Lean methane combustion over zeolite-supported Pd catalysts: Structure-performance relationship and deactivation mechanism.

Zeolites are a promising support for Pd catalysts in lean methane (CH4) combustion. Herein, three types of zeolites (H-MOR, H-ZSM-5 and H-Y) were selected to estimate their structural effects and deactivation mechanisms in CH4 combustion. We show that variations in zeolite structure and surface acidity led to distinct changes in Pd states. Pd/H-MOR with external high-dispersing Pd nanoparticles exhibited the best apparent activity, with activation energy (Ea) at 73 kJ/mol, while Pd/H-ZSM-5 displayed the highest turnover frequency (TOF) at 19.6 × 10-3 sec-1, presumably owing to its large particles with more step sites providing active sites in one particle for CH4 activation. Pd/H-Y with dispersed PdO within pore channels and/or Pd2+ ions on ion-exchange sites yielded the lowest apparent activity and TOF. Furthermore, Pd/H-MOR and Pd/H-ZSM-5 were both stable under a dry condition, but introducing 3 vol.% H2O caused the CH4 conversion rate on Pd/H-MOR drop from 100% to 63% and that on Pd/H-ZSM-5 decreased remarkably from 82% to 36%. The former was shown to originate from zeolite structural dealumination, and the latter principally owed to Pd aggregation and the loss of active PdO.

Vinyl-Addition Homopolymeization of Norbornenes with Bromoalkyl Groups.

Vinyl-addition polynorbornenes are of great interest as versatile templates for the targeted design of polymer materials with desired properties. These polymers possess rigid and saturated backbones, which provide them with high thermal and chemical stability as well as high glass transition temperatures. Vinyl-addition polymers from norbornenes with bromoalkyl groups are widely used as precursors of anion exchange membranes; however, high-molecular-weight homopolymers from such monomers are often difficult to prepare. Herein, we report the systematic study of vinyl-addition polymerization of norbornenes with various bromoalkyl groups on Pd-catalysts bearing N-heterocyclic carbene ligands ((NHC)Pd-systems). Norbornenes with different lengths of hydrocarbon linker (one, two, and four CH2 groups) between the bicyclic norbornene moiety and the bromine atom were used as model monomers, while single- and three-component (NHC)Pd-systems were applied as catalysts. In vinyl-addition polymerization, the reactivity of the investigated monomers varied substantially. The relative reactivity of these monomers was assessed in copolymerization experiments, which showed that the closer the bromine is to the norbornene double-bond, the lower the monomer's reactivity. The most reactive monomer was the norbornene derivative with the largest substituent (with the longest linker). Tuning the catalyst's nature and the conditions of polymerization, we succeeded in synthesizing high-molecular-weight homopolymers from norbornenes with bromoalkyl groups (Mn up to 1.4 × 106). The basic physico-chemical properties of the prepared polymers were studied and considered together with the results of vinyl-addition polymerization.

Constructing a Pd-Co Interface to Tailor a d-Band Center for Highly Efficient Hydroconversion of Furfural over Cobalt Oxide-Supported Pd Catalysts.

Cobalt is an alternative catalyst for furfural hydrogenation but suffers from the strong binding of H and furan ring on the surface, resulting in low catalytic activity and chemoselectivity. Herein, by constructing a Pd-Co interface in cobalt oxide-supported Pd catalysts to tailor the d-band center of Co, the concerted effort of Pd and Co boosts the catalytic performance for the hydroconversion of furfural to cyclopentanone and cyclopentanol. The increased dispersion of Pd on acid etching Co3O4 promotes the reduction of Co3+ to Co0 by enhancing hydrogen spillover, favoring the creation of the Pd-Co interface. Both experimental and theoretical calculations demonstrate that the electron transfer from Pd to Co at the interface results in the downshift of the d-band center of Co atoms, accompanied by the destabilization of H and furan ring adsorption on the Co surface, respectively. The former improves the furfural hydrogenation with TOF on Co elevating from 0.20 to 0.62 s-1, and the latter facilitates the desorption of formed furfuryl alcohol from the Co surface for subsequently hydrogenative rearrangement of the furan ring to cyclopentanone on acid sites. The resultant Pd/Co3O4-6 catalyst delivers superior activity with a 99% furfural conversion and 85% overall selectivity toward cyclopentanone/cyclopentanol. We anticipate that such a concept of tailoring the d-band center of Co via interface engineering provides novel insight and feasible approach for the design of highly efficient catalysts for furfural hydroconversion and beyond.

Reduced Tiara-like Palladium Complex for Suzuki Cross-Coupling Reactions.

The design of highly active and structurally well-defined catalysts has become a crucial issue for heterogeneous catalysed reactions while reducing the amount of catalyst employed. Beside conventional synthetic routes, the employment of polynuclear transition metal complexes as catalysts or catalyst precursors has progressively intercepted a growing interest. These well-defined species promise to deliver catalytic systems where a strict control on the nuclearity allows to improve the catalytic performance while reducing the active phase loading. This study describes the development of a highly active and reusable palladium-based catalyst on alumina (Pd8 /Al2 O3 ) for Suzuki cross-coupling reactions. An octanuclear tiara-like palladium complex was selected as active phase precursor to give isolated Pd-clusters of ca. 1 nm in size on Al2 O3 . The catalyst was thoroughly characterised by several complementary techniques to assess its structural and chemical nature. The high specific activity of the catalyst has allowed to carry out the cross-coupling reaction in 30 min using only 0.12 mol % of Pd loading under very mild and green reaction conditions. Screening of various substrates and selectivity tests, combined with recycling and benchmarking experiments, have been used to highlight the great potentialities of this new Pd8 /Al2 O3 catalyst.

Fabricating Uniform TiO2-CeO2 Solid Solution Supported Pd Catalysts by an In Situ Capture Strategy for Low-Temperature CO Oxidation.

Support properties regulation has been a feasible method for the improvement of noble metal catalytic performance. For Pd-based catalysts, TiO2-CeO2 material has been widely used as an important support. However, due to the considerable discrepancy in the solubility product constant between titanium and cerium hydroxides, it is still challenging to synthesize a uniform TiO2-CeO2 solid solution in the catalysts. Herein, an in situ capture strategy was constructed to fabricate a uniform TiO2-CeO2 solid solution as supports for an enhanced Pd-based catalyst. The obtained Pd/TiO2-CeO2-iC catalyst possessed enriched reactive oxygen species and optimized CO adsorption capability, manifesting a superior CO oxidation activity (T100 = 70 °C) and stability (over 170 h). We believe this work provides a viable strategy for precise characteristic modulation of composite oxide supports during the fabrication of advanced noble metal-based catalysts.

Zn Modification of Pd/TiO2/Ti Catalyst for CO Oxidation.

The main goal of this study was to modify the activity of Pd/TiO2/Ti catalyst in the reaction of CO oxidation by the addition of Zn. Plasma electrolytic oxidation (PEO) of Ti wire was conducted to produce a uniform porous layer of TiO2. A mixture of Pd and Zn was then introduced by means of adsorption. After reduction treatment, the activity of the samples was examined by oxidation of 5% CO in a temperature range from 80-350 °C. Model catalysts with sufficient amounts of the metals for physico-chemical investigation were prepared to further investigate the reaction between Pd and Zn during CO oxidation. The structures and compositions of the samples were investigated using scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), inductively coupled plasma mass spectrometry (ICP-MS), Fourier transform infrared (FTIR), and X-ray diffraction (XRD). Modification of Pd/TiO2/Ti catalyst by Zn with a Pd:Zn atomic ratio of 2:1 decreased the temperature of complete CO oxidation from 220 °C for Pd/TiO2/Ti to 180 °C for Pd-Zn/TiO2/Ti. The temperature of 50% CO conversion on Pd-Zn(2:1)/TiO2/Ti was around 55 °C lower than in the reaction on monometallic Pd catalyst. The addition of Zn to the Pd catalyst lowered the binding energy of CO on the surface and improved the dissociative adsorption of oxygen, facilitating the oxidation of CO. FTIR showed that the bridging form of adsorbed CO is preferred on bimetallic systems. Analysis of the surface compositions of the samples (SEM-EDS, TOF-SIMS) showed higher amounts of oxygen on the bimetallic systems.

Mechanism and Origins of Site-Selectivity of Template-Directed C-H Insertion of Quinolines.

The template-directed C-H insertion of α,ß-unsaturated esters into quinoline was interrogated by using computational quantum chemistry. An energetically viable mechanism for this complex multistep transformation was elucidated, with attention paid throughout to conformational flexibility and alternative ligand binding modes. The selectivity was found to correlate with distortion from a tetrahedral geometry for the carbon atom involved in C-H insertion, a parameter that can be applied to future template design.

Pyridinic Nitrogen Sites Dominated Coordinative Engineering of Subnanometric Pd Clusters for Efficient Alkynes' Semihydrogenation.

Supported metal catalysts have played an important role in optimizing selective semihydrogenation of alkynes for fine chemicals. There into, nitrogen-doped carbons, as a type of promising support materials, have attracted extensive attentions. However, due to the general phenomenon of random doping for nitrogen species in the support, it is still atremendous challenge to finely identify which nitrogen configuration dominates the catalytic property of alkynes' semihydrogenation. Herein, it is reported that uniform mesoporous N-doped carbon spheres derived from mesoporous polypyrrole spheres are used as supports to immobilized subnanometric Pd clusters, which provide a particular platform to research the influence of nitrogen configurations on the alkynes' semihydrogenation. Comprehensive experimental results and density functional theory calculation indicate that pyridinic nitrogen configuration dominates the catalytic behavior of Pd clusters. The high contents of pyridinic nitrogen sites offer abundant coordination sites, which greatly reduces the energy barrier of the rate-determining reaction step and makes Pd clusters own high catalytic activity. The electron effect between pyridinic nitrogen sites and Pd clusters makes the reaction highly selective. Additionally, the good mesostructures also promote the fast transport of substrate. Based on the above, catalyst Pd@PPy-600 exhibits high catalytic activity (99%) and selectivity (96%) for phenylacetylene (C8 H6 ) semihydrogenation.

Density Functional Theory Analysis of the Copolymerization of Cyclopropenone with Ethylene Using a Palladium Catalyst.

Density functional theory has been used to elucidate the mechanism of Pd copolymerization of cyclopropenone with ethylene. The results reveal that introducing ethylene and cyclopropenone to Pd catalyst is thermodynamically feasible and generates the α,ß-unsaturated ketone unit (UnitA). Cis-mode insertion and Path A1a are the most favorable reaction routes for ethylene and cyclopropenone, respectively. Moreover, cyclopropenone decomposition can generate CO in situ without a catalyst or with a Pd catalyst. The Pd-catalyzed decomposition of cyclopropenone exhibits a lower reaction barrier (22.7 kcal/mol) than its direct decomposition. Our study demonstrates that incorporating CO into the Pd catalyst can generate the isolated ketone unit (UnitB). CO is formed first; thereafter, UnitB is generated. Therefore, the total energy barrier of UnitB generation, accounting for the CO barrier, is 22.7 kcal/mol, which is slightly lower than that of UnitA generation (24.0 kcal/mol). Additionally, the possibility of copolymerizing ethylene, cyclopropenone, and allyl acetate (AAc) has been investigated. The free energy and global reactivity index analyses indicate that the cyclopropenone introduction reaction is more favorable than the AAc insertion, which is consistent with the experimental results. Investigating the copolymerization mechanism will help to develop of a functionalization strategy for polyethylene polymers.

Rapid detoxification of Microcystin-LR by selective catalytic hydrogenation of the Adda moiety using TiO2-supported Pd catalysts.

The hepatotoxicity of Microcystin-LR (MC-LR) is mainly caused by its Adda moiety. In this study, we used TiO2-supported Pd catalysts to selectively hydrogenate the CC bonds in the Adda moiety, achieving rapid detoxification of MC-LR in water under ambient conditions. MC-LR was removed within 5 min by catalytic hydrogenation on Pd(1.0)/TiO2 with a catalyst dosage normalized rate constant of 1.3 × 10-2 L mgcat-1 min-1, significantly more efficient than other catalytic treatment methods. The reactions proceeded in a highly selective manner towards catalytic hydrogenation at the CC bond of the Mdha moiety and subsequently the conjugated double bond of the Adda moiety, yielding two intermediates and one final product. Upon catalytic hydrogenation for 30 min on Pd(0.07)/TiO2, the toxicity of MC-LR (assessed by protein phosphatase 2A activity assay) drastically decreased by 90.8%, demonstrating effective detoxification. The influence of catalyst support, Pd content, initial MC-LR concentration, reaction pH, and catalytic stability were examined. Surface adsorption and the cationic Pd played a crucial role in the reaction kinetics. Our results suggest that catalytic hydrogenation is a highly effective and safe strategy for detoxifying MC-LR by selective reactions.

Co-Catalysis for Hydroamidocarbonylation of Alkynes with Amides over a Bifunctional Ligand-Based Pd Catalyst.

The hydroamidocarbonylation of alkynes with amides allows for the synthesis of α,ß-unsaturated imides with the advantage of 100% atomic economy. Herein, the bifunctional ligand (L1) containing a sulfonic acid group (-SO3 H) and phosphino-fragment enable the Pd catalyst to accomplish the hydroamidocarbonylation of alkynes with amides. It was found that, due to an intramolecular synergetic effect, the L1-based Pd-catalyst exhibited much higher activity than the individual mechanical mixtures of Xantphos-based Pd-complex and MeSO3 H. The formation and stability of Pd-H species were promoted by the presence of L1, which was verified by in situ high-pressure FT-IR analysis. Under the optimized conditions, the target products of the branched imides were obtained with yields in the range of 46-87% over the L1-based Pd-catalyst. Advantageously, as an ionic ligand, the L1-based Pd-catalyst could be recycled for 4 runs in the ionic liquid of [Bmim]NTf2 without any obvious activity loss and detectable metal leaching.

Electrochemical nitrate reduction of brines: Improving selectivity to N2 by the use of Pd/activated carbon fiber catalyst.

Contamination of water by nitrate has become a worldwide problem, being high levels of this ion detected in the surface, and groundwater, mainly due to the intensive use of fertilizers, and to the discharge of not properly treated effluents. This study aims to evaluate the electrocatalytic process, carried out in a cell divided into two compartments by a cation exchange membrane, and with a copper plate electrode as cathode, identifying the effects of current density, pH, the use of a catalyst in the nitrate reduction, and the production of gaseous compounds. The highest nitrate reduction was obtained with a current density of 2.0 mA cm-2, without pH adjustment and, in this condition, nitrite ion was mainly formed. The application of activated carbon fibers with palladium (1% wt. and 3% wt.) in an alkaline medium presented an increase in gaseous compounds formation. With 2.0 mA cm-2, pH adjustment, and applying 3% wt. Pd catalyst, the highest selectivity to gaseous compounds was obtained (95%) with no nitrite detection. These results highlight the viability of using the process developed at this work for the treatment of nitrate contaminated waters.

Manganese-cerium composite oxide pyrolyzed from metal organic framework supporting palladium nanoparticles for efficient toluene oxidation.

Manganese-cerium metal oxide with flocculent structure prepared via the pyrolysis of Mn/Ce-MOF and supported Pd were applied for the catalytic oxidation of toluene. The Pd/Mn3Ce2-300 catalyst could completely oxidize toluene at 190 °C, which presented excellent catalytic performance. Moreover, Pd/Mn3Ce2-300 possessed great reusability, stability and water resistance even under 10 vol% water vapors. A series of characterizations including X-ray diffraction (XRD), N2 adsorption-desorption, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and H2 temperature programmed reduction (H2-TPR) were used to investigate the physicochemical properties of the samples. It was found that Pd/Mn3Ce2-300 possessed a better reduction ability at low temperature, more surface absorbed oxygen and surface Pd species, and a strong interaction between Pd and Mn3Ce2-300, resulting in great catalytic performance for toluene degradation.

Synthesis of Supported Heterogeneous Catalysts by Laser Ablation of Metallic Palladium in Supercritical Carbon Dioxide Medium.

To obtain a supported heterogeneous catalyst, laser ablation of metallic palladium in supercritical carbon dioxide was performed in the presence of a carrier, microparticles of γ-alumina. The influence of the ablation process conditions-including supercritical fluid density, ablation, mixing time of the mixture, and laser wavelength-on the completeness and efficiency of the deposition of palladium particles on the surface of the carrier was studied. The obtained composites were investigated by scanning and transmission electron microscopy using energy dispersive spectroscopy. We found that palladium particles were nanosized and had a narrow size distribution (2-8 nm). The synthesized composites revealed high activity as catalysts in the liquid-phase hydrogenation of diphenylacetylene.

A Phosphorus-Doped Ag@Pd Catalyst for Enhanced CC Bond Cleavage during Ethanol Electrooxidation.

Ethanol is preferred to be oxidized into CO2 for the construction of a high-performance direct ethanol fuel cell since this complete ethanol oxidation reaction (EOR) transfers 12 electrons. However, this EOR is sluggish and has the low activity as well as poor selectivity. To promote such a favorable EOR, more exactly the cleavage selectivity of CC bonds in ethanol, phosphorus-doped silver-core-and-Pd-shell catalysts (denoted as Ag@PdP) are designed and synthesized. In the alkaline media, a Ag@Pd2 P0.2 catalyst is superior toward EOR into CO2 . It exhibits seven times higher mass activity and six times higher selectivity than the benchmark Pd/C catalyst. As confirmed by means of density functional theory calculation and in situ Fourier-transform infrared spectroscopy, such high performance stems from an increased adsorption energy of OH radicals on the Pd active sites. Meanwhile, the tensile strain effect of a core-shell structure of this Ag@Pd2 P0.2 catalyst favors the formation of adsorbed CH3 CO intermediate, the key species for the enhanced C-C cleavage into CO2 , instead of acetate. The proposed way to design and synthesize such high-performance EOR catalysts will explore the practical applications of direct alkaline ethanol fuel cells.

Catalytic dehydrogenation of liquid organic hydrogen carrier dodecahydro-N-ethylcarbazole over palladium catalysts supported on different supports.

The system based on liquid organic hydrogen carrier (LOHC) is one of the technologies to solve the problem of hydrogen storage and transportation capacity in large-scale applications. In this paper, the catalytic dehydrogenation of LOHC dodecahydro-N-ethylcarbazole (H12-NEC) over supported Pd nanoparticles (NPs) catalyst on four kinds of different supports, such as Pd/C, Pd/Al2O3, Pd/TiO2, and Pd/SiO2, was studied. It was found from catalyst characterization and dehydrogenation reaction that the volcano-type dependence of the activity on the Pd particle size, catalytic activity improvement with large specific surface area, and high Pd reduction degree indicated that the structure, particle size, and reduction degree of Pd NPs and textural properties of supports had a synergistic effect on the catalytic performance. Among all the catalysts, Pd/C displayed outstanding catalytic performance with the H12-NEC conversion of 99.9% and hydrogen storage capacity of 5.69 wt% at 180 °C after 12 h. The particle size of Pd/C distributes in the range of 1.5-6.0 nm with an average size of 3.0 nm. The results of dehydrogenation reaction kinetics showed that the rate limiting step and rate constant for different catalysts were mainly related to the physicochemical properties and adsorption and activation abilities towards the reactants and intermediates. In terms of the stationarity of dehydrogenation process, Pd/Al2O3 was excellent, indicating that it was best for dehydrogenation of H12-NEC.

Cascade Reaction-Based Chemiresistive Array for Ethylene Sensing.

Chemiresistive sensors, which are based on semiconducting materials, offer real-time monitoring of environment. However, detection of nonpolar chemical substances is often challenging because of the weakness of the doping effect. Herein, we report a concept of combining a cascade reaction (CR) and a chemiresistive sensor array for sensitive and selective detection of a target analyte (herein, ethylene in air). Ethylene was converted to acetaldehyde through a Pd-catalyzed heterogeneous Wacker reaction at 40 °C, followed by condensation with hydroxylamine hydrochloride to emit HCl vapor. HCl works as a strong dopant for single-walled carbon nanotubes (SWCNTs), enabling the main sensor to detect ethylene with excellent sensitivity (10.9% ppm-1) and limit of detection (0.2 ppm) in 5 min. False responses that occur in the main sensor are easily discriminated by reference sensors that partially employ CR. Moreover, though the sensor monitors the variation of normalized electric resistance (ΔR/R0) in the SWCNT network, temporary deactivation of CR yields a sensor system that does not require analyte-free air for a baseline correction (i.e., estimation of R0) and recovery of response. The concept presented here is generally applicable and offers a solution for several issues that are inherently present in chemiresistive sensing systems.

Pd-based nanoparticles: Plant-assisted biosynthesis, characterization, mechanism, stability, catalytic and antimicrobial activities.

Among various metal nanoparticles, palladium nanoparticles (Pd NPs) are one of the most important and fascinating nanomaterials. An important concern about the preparation of Pd NPs is the formation of toxic by-products, dangerous wastes and harmful pollutants. The best solution to exclude and/or minimize these toxic substances is plant mediated biosynthesis of Pd NPs. Biogenic Pd-based NPs from plant extracts have been identified as valuable nanocatalysts in various catalytic reactions because of their excellent activities and selectivity. They have captured the attention of researchers owing to their economical, sustainable, green and eco-friendly nature. This review attempts to cover the recent progresses in the fabrication, characterization and broad applications of biogenic Pd NPs in environmental and catalytic systems. In addition, the stability of biosynthesized Pd NPs and mechanism of their formation are investigated.

Highly Active and Durable Ultrasmall Pd Nanocatalyst Encapsulated in Ultrathin Silica Layers by Selective Deposition for Formic Acid Oxidation.

The low performance of palladium (Pd) is a considerable challenge for direct formic acid fuel cells in practical applications. Herein, we develop a simple strategy to synthesize a highly active and durable Pd nanocatalyst encapsulated in ultrathin silica layers with vertically aligned nanochannels covered graphene oxides (Pd/rGO@pSiO2) without blocking active sites by selective deposition. The Pd/rGO@pSiO2 catalyst exhibits very high performance for a formic acid oxidation (FAO) reaction compared with the Pd/rGO without protective silica layers and commercial Pd/C catalysts. Pd/rGO@pSiO2 shows an FAO activity 3.9 and 3.8 times better than those of Pd/rGO and Pd/C catalysts, respectively. The Pd/rGO@pSiO2 catalysts are also almost 6-fold more stable than Pd/C and more than 3-fold more stable than Pd/rGO. The outstanding performance of our encapsulated Pd catalysts can be ascribed to the novel design of nanostructures by selective deposition fabricating ultrasmall Pd nanoparticles encapsulated in ultrathin silica layers with vertically aligned nanochannels, which not only avoid blocking the active sites but also facilitate the mass transfer in encapsulated catalysts. Our work indicates an important method to the rational design of high-performance catalysts for fuel cells in practical applications.

Intramolecular Catalyst Transfer on a Variety of Functional Groups between Benzene Rings in a Suzuki-Miyaura Coupling Reaction.

Suzuki-Miyaura coupling reaction of BrC6 H4 -X-C6 H4 Br 1 (X=CH2 , CO, N-Bu, O, S, SO, and SO2 ) with arylboronic acid 2 was investigated in the presence of tBu3 PPd precatalyst and CsF/[18]crown-6 as a base to establish whether or not the Pd catalyst can undergo catalyst transfer on these functional groups. In the reaction of 1 (X=CH2 , CO, N-Bu, O, and SO2 ) with 2, aryl-disubstituted product 3 (Ar-C6 H4 -X-C6 H4 -Ar) was exclusively obtained, indicating that the Pd catalyst undergoes catalyst transfer on these functional groups. On the other hand, the reaction of 1 e (X=S) and 1 f (X=SO) with 2 afforded only aryl-monosubstituted product 4 (Ar-C6 H4 -X-C6 H4 -Br) and a mixture of 3 and 4, respectively, indicating that S and SO interfere with intramolecular catalyst transfer. Furthermore, we found that Suzuki-Miyaura polycondensation of 1 (X=CH2 , CO, N-Bu, O, and SO2 ) and phenylenediboronic acid 5 in the presence of tBu3 PPd precatalyst afforded high-molecular-weight polymer even when excess 1 was used. The polymers obtained from 1 (X=CH2 , N-Bu, and O) and 5 turned out to be cyclic.