Search Results (243)

The biogas dry reforming reaction offers a promising route for syngas production while simultaneously mitigating greenhouse gas emissions. Membrane reactors have proven to be an excellent option for hydrogen production and separation in a single unit, where conversion and yield can be enhanced over conventional processes. In this study, a Pd/YSZ membrane integrated with a Ru/CeO₂ catalyst was evaluated for biogas reaction under varying operating conditions. The selective removal of hydrogen through the palladium membrane improved reactant conversion and suppressed side reactions such as methanation and the reverse water–gas shift. Experiments were performed at temperatures ranging from 500 to 600 °C, pressures of 1–6 bar, and a gas hourly space velocity (GHSV) of 800 h⁻¹. Maximum conversions of CH₄ (43%) and CO₂ (46.7%) were achieved at 600 °C and 2 bar, while the maximum hydrogen recovery of 78% was reached at 6 bar. The membrane reactor outperformed a conventional reactor, offering up to 10% higher CH₄ conversion and improved hydrogen production and yield. Also, a comparative analysis between Ru/CeO₂ and Ni/Al₂O₃ catalysts revealed that while the Ni-based catalyst provided higher CH₄ conversion, it also promoted methane decomposition reaction and coke formation. In contrast, the Ru/CeO₂ catalyst exhibited excellent resistance to coke formation, attributable to ceria’s redox properties and oxygen storage capacity. The combined system of Ru/CeO₂ catalyst and Pd/YSZ membrane offers an effective and sustainable approach for hydrogen-rich syngas production from biogas, with improved performance and long-term stability. 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

A carbon-supported palladium-containing polysiloxane macrocatalyst (Pd-PDMS) was developed for pharmaceutical-grade cross-coupling reactions. The catalyst demonstrates exceptional year-long stability at room temperature while maintaining full catalytic activity. Pd-PDMS efficiently promotes three pharmaceutically relevant reactions: Suzuki coupling (80% yield), copper-free Sonogashira coupling (90% yield at 55 °C), and Heck coupling (80% yield at 90 °C). The copper-free Sonogashira protocol eliminates toxic copper cocatalysts, phosphine ligands, and organic bases while operating under mild conditions. Most significantly, palladium contamination in products reaches ultra-low levels of 22 ppb (Sonogashira, Suzuki) and 167 ppb (Heck), representing a 60–450-fold improvement over European Medicines Agency requirements (10 ppm). The catalyst exhibits excellent recyclability without activity loss over multiple cycles, with simple washing protocols between uses. Scanning electron microscopy and X-ray photoelectron spectroscopy confirmed uniform Pd-PDMS coating on carbon fibers, while density functional theory calculations revealed specific coordination interactions between the palladium complex and carbon support at 3.26 Å distance. This convergence of pharmaceutical-grade metal contamination control, exceptional stability, and multi-reaction versatility establishes a significant advancement for sustainable cross-coupling catalysis in pharmaceutical applications. Full article

Catalytic upgrading of bioethanol via a C–C coupling reaction is a sustainable method of producing 1-butanol, a high-performance biofuel. This reaction was studied using a flow-through microreactor system with Pd/MgO-Al₂O₃ and bimetallic Pd-Cu/MgO-Al₂O₃ mixed oxide-based catalysts in a H₂ carrier gas at a pressure of 21 bar and temperatures ranging from 200 to 350 °C. The effect of the metal promoter(s) on the hydrogen transfer reaction steps in the overall reaction was investigated. The palladium promoter significantly improved the activity and butanol selectivity across the entire temperature range. However, the yield of liquid products decreased significantly at temperatures higher than 250 °C, primarily because the decarbonylation side reaction of the acetaldehyde intermediate accelerated. The promoting effect of Pd was most beneficial below 250 °C because the decarbonylation reaction was inhibited by the reversible poisoning effect of CO on multiple Pd sites responsible for decarbonylation. Diluting the Pd phase with Cu increased liquid yields due to gradually decreasing decarbonylation activity. However, the dehydrogenation–hydrogenation activity decreased as well, as did the promoting effect on the corresponding reaction steps in the coupling reaction. Additionally, the product distribution changed dramatically, decreasing 1-butanol selectivity, because metallic Cu can catalyze the formation of ethyl acetate and ketone products. Full article

The design of sustainable nanomaterials for catalysis is a key challenge in green chemistry. Herein, we report the synthesis of halloysite nanotube (Hal)-based nanomaterials selectively functionalized with a bio-inspired polydopamine (PDA) coating, which enables the controlled anchoring of palladium and copper nanoparticles (PdNPs and CuNPs). This mild and ecofriendly strategy yields highly dispersed and ultrasmall (<5 nm) metal nanoparticles without the need for surfactants or harsh reagents. The resulting materials, Hal@PDA/PdNPs and Hal@PDA/CuNPs, were evaluated in two well-established model reactions commonly employed to probe catalytic performance: cinnamaldehyde hydrogenation and 4-nitrophenol reduction. Hal@PDA/PdNPs displayed complete conversion and >90% selectivity toward hydrocinnamaldehyde at low Pd loading (0.8 wt%) and maintained its efficiency over six catalytic cycles (TOF up to 0.1 s⁻¹), while Hal@PDA/CuNPs retained high activity through eight consecutive runs in the reduction of 4-nitrophenol. Hal@PDA/CuNPs proved to be an excellent recyclable catalyst for the reduction of 4-nitrophenol, retaining high activity through eight consecutive runs. Overall, this study introduces a robust and modular approach to fabricating halloysite-based nanocatalysts, demonstrating their potential as green platforms for metal nanoparticle-mediated transformation. Full article

A series of porous carbons (PPC) derived from pomegranate peel were synthesized as catalyst supports for Pd/PPC catalysts via hydrothermal-carbonization and incipient wetness impregnation in an acetylene hydrochlorination reaction. The optimal Pd/PPC (500) catalyst with more than 99% of acetylene conversion and vinyl chloride monomer (VCM) selectivity was obtained using an orthogonal experimental design (OED) and single-factor experiments. Based on the catalytic performance and characterization of the Pd/PPC catalyst, the deactivation mechanism of the catalysts, which was attributed to carbon deposition on the catalysts’ surface, and the loss of active Pd species have been studied, which provides insights for the rational design of high-performance biomass-based acetylene hydrochlorination catalysts. Full article

In this study, we investigated the influence of polymer nature and support characteristics on the performance of Pd-based heterogeneous catalysts. Catalysts were prepared via sequential adsorption of poly(4-vinylpyridine) (P4VP) or chitosan (CS) and palladium ions onto MgO and SBA-15 supports under ambient conditions. The resulting hybrid materials were characterized by IR spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectra (XPS). TEM analysis revealed that Pd nanoparticles with an average size of 2–3 nm were well-dispersed on P4VP/MgO, while larger and less uniformly distributed particles (8–10 nm) were observed on SBA-15-based systems. Catalytic tests in the hydrogenation of 2-propen-1-ol, phenylacetylene, and 2-hexyn-1-ol under mild conditions (40 °C, 1 atm H₂, ethanol) demonstrated that both the support and polymer type significantly influence activity and selectivity. P4VP-modified catalysts outperformed CS-containing analogs in all reactions. MgO-based systems showed higher activity and selectivity in 2-propen-1-ol hydrogenation compared to SBA-15-based catalysts. The 1%Pd–P4VP/MgO catalyst exhibited the best performance, with a reaction rate of 5.2 × 10⁻⁶ mol/s, 83.4% selectivity to propanol, and stable activity over 30 consecutive runs. In phenylacetylene and 2-hexyn-1-ol hydrogenation, all catalysts showed high selectivity to styrene (93–95%) and cis-2-hexen-1-ol (96–97%), respectively. The incorporation of P4VP polymer into the Pd/MgO catalyst leads to smaller and better-distributed palladium particles, resulting in enhanced catalytic activity and stability during hydrogenation reactions. These results confirm that the choice of polymer modifier and inorganic support must be tailored to the specific reaction, enabling the design of highly active and selective polymer-modified Pd catalysts for selective hydrogenation processes under mild conditions. Full article

This study presents a highly sensitive non-enzymatic electrochemical sensor for detecting Sunset Yellow, a common food additive in beverages, based on palladium-cerium oxide composite decorated carbon black (CB). The sensing material was prepared by depositing palladium nanoparticles onto cerium oxide nanocubes, followed by the uniform dispersion of CB through sonication in a water bath. The strong metal–support interaction between palladium and cerium oxide significantly enhances catalytic activity, while the CB ensures excellent conductivity and structural support for the catalyst. Under optimized conditions, the sensor exhibits a linear response to Sunset Yellow concentrations in the range from 1 to 100 nM, with a limit of detection (LOD) of 0.056 nM. Additionally, the sensor demonstrates remarkable selectivity and stability. Practical application in real orange juice samples yielded recoveries from 99.11% and 101.34%, confirming its reliability for real-world beverage analysis. Full article

Natural gas (NG) engine catalysts face unique challenges in emission control due to their distinct raw emission characteristics. This study investigates the exhaust conversion and by-product generation of a Palladium-based catalyst of an NG engine through small-sample catalyst experiments, mainly focusing on the effect of feed gas composition on the conversion efficiency and N₂O/NH₃ emissions. Results show that N₂O is generated via NO reduction by H₂ (80~275 °C) and CO (275~400 °C) in the temperature range of 80~400 °C. NH₃ generation occurs at 175~550 °C, mainly via NO reduction by H₂ (supplied from the water–gas shift (WGS) reaction) and CO below 425 °C and exclusively by H₂ (supplied from the steam reforming (SR) reaction) above 425 °C. An increase (0.9705~1.0176) in lambda enhances CO and CH₄ conversion while reducing N₂O and NH₃ emissions, but it inhibits NO conversion and promotes NO₂ formation. A lambda of 0.9941 achieves high conversion efficiency (≥90%) for CO, CH₄, and NO, with reduced N₂O and zero NH₃ emissions. An increase in H₂O (8~16%) accelerates the WGS and SR reactions, improving pollutant conversion. However, it aggravates N₂O and NH₃ emissions, with peak levels rising by 54% and 31%, respectively. Increased H₂ (500~1500 ppm) preferentially consumes NO and reversely shifts the equilibrium of the WGS and SR reactions, reducing CO and CH₄ conversion while improving NO conversion. And it promotes N₂O selectivity at high temperature and NH₃ selectivity at low temperature and peak emissions, with peak concentrations increasing by 58% and 15%, respectively. These findings reveal the by-product formation mechanism in the catalyst, providing valuable insights for the emission control of NG-fueled engines. Full article

In this study, a novel strategy to enhance the performance of palladium (Pd)-based catalysts by doping with metal oxides (Mn₃O₄, MoO₃, and SnO) has been developed in order to overcome the limitations of its low activity and high cost in the catalytic oxidation of formaldehyde (HCHO). The novelty of this strategy lies in the fact that by precisely controlling the types and doping ratios of the metal oxides, a significant enhancement of the electrochemical performance and catalytic activity of the Pd-based catalysts was achieved, while the dependence on precious metals was reduced and the cost-effectiveness of the catalysts was improved. The effects of different metal oxide doping on the catalytic performance were systematically investigated by electrochemical characterization and catalytic activity tests. Among the prepared catalysts, Pd-Mn₃O₄ showed the most excellent performance, with an electrochemically active surface area of 20.6 m²/g and a formaldehyde oxidation reaction (FOR) current density of 3.5 mA/cm², which were 31.6% and 169.2% higher than pure Pd, respectively. In a 1000 s timed current method stability test, the limiting current density of Pd-Mn₃O₄ reached 0.48 mA/cm², which is 4.4 times higher than that of pure Pd. The excellent catalytic performance is attributed to the abundant surface hydroxyl (-OH) groups provided by Mn₃O₄, which contribute to the oxidation of formaldehyde intermediates, as well as the electronic synergistic effect between Pd and Mn₃O₄, which is manifested as a 0.4 eV downshift of the Pd 3d binding energy. In addition, the sensor evaluation showed that the Pd-Mn₃O₄-based formaldehyde sensor exhibited a high sensitivity (1.5 μA/ppm), excellent linearity (R² = 0.995), minimal long-term degradation (<7% in 30 days), and ~20-fold selectivity for formaldehyde over interfering gases (e.g., ethanol). This study provides a theoretical basis and practical material reference for the development of efficient and low-cost catalysts for formaldehyde oxidation. Full article

Mechanochemical and transition-metal-catalyzed reactions of alkynes, exhibiting significant advantages like short reaction time, solvent-free, high yield and good selectivity, were considered to be green and sustainable pathways to access functionalized molecules and obtained increasing attention due to the superiorities of mechanochemical processes and the reactivities of alkynes. The ball milling and CuI-catalyzed Sonogashira coupling of alkyne and aryl iodide avoided the use of common palladium catalysts. The mechanochemical Rh(III)- and Au(I)-catalyzed C–H alkynylations of indoles formed the 2-alkynylated and 3-alkynylated indoles selectively. The mechanochemical and copper-catalyzed azide-alkyne cycloaddition (CuAAC) between alkynes and azides were developed to synthesize 1,2,3-triazoles. Isoxazole could be formed through ball-milling-enabled and Ru-promoted cycloaddition of alkyne and hydroxyimidel chloride. In this review, the generation of mechanochemical and transition-metal-catalyzed reactions of alkynes was highlighted. Firstly, the superiority and application of transition-metal-catalyzed reactions of alkynes were briefly introduced. After presenting the usefulness of green chemistry and mechanochemical reactions, mechanochemical and transition-metal-catalyzed reactions of alkynes were classified and demonstrated in detail. Based on different kinds of reactions of alkynes, mechanochemical and transition-metal-catalyzed coupling, cycloaddition and alkenylation reactions were summarized and the proposed reaction mechanisms were disclosed if available. Full article

Hexavalent chromium [Cr(VI)] is a hazardous environmental contaminant, and palladium nanoparticles (PdNPs) have shown promise as catalysts for its reduction. This study explores the primary factor influencing the catalytic performance of PdNPs in Cr(VI) reduction by investigating the crystal structure and composition of PdNPs in fungal-based catalysts. Five Pd-loaded catalysts were synthesized by treating fungal biomass with different chemical reagents, resulting in varying Pd(0) contents. The nanoparticle morphology, chemical states, and functional group interactions during Pd adsorption and reduction were investigated using multiple analytical techniques. The results showed that fungal hyphae remained structurally intact throughout the treatment process. PdNPs smaller than 2 nm were observed, with both Pd(0) and PdO present. The proportion of Pd(0) ranged from 6.4% to 37.2%, depending on the chemical reagent used. In addition, functional groups such as phosphate, amine, hydroxyl, and carboxyl were found to play key roles in palladium binding, underscoring the importance of surface chemistry in the adsorption and reduction process. A strong positive correlation was observed between the Pd(0) content and catalytic activity. Notably, the NCPdSF sample (palladium-loaded biomass treated with sodium formate) exhibited the highest Pd(0) content of 59.2% and achieved the most effective Cr(VI) reduction. These results suggest that Pd(0) content is a key determinant of catalytic efficiency in Cr(VI) reduction and that optimizing chemical treatments to enhance Pd(0) levels can substantially improve catalyst performance. Full article

In this work, the effect of the palladium precursor on the Oxygen Reduction Reaction (ORR) performance of lignin-based electrospun carbon fibers was studied. The fibers were spun from a lignin-ethanol solution free of any binder, where different Pd salts were added at two concentration levels. The system implemented to perform the spinning was a coaxial setup in which the internal flow contains the precursor dispersion with the metallic precursor, and ethanol was used as external flow to help fiber formation and prevent drying before generating the Taylor cone. The obtained cloths were thermostabilized in air at 200 °C and carbonized in nitrogen at 900 °C. The resulting carbon fibers were characterized by physicochemical and electrochemical techniques. The palladium precursor significantly affects nanoparticle distribution and size, fiber diameter, pore distribution, surface area and electrochemical behavior. The fibers prepared with palladium acetylacetonate at high Pd loading and carbonized at 900 °C under a CO₂ atmosphere showed high mechanical stability and the best ORR activity, showing near total selectivity towards the 4-electron path. These features are comparable to those of the commercial Pt/C catalyst but much lower metal loading (10.6 wt.% vs. 20 wt.%). The most promising fibers have been evaluated as cathodes in a zinc–air battery, delivering astonishing stability results that surpassed the performance of commercial Pt/C materials in both charging and discharging processes. Full article

A separable bamboo-like carbon nanotube-based catalyst was prepared by the spherfication method using sodium alginate and nickel. The spheres were carbonized and then decorated with palladium nanoparticles before they were tested in nitrobenzene hydrogenation. The test was repeated with five different commonly used solvents (methanol, ethanol, isopropanol, tetrahydrofuran, and acetonitrile). According to the results, polar solvents showed a significantly higher aniline yield than the more apolar solvents and exceptional results were reported for ethanol (~100%). The catalyst was reused two more times (four hours each) to check the Pd leaching where the spheres kept their shape (despite the high mechanical friction caused by the mixer) and only a relatively low Pd amount was lost (5.48 rel.%). The catalyst was easily retrievable. Full article

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