacancy-rich i-MXene, W_1.33C matrix. This robust Pt-W_1.33C interaction effectively restricts Pt overgrowth, producing uniformly dispersed nanoparticles with an average physical size of 3.1 nm. The results show that the modulated electronic structure facilitates electron transfer from W_1.33C to neighboring Pt sites, which reduces the energy barriers of chemical reactions and enhances the intrinsic electrochemical catalytic activity of the hybridized catalysts. As a result, the Pt-W_1.33C catalyst with low Pt loading achieves an ORR overpotential of 320 mV at 0.1 mA cm⁻², an HER overpotential of 36 mV at 10 mA cm⁻², and Tafel slopes of 66 and 27.8 mV dec⁻¹ for ORR and HER, respectively. The enhanced ORR and HER performance of Pt-W_1.33C can be attributed to the synergistic interplay between Pt and W_1.33C, including the disordered stacking of W_1.33C, high conductivity of W_1.33C, high catalytic activity of Pt, and strong Pt-W_1.33C interfacial coupling, which, together, optimize electronic interaction and active-site accessibility in the hybrid catalyst. Full article

Metal nanoparticles (NPs) with enzyme-mimicking activities, known as nanozymes, are being actively explored for biomedical and analytical applications. Enhancing their catalytic activity and metal utilization efficiency is crucial for advancing these technologies. Here, we report an aqueous-phase, room-temperature synthesis of tetra-metallic Au@Ag-Pd-Pt NPs that exhibit superior peroxidase-like activity compared to their mono-, bi-, and trimetallic counterparts. The synthesis involves a sequential, seed-mediated approach comprising the formation of Au NP seeds, the overgrowth of a Ag shell, and the galvanic replacement of Ag with Pd and Pt ions. We systematically investigated the effects of the Au core diameter (15, 40, 55 nm), Ag precursor concentration (50–400 µM), and the Pd-to-Pt ratio on the optical and catalytic properties. By changing the particle composition, we were able to tune the absorbance maximum from 520 nm to 650 nm while maintaining high extinction coefficients (10⁹–10¹⁰ M⁻¹cm⁻¹) comparable to that of the initial Au nanoparticles. Mapping of chemical element distributions in the nanoscale range confirmed a core–shell–shell architecture with surface-enriched Pd and Pt. This structure ensures the surface-exposed localization of catalytically active atoms, yielding a more than 10-fold improvement in specific peroxidase-like activity while utilizing up to two orders of magnitude less Pt and Pd than bimetallic particles. The synthesized NPs thus combine high catalytic activity with tunable optical properties, making them promising multifunctional labels for biosensing. Full article

The aim of this work was high-temperature synthesis of PtPdCoNiCu/C nanoparticles with high-entropy alloy (HEA) structure as catalysts for oxygen reduction reaction. The materials were synthesized using a highly dispersed PtPd/C support, which was impregnated with Cu, Ni, and Co precursors followed by their precipitation with an alkali. Subsequently, the material was subjected to thermal treatment in a tube furnace at 600 °C for 1 h in a stream of argon containing 5% hydrogen. In combination with HRTEM, element mapping and line scan, XRD, and XPS data, these results confirm the successful synthesis of five-component PtPdCoNiCu high-entropy alloy nanoparticles on the surface of the carbon support. The obtained materials are characterized by a high electrochemical surface area of up to 63 m²/g(PGM), as determined by hydrogen adsorption/desorption and CO-stripping, and a high specific oxygen reduction reaction (ORR) activity of approximately 269 A/g(PGM) at 0.9 V vs. RHE. The synthesized material demonstrated outstanding stability, as confirmed by an accelerated stress test of 10,000 cycles. After the test, the electrochemical surface area decreased by only 12%, while the catalytic activity for ORR even increased. The proposed synthetic strategy opens a new pathway for obtaining promising highly stable five-component HEA nanoparticles of various compositions for application in catalysts. Full article

In this study, we report the preparation of platinum nanoparticles (Pt NPs) deposited on HTiNbO₅ and the application of the resultant material in the catalytic decomposition of sodium borohydride (NaBH₄) to generate hydrogen. The starting material, KTiNbO₅, was prepared through a solid-state process involving Nb₂O₅, K₂CO₃, and TiO₂. The subsequent treatment with HNO₃ resulted in the exchange of potassium by protons, rendering HTiNbO₅. This material served as support for Pt nanoparticles (3.6 ± 0.7 nm), producing Pt NPs/HTiNbO₅. All compounds were characterized using TGA, FTIR, XRD, Raman, SEM-EDS, and HRTEM. The influence of different factors on the reaction kinetics was evaluated, resulting in a hydrogen generation rate (HGR) of 22,790.18 $\mathrm{m}\mathrm{L} {\mathrm{m}\mathrm{i}\mathrm{n}}^{-1}{\mathrm{g}}_{\mathrm{c}\mathrm{a}\mathrm{t}}^{-1}$ at 50 °C. The activation energy (41.83 kJ mol⁻¹) was also determined. A mechanistic study with deuterated water revealed a kinetic isotopic effect (KIE) value of 1.27, indicating the dissociation of B-H from BH₄⁻ as the rate-determining step of the process. Furthermore, the reuse and durability of the material were evaluated, revealing a catalyst performance close to 100% over the 10 tested cycles. Therefore, it can be concluded that the synthesized material, Pt-nanoparticles dispersed on HTiNbO₅, exhibits excellent performance and is suitable for hydrogen evolution from NaBH₄. Full article

Tin(IV) oxide (SnO₂) was deposited onto acid-washed multiwalled carbon nanotubes (MWCNTs) to be used as a support for platinum nanoparticles (PtNPs). The effect of the SnO₂–CNT support on the electrocatalytic activity of the PtNPs for the oxygen reduction reaction (ORR) in 0.1 M HClO₄ solution was investigated. The physical characterization of the catalyst confirms the presence of Pt, Sn and C on the catalyst as well as the presence of the PtNPs on SnO₂. The synthesized catalyst possesses a specific activity of 0.15 mA cm⁻² at 0.9 V, while the commercial Pt/C catalyst showed a specific activity of 0.05 mA cm⁻². Accelerated durability testing (ADT) was performed on both catalysts, with the synthesized PtNP/SnO₂–CNT catalyst retaining over 50% of its initial electrochemically active surface area (ECSA). Thus, the results obtained in this study confirm the positive influence of SnO₂-decorated CNTs on the overall electrocatalytic activity of PtNPs and their stability toward the ORR. Full article

Different morphologies of cobalt oxide (Co₃O₄) electrodes were prepared through the electrochemical deposition technique with various electrodeposition times from 10 min to 50 min. Platinum (Pt) nanoparticles were deposited on the Co₃O₄ electrodes through sputter coating. The crystallographic, microstructural, surface functional, textural–structural, and electric properties of the Co₃O₄ electrodes were investigated. X-ray diffraction analysis identified a pure cubic Co₃O₄ crystal structure in the samples. In the electrodeposition process, the microstructure of the electrodes varied from hierarchical 3D flower-like to 2D hexagonal porous nanoplates due to an increase in oxygen vacancies. The carrier densities of all samples were between 5.77 × 10¹⁴ cm⁻³ and 8.77 × 10¹⁴ cm⁻³. The flat band potentials of all samples were between −5.91 V and −6.21 V vs. an absolute electron potential, and the potential values for electrodes became more positive as the oxygen vacancy concentration in the film structure increased. The 2D hexagonal porous nanoplate Pt/Co₃O₄ electrodes offered the highest oxygen vacancies and thus the maximum current density of 102.66 mA/cm², with an external potential set at 1.5 V vs. an Ag/AgCl reference electrode. Full article

This study introduces nitrogen- and silicon-containing carbon quantum dots (N,Si-CQDs), synthesized hydrothermally from the sustainable bioresource stinging nettle (Urtica dioica L.), as chemically active supports for Pt, Pd, and Pt₃Pd₁ electrocatalysts. The N,Si-CQDs were characterized by a high concentration of N/O surface functionalities and the presence of biogenic Si. A significant finding is that, with this support, biogenic Si acts as a nucleation template: Pd forms in situ as orthorhombic Pd₉Si₂ nanorods alongside spherical particles, whereas Pt predominantly develops as cubic/quasi-cubic crystals. This templating process promotes faceted (cubic) Pt₃Pd₁ alloy nanoparticles with robust interfacial contact with the support and a log-normal size distribution (14.2 ± 4.3 nm) on N,Si-CQDs (4.7 ± 1.4 nm). This configuration enhanced the electrochemically active surface area to 181 m² gPt⁻¹, significantly exceeding those of commercial Pt₁Pd₁/XC-72 (27.7 m² gPt⁻¹) and monometallic Pt/N,Si-CQDs (14.3 m² gPt⁻¹). Consequently, the catalyst demonstrated superior methanol oxidation performance, evidenced by a low onset potential (0.17 V), approximately 10-fold higher mass activity compared to Pt₁Pd₁/XC-72, and 53% activity retention after a 16 h accelerated durability test. The enhanced performance is attributed to the strong nanoparticle anchoring by N,Si-CQDs, the bifunctional/ligand effects of the Pt–Pd alloy that improve CO tolerance, and the templating role of biogenic Si. Full article

Current Pt-based methane combustion catalysts require high noble metal loadings (≥1 wt%) and exhibit insufficient low-temperature activity. To address this, we developed a 0.5 wt% Pt catalyst supported by sulfate-modified Fe-Ce-TiO₂ (denoted 0.5Pt/CFT-TS) via sol–gel synthesis using titanium oxysulfate (TiOSO₄) precursor. Control catalysts prepared with TiCl₄, titanium butoxide, or commercial TiO₂ showed inferior performance. Structural characterization revealed that the TiOSO₄ derived carrier possesses a mesoporous framework (156.2 m²/g surface area, 8.1 nm pore size) with residual SO₄²⁻ inducing strong Brønsted acidity (1.23 mmol/g NH₃ adsorption) and elevated Ce³⁺ concentration (49.45%). These properties synergistically enhanced oxygen vacancy density (51.16% O_α fraction) and stabilized sub-nm Pt nanoparticles. The resulting Pt⁰-Fe³⁺/Ce⁴⁺-Oᵥ interface facilitated dynamic redox cycling (Fe³⁺ + Ce⁴⁺ + 0.5O²⁻ ⇌ Fe²⁺ + Ce³⁺ + 0.5Oᵥ + 0.25O₂), lowering oxygen vacancy regeneration barriers (H₂-TPR peak reduced by 45 °C) and decreasing methane activation energy to 46.77 kJ/mol. This catalyst achieved T₉₀ = 163 °C and complete conversion at 450 °C under industrial conditions (1% CH₄/4% O₂, GHSV = 30,000 h⁻¹), establishing a novel design strategy for low-Pt combustion catalysts. Full article

The development of effective catalysts for the oxygen reduction reaction (ORR) is crucial for improving the performance of fuel cells. Efficient carbon-supported Pt-Co nanocatalysts were successfully prepared by a generic two-step method: (i) electroless deposition of a Co-P coating on Vulcan XC72R carbon powder and (ii) subsequent spontaneous partial galvanic replacement of Co by Pt, upon immersion of the Co/C precursor in a chloroplatinate solution. The prepared Pt-Co particles (of a core-shell structure) are dispersed on a Vulcan XC-72 support, forming agglomerates made of nanoparticles smaller than 10 nm. The composition and surface morphology of the samples were characterized by scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM/EDS) as well as transmission electron microscopy (TEM). The crystal structures of the Co-P/C precursor and Pt-Co/C catalyst were investigated by X-ray diffraction (XRD). XPS analysis was performed to study the chemical state of the surface layers of the precursor and catalyst. The electrochemical behavior of the Pt-Co/C composites was evaluated by cyclic voltammetry (CV). Linear sweep voltammetry (LSV) experiments were used to assess the catalytic activity towards the ORR and compared with that of a commercial Pt/C catalyst. The Pt-Co/C catalysts exhibit mass-specific and surface-specific activities (of j_m = 133 mA mg⁻¹ and j_esa = 0.661 mA cm⁻², respectively) at a typical overpotential value of 380 mV (+0.85 V vs. RHE); these are superior to those of similar electrodes made of a commercial Pt/C catalyst (j_m = 50.6 mA mg⁻¹; j_esa = 0.165 mA cm⁻²). The beneficial effect of even small (<1% wt.%) quantities of Co in the catalyst on Pt ORR activity may be attributed to an optimum catalyst composition and particle size resulting from the proposed preparation method. Full article