Search Results (64)

Slow reaction kinetics of the hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) under alkaline conditions limits the performance of anion exchange membrane fuel cells and water electrolysers (AEMFC and AEMWE). Consequently, high loadings of PGM metal-based compounds such as Pd-CeO₂ and PtRu are required to obtain competitive performance. The amount of precious metals present can be reduced by exploiting interaction with an active support material that tunes both hydrogen desorption and hydroxyl adsorption, processes that are key descriptors of HOR activity. In this work, NiWO_3−xC is prepared, composed of oxygen-deficient tungsten oxide (WO_3−x) doped with Ni nanoparticles and mixed with conductive carbon (50:50 wt%). This material is decorated with Pd nanoparticles (6.6 wt% Pd loading). Structural analysis (XRD, XPS, and HR-TEM/STEM) confirm a hybrid morphology of Pd nanoparticles deposited on both the Ni and W portions of the support. The HOR and HER activity was studied using electrochemical tests and compared to the performance of both a Pd/C standard with equivalent Pd loading (6.9 wt%) and the NiWO_3−xC support. The Pd-normalized exchange current densities for the HOR (I⁰) are 18.7 A g_Pd⁻¹ for Pd/NiWO_3−xC and 3.21 A g⁻¹ for Pd/C. The enhanced HOR activity of Pd/NiWO_3−xC translates to high power densities in AEM fuel cell tests with this catalyst applied to the anode electrode (up to 0.9 W cm⁻²). Full article

Catalysis has entered everyday life through a range of technological processes that rely on different catalytic systems. The increasing demand for such systems requires rationalization of the use of their expensive components, such as noble-metal catalysts. As such, a catalyst with low noble-metal concentration, in which each one of the noble atoms is active, would reach the lowest price possible. Nevertheless, no clear reactivity descriptors have been outlined for this type of low-coordinated supported atom. Using DFT calculations, we consider three diverse systems as models of single-atom catalysts. We investigate monomers and bimetallic dimers of Ru, Rh, Pd, Ir, and Pt on MgO(001), Cu adatom on thin Mo(001)-supported films (NaF, MgO, and ScN), and single Pt adatoms on oxidized graphene surfaces. The reactivity of these metal atoms was probed by CO. In each case, we see the interaction through the donation–backdonation mechanism. In some cases, CO adsorption energies can be linked to the position of the d-band center and the adatom’s charge. A higher-lying d-band center and less-charged, supported single atoms bind CO more weakly. Also, in some cases, metal atoms that are less strongly bound to the substrate bind CO more strongly. The results suggest that the identification of common activity descriptor(s) for single metal atoms on foreign supports is a difficult task with no unique solution. However, it is also suggested that the stability of adatoms and strong anchoring to the support are prerequisites for the application of descriptor-based search to novel single-atom catalysts. Full article

Developing cost-effective and durable electrocatalysts is essential for advancing anion exchange membrane fuel cells (AEMFCs). This work evaluates Pd-based catalysts supported on β-MnO₂, Vulcan carbon (C), and their physical blend (Pd/MnO₂:Pd/C) as bifunctional electrodes for the oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR). The catalysts were synthesized via chemical reduction and characterized by TGA, ICP-OES, TEM, BET, and XRD. Rotating disk electrode studies revealed that the hybrid exhibited superior activity and kinetics, with lower Tafel slopes and higher exchange current densities compared to the individual supports. In AEMFCs, the hybrid reached 128.0 mW cm⁻² as a cathode and 221.7 mW cm⁻² as an anode, outperforming individual components. This enhanced performance arises from the synergistic interaction between Pd nanoparticles and MnO₂, where MnO₂ modulates the catalyst’s microstructure and local reaction environment while the carbon phase ensures efficient electron transport. MnO₂, although inactive for the HOR alone, acted as a structural spacer, enhancing mass transport and stability. Durability tests confirmed that the hybrid electrocatalyst retained over 99% of its initial activity after 3000 cycles. These results highlight the hybrid Pd/MnO₂:Pd/C as a promising, bifunctional, and durable electrocatalyst for AEMFC applications. Full article

The continuous tightening of emission regulations and the escalating costs of palladium (Pd) and rhodium (Rh) have renewed interest in platinum (Pt)-based three-way catalysts (TWCs) as cost-effective alternatives for gasoline aftertreatment. However, despite extensive studies on Pt/CeO₂ and Pt/Ba-based formulations, the cooperative roles of Ba and Ce and, in particular, the fundamental influence of the Ba/Ce ratio on oxygen mobility, NO_x storage behavior, and Pt–support interactions remain poorly understood. In this work, we address this gap by systematically tuning the Ba/Ce molar ratio in a series of Pt–Ba–Ce/Al₂O₃ catalysts prepared from Ba(CH₃COO)₂ and CeO₂ precursors, and evaluating their structure–function relationships in both fresh and hydrothermally aged states. Through comprehensive characterization (N₂ physisorption, XRD, XPS, H₂-TPR, NO_x-TPD, SEM, CO pulse adsorption, and dynamic light-off testing), we establish previously unrecognized correlations between Ba/Ce ratio–dependent structural evolution and TWC performance. The results reveal that the Ba/Ce ratio exerts a decisive control over catalyst textural properties, Pt dispersion, and interfacial Pt–CeO₂ oxygen species. Low Ba/Ce ratios uniquely promote Pt–Ce interfacial oxygen and O₂ spillover—providing a new mechanistic basis for enhanced low-temperature oxidation and reduction reactions—while higher Ba loading selectively drives BaCO₃ formation and boosts NO_x storage capacity. A clear volcano-type dependence of NO_x storage on the Ba/Ce ratio is demonstrated for the first time. Hydrothermal aging at 850 °C induces PtO_x decomposition, BaCO₃–Al₂O₃ solid-state reactions forming inactive BaAl₂O₄, and Pt sintering, collectively suppressing Pt–Ce interactions and reducing TWC activity. Importantly, an optimized Ba/Ce ratio is shown to mitigate these degradation pathways, offering a new design principle for thermally durable Pt-based TWCs. Overall, this study provides new mechanistic insight into Ba–Ce cooperative effects, establishes the Ba/Ce ratio as a critical and previously overlooked parameter governing Pt–support interactions and NO_x storage, and presents a rational strategy for designing cost-effective, hydrothermally robust Pt-based alternatives to Pd/Rh commercial TWCs. Full article

The photocatalytic reduction of CO₂ in aqueous media offers a sustainable route for solar-to-fuel conversion, yet remains challenged by CO₂’s thermodynamic stability and kinetic inertness, low solubility, and competitive hydrogen evolution. Here, we investigate the interplay between ionic liquids (ILs), photocatalyst supports, and additive composition in directing product selectivity among CO, CH₄, and H₂. Using imidazolium acetate as a benchmark, we demonstrate that ILs not only pre-activate CO₂ but can also undergo decomposition pathways under illumination, notably Kolbe-type reactions leading to methane formation from acetate rather than from CO₂. Comparative studies of Pd-decorated TiO₂ and g-C₃N₄ nanosheets reveal distinct behaviors driven by their interfacial interactions with the imidazolim-based ionic liquid: weak interaction with TiO₂ strongly promotes hydrogen evolution, whereas strong coupling with g-C₃N₄ synergizes with C₁C₄ImOAc to trigger acetate-derived Kolbe reactivity. The systematic evaluation of alternative salts confirms the determinant role of anion basicity and medium-pH-basic anions facilitate CO₂ activation, whereas weakly basic or non-coordinating anions favor water splitting. Overall, these results clarify the dual role of ionic liquids as both CO₂ activators and sacrificial agents, and highlight design principles for improving product selectivity and efficiency in aqueous CO₂ photoreduction systems. Full article

The development of heterogeneous nanocatalysts with high performance is essential for improving hydrogen production through formic acid dehydrogenation, but challenging. Herein, highly dispersed Pd nanoparticles (NPs) were successfully immobilized on porous nitrogen-doped carbon cages (PNCCs) derived from zeolitic imidazole frameworks. By virtue of the synergistic effect, the optimized Pd/PNCC nanocatalytic systems exhibit an excellent catalytic kinetics toward catalyzing FA dehydrogenation with a turnover frequency (TOF) value as high as 3174 h⁻¹ at 323 K, which is 59 times relative to that of Pd nanoparticles. The exceptional activity may be ascribed to the PNCC solid support may induce a strong electronic metal–support interaction to optimize the electron configuration of Pd active sites and accelerate the kinetics of O-H bond cleavage, resulting in an enhanced catalytic performance toward FA dehydrogenation. This work will supply a novel strategy for the development of supported nanocatalysts with high performance for tremendous catalytic applications in the future. Full article

Motor impairments significantly affect individuals’ ability to perform activities of daily living, reducing autonomy and quality of life. In response to this, robot-assisted rehabilitation has emerged as an effective and practical solution, enabling controlled limb movements and supporting functional recovery. This study presents the development of an upper-limb exoskeleton designed to assist rehabilitation by integrating neurophysiological signal processing and real-time control strategies. The system incorporates a proportional–derivative (PD) controller to execute cyclic flexion and extension movements based on a sinusoidal reference signal, providing repeatability and precision in motion. The exoskeleton integrates a brain–computer interface (BCI) that utilizes electroencephalographic signals for therapy selection and engagement enabling user-driven interaction. The EEG data extraction was possible by using the UltraCortex Mark IV headset, with electrodes positioned according to the international 10–20 system, targeting alpha-band activity in channels O1, O2, P3, P4, Fp1, and Fp2. These channels correspond to occipital (O1, O2), parietal (P3, P4), and frontal pole (Fp1, Fp2) regions, associated with visual processing, sensorimotor integration, and attention-related activity, respectively. This approach enables a more adaptive and personalized rehabilitation experience by allowing the user to influence therapy mode selection through real-time feedback. Experimental evaluation across five subjects showed an overall mean accuracy of 86.25% in alpha wave detection for EEG-based therapy selection. The PD control strategy achieved smooth trajectory tracking with a mean angular error of approximately 1.70°, confirming both the reliability of intention detection and the mechanical precision of the exoskeleton. Also, our core contributions in this research are compared with similar studies inspired by the rehabilitation needs of stroke patients. In this research, the proposed system demonstrates the potential of integrating robotic systems, control theory, and EEG data processing to improve rehabilitation outcomes for individuals with upper-limb motor deficits, particularly post-stroke patients. By focusing the exoskeleton on a single degree of freedom and employing low-cost manufacturing through 3D printing, the system remains affordable across a wide range of economic contexts. This design choice enables deployment in diverse clinical settings, both public and private. Full article

A density functional theory (DFT) investigation was conducted to study the O₂ and CO₂ adsorption on very small Pd_3−nNi_n (n = 0–2) clusters supported on N-doped graphene quantum dots (N-GQDs). The study was carried out in two stages. First, the interaction between Pd_3−nNi_n (n = 0–2) clusters and N-GQDs was analyzed. Subsequently, the adsorption behavior of O₂ and CO₂ molecules on the supported clusters was examined. The calculated interaction energies (E_int) of Pd_3−nNi_n (n = 0–2) clusters on N-GQDs were found to be higher than those on pristine graphene, indicating enhanced cluster stability on N-GQDs. Furthermore, the adsorption energies (E_ads) of the O₂ molecule on the Pd₃ and Pd₂Ni clusters deposited on N-GQDs were similar. Meanwhile, the PdNi₂ cluster deposited on N-GQDs exhibited the highest E_ads (−1.740). The E_ads of CO₂ on Pd_3−nNi_n (n = 0–2) clusters embedded in N-GQDs were observed to be close to or exceed 1 eV. Upon adsorption of O₂ and CO₂ on the Pd_3−nNi_n (n = 0–2) clusters supported on N-GQDs, an elongation of the O–O and C–O bond lengths was observed, respectively. This structural change may facilitate the dissociation of these molecules on the supported clusters. Full article

Supported Pd-based catalysts have been widely applied in the hydrogenation of specific functional groups. Recent trends have focused on employing Pd-based heterogeneous catalysts supported on inorganic nanotubes, wherein inner surface functionalization modulates both palladium nanoparticle (Pd-NP) dispersion and the interaction between reactants and the catalyst surface, thereby influencing catalytic properties. This study aims to develop a catalytic system using amine-lumened halloysite nanotubes immobilizing Pd-NPs (Pd/HNTA) as catalysts for hydrogenation reactions. The formation of Pd-NPs within the organo-functionalized lumen—modified by 3-aminopropyltrimethoxysilane—is confirmed by transmission electron microscopy (TEM) imaging, which reveals a particle size of 2.2 ± 0.4 nm. For comparison, Pd-NPs supported on pristine halloysite (Pd/HNTP) were used as control catalysts, displaying a metal particle size of 2.8 ± 0.8 nm and thereby demonstrating the effect of organic functionalization on the halloysite nanotubes. Both catalysts were employed in the hydrogenation of furfural (FUR) and nitrobenzene (NB) as model reactions. Pd/HNTA demonstrated superior catalytic performance for both substrates, with TOF values of 880 h⁻¹ for FUR and 946 h⁻¹ for NB, and selectivities exceeding 98% for tetrahydrofurfuryl alcohol (THFOH) and aniline (AN), respectively. However, recyclability studies displayed that Pd/HNTA was deactivated at the 10 catalytic cycles during the hydrogenation of FUR, whereas, in the hydrogenation of NB, 5 catalytic cycles were achieved with maximum conversion and selectivity at 360 min. These results revealed that the liquid-phase environment plays a pivotal role in catalyst stability. In the hydrogenation of NB, the coproduction of H₂O adversely affects the interaction between the Pd particles and the inner amine-modified surface, increasing the deactivation of the catalyst with reuse. Thus, the Pd/HNTA catalyst holds significant promise for the development of noble-metal-based catalysts and their application in the transformation of other reducible organic functional groups via hydrogenation reaction. Full article

The present study aims to investigate a Pd catalyst on a complex multi-oxide medium-entropy support interlayer La₂O₃-CeO₂-ZrO₂-Al₂O₃ and its possible use as catalysts for methane abatement applications. The low-temperature N₂-adsorption, XRD, TEM, XPS, TPD, and TPR techniques were used to characterize the catalyst. The palladium deposition on the supports leads to the formation of PdO. After the catalytic tests, the metal-Pd phase was observed. The complete oxidation of methane on Pd/La-Ce-Zr-Al catalyst takes place at temperatures above 250 °C, and in the presence of water vapor, the reaction temperature increases to about 70 °C. The careful choice of constituent oxides provides a balance between structural stability and flexibility. The alumina and lanthanum oxide ensure the high specific surface area, while the simultaneous presence of zirconia and ceria leads to the formation of a mixed-oxide phase able to interact with palladium ions by incorporating and de-incorporating them at different conditions. The mechanism of Mars–van Kerevelen was considered as the most probable for the reaction of complete methane oxidation. The possibility of the practical application of Pd-modified La-Ce-Zr-Al catalyst is evaluated. The use of a mix of multiple rare and abundant oxides makes the proposed catalyst a cost-effective alternative. Full article

1,2-Propanediol, with its highly functionalized molecular structure and abundant availability, serves as a viable feedstock for high-value chemicals. The oxidation of 1,2-propanediol can potentially yield lactic acid, an important commodity chemical. Herein, we report the catalytic oxidation of 1,2-propanediol in the presence of NaOH, using Pd nanoparticles (NPs) supported on various functionalized multi-walled carbon nanotubes (MWCNTs). Both single-factor experiments and the response surface methodology were employed to investigate the optimal operating parameters. It was found that nitrogen doping promotes strong metal–support interactions between the active components and the support. Under optimal reaction conditions (123 °C, 1.25 MPa O₂ pressure, 4 h, and a NaOH/1,2-PDO molar ratio of 4.0), a high lactic acid yield of 68.3% was achieved using nitrogen-doped MWCNT-supported Pd nanoparticles as the catalyst. The selectivity for lactic acid decreased with increasing reaction time, temperature, NaOH/1,2-PDO molar ratio, and O₂ pressure, while the conversion rate increased correspondingly. After five cycles, the conversion of 1,2-PDO slightly decreased to 76.2%, while the LA selectivity remained high at 84.9%. Additionally, the reaction pathway was further investigated, confirming the formation mechanism of lactic acid. Full article

The proposed paper describes a simple and environmentally friendly method for the synthesis of three-component polymer–inorganic composites, which includes the modification of zinc oxide or montmorillonite (MMT) with chitosan (CS), followed by the immobilization of palladium on the resulting two-component composites. The structures and properties of the obtained composites were characterized by physicochemical methods (IRS, TEM, XPS, SEM, EDX, XRD, BET). Pd–CS species covered the surface of inorganic materials through two different mechanisms. The interaction of chitosan polyelectrolyte with zinc oxide led to the deprotonation of its amino groups and deposition on the surface of ZnO. The immobilization of Pd on CS/ZnO occurred by the hydrolysis of [PdCl₄]²⁻, followed by forming PdO particles by interacting with amino groups of chitosan. In the case of CS/MMT, protonated amino groups of CS interacted with negative sites of MMT, forming a positively charged CS/MMT composite. Furthermore, [PdCl₄]²⁻ interacted with the –NH³⁺ sites of CS/MMT through electrostatic force. According to TEM studies of 1%Pd–CS/ZnO, the presence of Pd nanoclusters composed of smaller Pd nanoparticles of 3–4 nm in size were observed on different sites of CS/ZnO. For 1%Pd–CS/MMT, Pd nanoparticles with sizes of 2 nm were evenly distributed on the support surface. The prepared three-component CS–inorganic composites were tested through the hydrogenation of 2-propen-1-ol and acetylene compounds (phenylacetylene, 2-hexyn-1-ol) under mild conditions (T—40 °C, P_H2—1 atm). It was shown that the efficiency of 1%Pd–CS/MMT is higher than that of 1%Pd–CS/ZnO, which can be explained by the formation of smaller Pd particles that are evenly distributed on the support surface. The mechanism of 2-hexyn-1-ol hydrogenation over an optimal 1%Pd–CS/MMT catalyst was proposed. Full article

The traditional catalytic oxidation of carbon monoxide (CO) using metal oxide catalysts often requires either high temperatures (thermocatalysis) or ultraviolet light (UV) excitation (photocatalysis), limiting practical applications under ambient conditions. Our research aimed to develop a catalytic system capable of oxidizing CO to CO₂ at room temperature and in the dark. Using the Strong Metal–Support Interaction (SMSI) methodology, several titanium oxide (TiO₂)-complexed metals were prepared (Ag, Au, Pd, and Pt). The highest catalytic efficiency of CO oxidation at room temperature was demonstrated for the TiO₂-Pt complex. Therefore, this complex was further examined structurally and functionally. Two modes of operation were addressed. The first involved applying the catalytic system to remove CO from an individual’s environment (environmental system), while the second involved the installation of the catalysis chamber as a part of a personal protection unit (e.g., a mask). The catalytic activity exhibited a significant reduction in CO levels in both the environmental and personal protection scenarios. The practical application of the system was demonstrated through efficient CO oxidation in air emitted from a controlled fire experiment conducted in collaboration with the Israel Fire and Rescue Authority. Full article

As a widely used support, TiO₂ has often been combined with Pd to form highly sensitive gas-chromic materials. Herein, we prepared a series of Pd/TiO₂ catalysts with different Pd content (from 0.1 to 5 wt.%) by the impregnation method for their utilization in fast room-temperature CO detection. The detection was simply based on visible color change when the Pd/TiO₂ was exposed to CO. The sample with 1 wt.% Pd/TiO₂ presented an excellent CO gasochromic character, associated with a maximum chromatic aberration value of 90 before and after CO exposure. Systematic catalyst characterizations of XPS, FT-IR, CO-TPD, and N₂ adsorption–desorption and density functional theory calculations for the CO adsorption and charge transfer over the Pd and PdO surfaces were further carried out. It was found that the interaction between CO and the Pd surface was strong, associated with a large adsorption energy of −1.99 eV and charge transfer of 0.196 e. The color change was caused by a reduction in Pd²⁺ to metallic Pd⁰ over the Pd/TiO₂ surface after CO exposure. Full article

CeO₂-ZrO₂-La₂O₃ supported Pt-Pd bimetallic three-way catalysts (0.6Pt-0.4Pd/CZL) were synthesized through the conventional impregnation method and then subjected to severe thermal aging. Reactivating treatments under different temperatures were then applied to the aged catalysts above. Three-way catalytic performance evaluations and dynamic operation window tests along with detailed physio-chemical characterizations were carried out to explore possible structure–activity evolutions during the reactivating process. Results show that the reactivating process conducted at proper temperatures (500~550 °C) could effectively restore the TWC catalytic performance and widen the operation window width. The suitable reactivating temperature ranges are mainly determined by the decomposing temperature of PMO_x species, the thermal stability of PM-O-Ce species, and the encapsulation temperature of precious metals by CZL support. Reactivating under appropriate temperature helps to restore the interaction between Pt and CZL support to a certain extent and to re-expose part of the encapsulated precious metals. Therefore, the dynamic oxygen storage/release capacity, redox ability, as well as thermal stability of PtOx species, can be improved, thus benefiting the TWC catalytic performances. However, the excessively high reactivating temperature would cause further embedment of Pd by CZL support, thus leading to a further decrease in both dynamic oxygen storage/release capacity and the TWC catalytic performance after reactivating treatment. Full article