Search Results (43)

The importance and challenges of ethylene detection based on combustion-type low-cost commercial sensors for agricultural and industrial applications are well-established. This work summarizes the significant progress in ethylene detection based on an innovative Gas Metal Oxide Semiconductor (GMOS) sensor and a new catalytic composition of metallic nanoparticles. The paper presents a study on ethylene and ethanol sensing using a miniature catalytic sensor fabricated by Complementary Metal Oxide Semiconductor–Silicon-on-Insulator–Micro-Electro-Mechanical System (CMOS-SOI-MEMS) technology. The GMOS performance with bimetallic palladium–platinum (Pd-Pt) and monometallic palladium (Pd) and platinum (Pt) catalysts is compared. The synergetic effect of the Pd-Pt catalyst is observed, which is expressed in the shift of combustion reaction ignition to lower catalyst temperatures as well as increased sensitivity compared to monometallic components. The optimal catalysts and their temperature regimes for low and high ethylene concentrations are chosen, resulting in lower power consumption by the sensor. Full article

The electrochemical CO₂ reduction reaction (eCO₂RR), driven by renewable energy, represents a promising strategy for mitigating atmospheric CO₂ levels while generating valuable fuels and chemicals. Its practical implementation hinges on the development of highly efficient electrocatalysts. In this study, a novel dual-metal atomic catalyst (DAC), composed of niobium and palladium single atoms anchored on a ferroelectric α-In₂Se₃ monolayer (Nb-Pd@In₂Se₃), is proposed based on density functional theory (DFT) calculations. The investigation encompassed analyses of structural and electronic characteristics, CO₂ adsorption configurations, transition-state energetics, and Gibbs free energy changes during the eCO₂RR process, elucidating a synergistic catalytic mechanism. The Nb-Pd@In₂Se₃ DAC system demonstrates enhanced CO₂ activation compared to single-atom counterparts, which is attributed to the complementary roles of Nb and Pd sites. Specifically, Nb atoms primarily drive carbon reduction, while neighboring Pd atoms facilitate oxygen species removal through proton-coupled electron transfer. This dual-site interaction lowers the overall reaction barrier, promoting efficient CO₂ conversion. Notably, the polarization switching of the In₂Se₃ substrate dynamically modulates energy barriers and reaction pathways, thereby influencing product selectivity. Our work provides theoretical guidance for designing ferroelectric-supported DACs for the eCO₂RR. Full article

Declining natural resources make the recovery of metals from waste solutions a promising alternative. Moreover, processing waste into a finished product has its economic justification and benefits. Thus, the aim of this research was developing a Waste for Product strategy, indicating the possibility of processing solutions with a low content of platinum-group metals for catalyst synthesis. The results obtained confirmed that diluted synthetic waste solutions containing trace amount of valuable metal ions (Pd, Pt) can be used for the process of catalyst synthesis. Catalysts produced in the form of palladium and platinum nanoparticles were successfully deposited on a Ni foam due to the galvanic displacement mechanism. Synthesized catalysts were characterized using UV-Vis spectrophotometry, SEM/EDS, and XRD techniques. Electro- and catalytic properties were tested for hydrogen/oxygen evolution reactions and methyl orange degradation, respectively. The results obtained from electrocatalytic tests indicated that the modification of the nickel foam surface by waste solutions consisting of noble metals ions as Pd and Pt can significantly increase the activity in hydrogen and oxygen evolution reactions in comparison to non-treated samples. Catalytic tests performed for the process of methyl orange degradation shorten the time of the process from several hours to 15 min. The most favorable results were obtained for the catalysts in the following order Pd1.0Pt0@Ni > Pd0Pt1.0@Ni > Pd0.5Pt0.5@Ni > Ni foam > no catalyst, indicating the best catalytic performance for catalyst containing pure palladium nanoparticles deposited on the nickel surface. Full article

This work investigates the relationship between the mean diameter of palladium (Pd) nanoparticles and their surface energy, specifically in the context of alkaline ethanol electro-oxidation for fuel cell applications. Employing a recent generalization of the classical Laviron equation, we derive crucial parameters such as surface energy (σ), adsorption–desorption equilibrium constant (K_eq), and electron transfer coefficient (α) from linear voltammograms obtained from Pd-based nanoparticles supported on Vulcan carbon. Synthesized using two distinct methods, these nanocatalysts exhibit mean diameters ranging from 10 to 41 nm. Our results indicate that the surface energy of the Pd/C nanocatalysts spans σ ~ 0.5–2.5 J/m², showing a linear correlation with particle size while remaining independent of ethanol bulk concentration. The adsorption–desorption equilibrium constant varies with nanoparticle size (~0.1–6 × 10⁻⁶ mol⁻¹) but is unaffected by ethanol concentration. Significantly, we identify an optimal mean diameter of approximately 28 nm for enhanced electrocatalytic activity, revealing critical size-dependent effects on catalytic efficiency. This research contributes to the ongoing development of cost-effective and durable fuel cell components by optimizing nanoparticle characteristics, thus advancing the performance of Pd-based catalysts in practical applications. Our findings are essential for the continued evolution of nanomaterials in fuel cell technologies, particularly in improving efficiency and reducing reliance on critical raw materials. Full article

For the first time, carbon-particle-supported palladium-based cobalt composite electrocatalysts (abbreviated as Pd_xCo_y/CPs) were prepared using a calcination–hydrothermal process–hydrothermal process (denoted as CHH). The catalysts of Pd_xCo_y/CPs prepared using CoC₂O₄·2H₂O, (CH₃COO)₂Co·4H₂O, and metallic cobalt were named catalyst c₁, c₂, and c₃, respectively. For comparison, the catalyst prepared in the absence of a Co source (denoted as Pd/CP) was identified as catalyst c₀. All fabricated catalysts were thoroughly characterized by XRD, EDS, XPS, and FTIR, indicating that PdO, metallic Pd, carbon particles, and a very small amount of cobalt oxide were the main components of all produced catalysts. As demonstrated by the traditional electrochemical techniques of CV and CA, the electrocatalytic performances of Pd_xCo_y/CP towards the ethanol oxidation reaction (EOR) were significantly superior to that of Pd/CP. In particular, c₁ showed an unexpected electrocatalytic activity for EOR; for instance, in the CV test, the peak f current density of EOR on catalyst c₁ was 129.3 mA cm⁻², being about 10.7 times larger than that measured on Pd/CP, and in the CA test, the polarized current density of EOR recorded for c₁ after 7200 s was still about 2.1 mA cm⁻², which was larger than that recorded for Pd/CP (0.6 mA cm⁻²). In the catalyst preparation process, except for the elements of C, O, Co, and Pd, no other elements were involved, which was thought to be the main contribution of this preliminary work, being very meaningful to the further exploration of Pd-based composite EOR catalysts. Full article

Graphene oxide (GO) has recently gained significant attention in electrocatalysis as a promising electrode material owing to its unique physiochemical properties such as enhanced electron transfers due to a conjugated π-electron system, high surface area, and stable support for loading electroactive species, including metal nanoparticles. However, only a few studies have been directed toward the structural characteristics of GO, elaborating on the roles of oxygen-containing functional groups, the presence of defects, interlayer spacing between the layered structure, and nonuniformity in the carbon skeleton along with their influence on electrochemical performance. In this work, we aim to understand these properties in various GO materials derived from different graphitic sources. Both physiochemical and electrochemical characterization were employed to correlate the above-mentioned features and explore the effect of the location of the palladium nanoparticles (Pd NPs) on various GO supports for the hydrogen evolution reaction (HER). The interaction of the functional groups has a crucial role in the Pd dispersion and its electrochemical performance. Among the different GO samples, Pd supported on GO derived from graphene nanoplate (GNP), Pd/GO-GNP, exhibits superior HER performance; this could be attributed to the optimal balance among particle size, defect density, less in-plane functionalities, and higher electrochemical surface area. This study, thus, helps to identify the optimal conditions that lead to the best performance of Pd-loaded GO, contributing to the design of more effective HER electrocatalysts. Full article

Bimetallic platinum-containing catalysts are deemed promising for electrolyzers and proton-exchange membrane fuel cells (PEMFCs). A significant number of laboratory studies and commercial offers are related to PtNi/C and PtCo/C electrocatalysts. The behavior of PtPd/C catalysts has been studied much less, although palladium itself is the metal closest to platinum in its properties. Using a series of characterization methods, this paper presents a comparative study of structural characteristics of the commercial PtPd/C catalysts containing 38% wt. of precious metals and the well-known HiSpec4000 Pt/C catalyst. The electrochemical behavior of the catalysts was studied both in a three-electrode electrochemical cell and in the membrane electrode assemblies (MEAs) of hydrogen–air PEMFCs. Both PtPd/C samples demonstrated higher values of the electrochemically active surface area, as well as greater specific and mass activity in the oxygen reduction reaction in comparison with conventional Pt/C, while not being inferior to the latter in durability. The MEA based on the best of the PtPd/C catalysts also exhibited higher performance in single tests and long-term durability testing. The results of this study conducted indicate the prospects of using bimetallic PtPd/C materials for cathode catalysts in PEMFCs. Full article

The presented research is the seed of a vision for the development of a waste-for-product strategy. Following this concept, various synthetic solutions containing low concentrations of platinum group metals were used to model their recovery and to produce catalysts. This is also the first report that shows the method for synthesis of a pyramid-like structure deposited on activated carbon composed of Pd and Pt. This unique structure was obtained from a mixture of highly diluted aqueous solutions containing both metals and chloride ions. The presence of functional groups on the carbon surface and experimental conditions allowed for: the adsorption of metal complexes, their reduction to metal atoms and enabled further hierarchical growth of the metal layer on the carbon surface. During experiments, spherical palladium and platinum nanoparticles were obtained. The addition of chloride ions to the solution promoted the hierarchical growth and formation of palladium nanopyramids, which were enriched with platinum nanoparticles. The obtained materials were characterized using UV–Vis, Raman, IR spectroscopy, TGA, SEM/EDS, and XRD techniques. Moreover, Pd@ROY, Pt@ROY, and Pd-Pt@ROY were tested as possible electrocatalysts for hydrogen evolution reactions. Full article

The sluggish kinetics of oxygen reduction reactions (ORRs) require considerable Pd in the cathode, hindering the widespread of alkaline fuel cells (AFCs). By alloying Pd with transition metals, the oxygen reduction reaction’s catalytic properties can be substantially enhanced. Nevertheless, the utilization of Pd-transition metal alloys in fuel cells is significantly constrained by their inadequate long-term durability due to the propensity of transition metals to leach. In this study, a nonmetallic doping strategy was devised and implemented to produce a Pd catalyst doped with P that exhibited exceptional durability towards ORRs. Pd₃P_0.95 with an average size of 6.41 nm was synthesized by the heat-treatment phosphorization of Pd nanoparticles followed by acid etching. After P-doping, the size of the Pd nanoparticles increased from 5.37 nm to 6.41 nm, and the initial mass activity (MA) of Pd₃P_0.95/NC reached 0.175 A mg_Pd⁻¹ at 0.9 V, slightly lower than that of Pd/C. However, after 40,000 cycles of accelerated durability testing, instead of decreasing, the MA of Pd₃P_0.95/NC increased by 6.3% while the MA loss of Pd/C was 38.3%. The durability was primarily ascribed to the electronic structure effect and the aggregation resistance of the Pd nanoparticles. This research also establishes a foundation for the development of Pd-based ORR catalysts and offers a direction for the future advancement of catalysts designed for practical applications in AFCs. Full article

The aim of this work is to establish the Oxygen Reduction Reaction (ORR) activity of self-standing electrospun carbon fiber catalysts obtained from different metallic salt/lignin solutions. Through a single-step electrospinning technique, freestanding carbon fiber (CF) electrodes embedded with various metal nanoparticles (Co, Fe, Pt, and Pd), with 8–16 wt% loadings, were prepared using organosolv lignin as the initial material. These fibers were formed from a solution of lignin and ethanol, into which the metallic salt precursors were introduced, without additives or the use of toxic reagents. The resulting non-woven cloths were thermostabilized in air and then carbonized at 900 °C. The presence of metals led to varying degrees of porosity development during carbonization, improving the accessibility of the electrolyte to active sites. The obtained Pt and Pd metal-loaded carbon fibers showed high nanoparticle dispersion. The performance of the electrocatalyst for the oxygen reduction reaction was assessed in alkaline and acidic electrolytes and compared to establish which metals were the most suitable for producing carbon fibers with the highest electrocatalytic activity. In accordance with their superior dispersion and balanced pore size distribution, the carbon fibers loaded with 8 wt% palladium showed the best ORR activity, with onset potentials of 0.97 and 0.95 V in alkaline and acid media, respectively. In addition, this electrocatalyst exhibits good stability and selectivity for the four-electron energy pathway while using lower metal loadings compared to commercial catalysts. Full article

This study investigates the use of Au-doped Pd anodic electrocatalysts on ATO support for the conversion of methane to methanol. The study uses cyclic voltammetry, in situ Raman spectra, polarization curves, and FTIR analysis to determine the optimal composition of gold and palladium for enhancing the conversion process. The results demonstrate the potential for utilizing methane as a feedstock for producing sustainable energy sources. The Pd₇₅Au₂₅/ATO electrode exhibited the highest OCP value, and Pd₅₀Au₅₀/ATO had the highest methanol production value at a potential of 0.05 V. Therefore, it can be concluded that an optimal composition of gold and palladium exists to enhance the conversion of methane to methanol. The findings contribute to the development of efficient and sustainable energy sources, highlighting the importance of exploring alternative ways to produce methanol. Full article

This study determined the critical parameters for the morphological development of the electrode surface (the critical potential and the critical charge) during anodic selective dissolution of a Cu–Pd alloy with a volume concentration of 15 at.% palladium. When the critical values were exceeded, a phase transition occurred with the formation of palladium’s own phase. Chronoamperometry aided in the determination of the partial rates of copper ionization and phase transformation of palladium under overcritical selective dissolution conditions. The study determined that the formation of a new palladium phase is controlled by a surface diffusion of the ad-atom to the growing three-dimensional nucleus under instantaneous activation of the nucleation centres. We also identified the role of this process in the formation of the electrocatalytic activity of the anodically modified alloy during electro-oxidation of formic acid. This study demonstrated that HCOOH is only oxidated at a relatively high rate on the surface of the Cu₈₅Pd₁₅ alloy, which is subjected to selective dissolution under overcritical conditions. This can be explained by the fact that during selective dissolution of the alloy, a pure palladium phase is formed on its highly developed surface which has prominent catalytic activity towards the electro-oxidation of formic acid. The rate of electro-oxidation of HCOOH on the surface of the anodically modified alloy increased with the growth of the potential and the charge of selective dissolution, which can be used to obtain an electrode palladium electrocatalyst with a set level of electrocatalytic activity towards the anodic oxidation of formic acid. Full article

The main obstacle to the widespread dissemination of fuel cells is the high cost, so researchers are actively searching for ways to replace the expensive platinum catalyst with cheaper analogs. In this paper we studied the Ag- and Pd-containing carbon catalysts based on carbon nanotubes and graphene oxide. The study of the textural characteristics of the catalysts showed that the greatest specific surface area has a catalyst based on MWCNT containing 10% silver, all synthesized catalysts are mainly mesoporous, and the content of micropores is insignificant. Raman spectroscopy and SEM data indicate a significant change in the structure of the modified carriers compared to pure MWCNT and GO. An electrochemical experiment was performed and linear voltammetric diagrams were obtained and compared with the voltammetric diagrams obtained on the platinum catalyst. GO_Ag 10% and MWCNT_Ag 10% Pd 10% are closest in the values of kinetic parameters in both kinetic and diffusion regions. GO_Ag 10% has the highest initial potential E_onset = −0.145 V and MWCNT_Ag 10% Pd 10% has the highest half-wave potential E½ = −0.23 V. The studied catalysts have characteristics comparable to those presented in the literature. Full article

A continuous electrocatalytic reactor offers a promising method for producing fuels and value-added chemicals via electrocatalytic hydrogenation of biomass-derived compounds. However, such processes require a better understanding of the impact of different types of active electrodes and reaction conditions on electrocatalytic biomass conversion and product selectivity. In this work, Ni_1−xPd_x (x = 0.25, 0.20, and 0.15) alloyed nanostructures were synthesized as heterogeneous catalysts for the electrocatalytic conversion of furfural. Various analytical tools, including XRD, SEM, EDS, and TEM, were used to characterize the Ni_1−xPd_x catalysts. The alloyed catalysts, with varying Ni to Pd ratios, showed a superior electrocatalytic activity of over 65% for furfural conversion after 4.5 h of reaction. In addition, various experimental parameters on the furfural conversion reactions, including electrolyte pH, furfural (FF) concentration, reaction time, and applied potential, were investigated to tune the hydrogenated products. The results indicated that the production of 2-methylfuran as a primary product (S = 29.78% after 1 h), using Ni_0.85Pd_0.15 electrocatalyst, was attributed to the incorporation of palladium and thus the promotion of water-assisted proton transfer processes. Results obtained from this study provide evidence that alloying a common catalyst, such as Ni with small amounts of Pd metal, can significantly enhance its electrocatalytic activity and selectivity. Full article

Palladium (Pd) nanostructures are highly active non-platinum anodic electrocatalysts in alkaline direct methanol fuel cells (DMFCs), and their electrocatalytic performance relies highly on their morphology and composition. This study reports the preparation, characterizations, and electrocatalytic properties of palladium-copper alloys loaded on the carbon support. XC-72 was used as a support, and hydrazine hydrate served as a reducing agent. Pd_xCu_y/XC-72 nanoalloy catalysts were prepared in a one-step chemical reduction process with different ratios of Pd and Cu. A range of analytical techniques was used to characterize the microstructure and electronic properties of the catalysts, including transmission electron microscopy (TEM), X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), and inductively coupled plasma emission spectroscopy (ICP-OES). Benefiting from excellent electronic structure, Pd₃Cu₂/XC-72 achieves higher mass activity enhancement and improves durability for MOR. Considering the simple synthesis, excellent activity, and long-term stability, Pd_xCu_y/XC-72 anodic electrocatalysts will be highly promising in alkaline DMFCs. Full article