Green synthesis of palladium nanoparticles using lentinan for catalytic activity and biological applications

The green synthesis of palladium nanoparticles (Pd NPs) for catalysis and biological applications has been gaining great interest. To replace complex plant extracts, lentinan (LNT) may be a good reducing and stabilizing agent. In this work, a simple and green method using LNT to reduce and stabilize palladium Pd NPs was verified. The resulting LNT stabilized palladium nanoparticles (Pd_n-LNT NPs) were characterized by UV-Vis spectroscopy, DLS, TEM, and XPS. The results indicated that Pd NPs inside of Pd_n-LNT NPs had a small size (2.35–3.32 nm). Pd_n-LNT NPs were stable in solution for 7 days. In addition, Pd_n-LNT NPs had higher catalytic activity towards the reduction of 4-nitrophenol than other catalysts. More importantly, Pd_n-LNT NPs had negligible cytotoxicity towards cells and showed good antioxidant activity. Taken together, the prepared Pd_n-LNT NPs have great potential bio-related applications.

Lentinan stabilized palladium nanoparticles had high catalytic activity, negligible cytotoxicity and good antioxidant activity.     

Comparison of electrocatalytic activity of Pt1−xPdx/C catalysts for ethanol electro-oxidation in acidic and alkaline media

In this paper, a comparision of Pt_1−xPd_x/C catalysts for ethanol-oxidation in acidic and alkaline media has been investigated. We prepared Pt_1−xPd_x/C catalysts with different ratios of Pt/Pd (x at% = 0, 27, 53, 77 and 100) by the formic acid reduction method. The obtained Pt_1−xPd_x/C catalysts were characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), induced coupled plasma-atomic emission spectroscopy (ICP-AES), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Structural and morphological investigations of the as-prepared catalysts revealed that the metallic particle size increases with increasing Pd content in the catalyst. The electrocatalytic performances and stabilities of Pt_1−xPd_x/C catalysts were tested by cyclic voltammetry (CV), linear sweep voltammetry (LSV) and chronoamperometry (CA) measurements for ethanol oxidation in acidic and alkaline media. The electrochemical measurements demonstrate that Pt_1−xPd_x/C catalysts exhibit much higher electrocatalytic activity for alcohol oxidation in alkaline media than that in acidic media. The composition of Pt/Pd has a significant impact on the ethanol-oxidation in both acidic and alkaline media. The Pt₂₃Pd₇₇/C catalyst shows the highest electrocatalytic performance with a mass specific peak current of 2453.7 mA mg_PtPd⁻¹ in alkaline media, which is higher than the Pt₇₇Pd₂₃/C with the maximum of peak current of 339.7 mA mg_PtPd⁻¹ in acidic media. Meanwhile, the effect of electrolyte, CH₃CH₂OH concentrations and scan rates was also studied for ethanol-oxidation in acidic and alkaline media.

The Pt_1−xPd_x/C catalysts exhibit much higher electrocatalytic activity in alkaline media than in acid media.     

Insights into the spontaneous formation of hybrid PdOx/PEDOT films: electroless deposition and oxygen reduction activity

Hybrid palladium oxide/poly(3,4-ethylenedioxythiophene) (PdO_x/PEDOT) films were prepared through a spontaneous reaction between aqueous PdCl₄²⁻ ions and a nanostructured film of electropolymerized PEDOT. Spectroscopic and electrochemical characterization indicate the presence of mixed-valence Pd species as-deposited (19 ± 7 at% Pd⁰, 64 ± 3 at% Pd²⁺, and 18 ± 4 at% Pd⁴⁺ by X-ray photoelectron spectroscopy) and the formation of stable, electrochemically reversible Pd⁰/α-PdO_x active species in alkaline electrolyte and furthermore in the presence of oxygen. The elucidation of the Pd speciation as-deposited and in solution provides insight into the mechanism of electroless deposition in neutral aqueous conditions and the electrocatalytically active species during oxygen reduction in alkaline electrolyte. The PdO_x/PEDOT film catalyses 4e⁻ oxygen reduction (n = 3.97) in alkaline electrolyte at low overpotential (0.98 V vs. RHE, onset potential), with mass- and surface area-based specific activities competitive with, or superior to, commercial 20% Pt/C and state-of-the-art Pd- and PEDOT-based nanostructured catalysts. The high activity of the nanostructured hybrid PdO_x/PEDOT film is attributed to effective dispersion of accessible, stable Pd active sites in the PEDOT matrix.

Hybrid PdO_x/PEDOT films efficiently catalyse the direct 4e⁻ oxygen reduction reaction in alkaline electrolyte.     

Structural exploration of AuxM− (M = Si,Ge, Sn; x = 9–12) clusters with a revised genetic algorithm

We used a revised genetic algorithm (GA) to explore the potential energy surface (PES) of Au_xM⁻ (x = 9–12; M = Si, Ge, Sn) clusters. The most interesting finding in the structural study of Au_xSi⁻ (x = 9–12) is the 3D (Au₉Si⁻ and Au₁₀Si⁻) → quasi-planar 2D (Au₁₁Si⁻ and Au₁₂Si⁻) structural evolution of the Si-doped clusters, which reflects the competition of Au–Au interactions (forming a 2D structure) and Au–Si interactions (forming a 3D structure). The Au_xM⁻ (x = 9–12; M = Ge, Sn) clusters have quasi-planar structures, which suggests a lower tendency of sp³ hybridization and a similarity of electronic structure for the Ge or Sn atom. Au₉Si⁻ and Au₁₀Si⁻ have a 3D structure, which can be viewed as being built from Au₈Si⁻ and Au₉Si⁻ with an extra Au atom bonded to a terminal gold atom, respectively. In contrast, the quasi-planar structures of Au_xM⁻ (x = 9–12; M = Ge, Sn) reflect the domination of the Au–Au interactions. Including the spin–orbit (SO) effects is very important to calculate the simulated spectrum (structural fingerprint information) in order to obtain quantitative agreement between theoretical and future experimental PES spectra.

We used a revised genetic algorithm (GA) to explore the potential energy surface (PES) of Au_xM⁻ (x = 9–12; M = Si, Ge, Sn) clusters.     

Enhanced oxygen reduction activity of Pt shells on PdCu truncated octahedra with different compositions

Pd@Pt core–shell nanocrystals with ultrathin Pt layers have received great attention as active and low Pt loading catalysts for oxygen reduction reaction (ORR). However, the reduction of Pd loading without compromising the catalytic performance is also highly desired since Pd is an expensive and scarce noble-metal. Here we report the epitaxial growth of ultrathin Pt shells on Pd_xCu truncated octahedra by a seed-mediated approach. The Pd/Cu atomic ratio (x) of the truncated octahedral seeds was tuned from 2, 1 to 0.5 by varying the feeding molar ratio of Pd to Cu precursors. When used as catalysts for ORR, these three Pd_xCu@Pt core–shell truncated octahedra exhibited substantially enhanced catalytic activities compared to commercial Pt/C. Specifically, Pd₂Cu@Pt catalysts achieved the highest area-specific activity (0.46 mA cm⁻²) and mass activity (0.59 mA μg_Pt⁻¹) at 0.9 V, which were 2.7 and 4.5 times higher than those of the commercial Pt/C. In addition, these Pd_xCu@Pt core–shell catalysts showed a similar durability with the commercial Pt/C after 10 000 cycles due to the dissolution of active Cu and Pd in the cores.

Pd_xCu@Pt core–shell truncated octahedra were synthesized and exhibited substantially enhanced catalytic properties for oxygen reduction reaction relative to Pt/C.     

Ginkgo biloba leaf polysaccharide stabilized palladium nanoparticles with enhanced peroxidase-like property for the colorimetric detection of glucose

Sensitive glucose detection based on nanoparticles is good for the prevention of illness in our bodies. However, many nanoparticles lack stability and biocompatibility, which restrict their sensitivity to glucose detection. Herein, stable and biocompatible Ginkgo biloba leaf polysaccharide (GBLP) stabilized palladium nanoparticles (Pd_n-GBLP NPs) were prepared through a green method where GBLP was used as a reducing and stabilizing agent. The results of Pd_n-GBLP NPs characterized by UV-visible spectroscopy (UV-Vis), Fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (TEM) and X-ray photoelectron spectra (XPS) confirmed the successful preparation of Pd_n-GBLP NPs. TEM results indicated that the sizes of Pd NPs inside of Pd_n-GBLP NPs (n = 41, 68, 91 and 137) were 7.61, 9.62, 11.10 and 13.13 nm, respectively. XPS confirmed the successful reduction of PdCl₄²⁻ into Pd (0). Dynamic light scattering (DLS) results demonstrated the long-term stability of Pd_n-GBLP NPs in different buffer solutions. Furthermore, Pd₉₁-GBLP NPs were highly biocompatible after incubation (500 μg mL⁻¹) with HeLa cells for 24 h. More importantly, Pd₉₁-GBLP NPs had peroxidase-like properties and followed a ping-pong mechanism. The catalytic oxidation of substrate 3,3′,5,5′-tetramethylbenzidine (TMB) into blue oxidized TMB (oxTMB) by Pd₉₁-GBLP NPs was used to detect the glucose concentration. This colorimetric method had high selectivity, wide linear range from 2.5 to 700 μM and a low detection limit of 1 μM. This method also showed good accuracy for the detection of glucose concentrations in blood. The established method has great potential in biomedical detection in the future.

Ginkgo biloba leaf polysaccharide stabilized palladium nanoparticles had high stability, good biocompatibility and low detection limit for glucose.     

Cu2−xSe nanoparticles (Cu2−xSe NPs) mediated neurotoxicity via oxidative stress damage in PC-12 cells and BALB/c mice

Cu_2−xSe nanoparticles (Cu_2−xSe NPs) are widely used for optical diagnostic imaging and photothermal therapy due to their strong near-infrared (NIR) optical absorption. With the continuous expansion of applications using Cu_2−xSe NPs, their biosafety has received increasing attention in recent years. Cu_2−xSe NPs can enter the brain by crossing the blood–brain barrier, but the neurotoxicity of NPs remains unclear. The present investigation provides direct evidence that the toxicity of Cu_2−xSe NPs can be specifically exploited to kill rat pheochromocytoma PC-12 cells (a cell line used as an in vitro model for brain neuron research) in dose- and time-dependent manners. These cytotoxicity events were accompanied by mitochondrial damage, adenosine triphosphate (ATP) depletion, production of oxidizing species (including reactive oxygen species (ROS), malondialdehyde (MDA) and hydrogen peroxide (H₂O₂)), as well as reductions in antioxidant defense systems (glutathione (GSH) and superoxide dismutase (SOD)). Moreover, our in vivo study also confirmed that Cu_2−xSe NPs markedly induced neurotoxicity and oxidative stress damage in the striatum and hippocampal tissues of BALB/c mice. These findings suggest that Cu_2−xSe NPs induce neurotoxicity in PC-12 cells and BALB/c mice via oxidative stress damage, which provides useful information for understanding the neurotoxicity of Cu_2−xSe NPs.

Cu_2−xSe nanoparticles (Cu_2−xSe NPs) are widely used for optical diagnostic imaging and photothermal therapy due to their strong near-infrared (NIR) optical absorption.     

Bimetallic gold and palladium nanoparticles supported on copper oxide nanorods for enhanced H2O2 catalytic reduction and sensing

The emergence of nanoscience and nanotechnology has revitalised research interest in using copper and its derived nanostructures to find exciting and novel applications. In this work, mono- and bimetallic gold and palladium nanoparticles supported on copper oxide nanorods (CuONRs) were prepared and their catalytic performance towards the reduction of H₂O₂ to form reactive oxygen radical species (ROS) was evaluated. The characterisation using microscopy and spectroscopic techniques confirms the successful synthesis of CuONRs, CuONRs@Au₆NPs, CuONRs@Pd₆NPs and CuONRs@Au₃Pd₃NPs. The efficient generation of ROS was confirmed using UV-vis spectroscopy and 1,3-diphenylisobenzofuran (DPBF) as a radical scavenger. The CuONRs possess excellent catalytic reduction activity for H₂O₂ by generating ROS. However, CuONRs also have lattice oxygens which do not participate in the catalytic reduction step. The lattice oxygens however allowed for the adsorption of gold and palladium nanoparticles (Au₆NPs, Pd₆NPs and Au₃Pd₃NPs) and thus enhanced catalytic reduction of H₂O₂ to produce ROS. The produced ROS was subsequently involved in the catalytic oxidation of a chromogenic substrate (TMB), resulting in blue coloured diimine (TMBDI) complex which was monitored using UV-vis and could also be observed using the naked eye. The catalyst dependence on pH, temperature, and H₂O₂ concentration towards efficient ROS generation was investigated. The gold and palladium-supported CuONRs nanocatalysts were evaluated for their potential applications in the fabrication of colorimetric biosensors to detect glucose oxidation by glucose oxidase (GOx). Glucose was used as a model analyte. The enzymatic reaction between GOx and β-d-glucose produces H₂O₂ as a by-product, which is then catalytically converted to ROS by the nanoparticles.

Mono- and bimetallic gold and palladium nanoparticles supported on copper oxide nanorods were prepared. Their catalytic performance towards the catalytic reduction of H₂O₂ to produce reactive oxygen radical species was evaluated.     

Enhanced catalytic activity over palladium supported on ZrO2@C with NaOH-assisted reduction for decomposition of formic acid

A ZrO₂@C support based on t-ZrO₂ embedded in amorphous carbon was obtained via the pyrolysis of a UiO-66 precursor. Highly dispersed Pd nanoparticles (NPs) were subsequently deposited onto this support, using NaOH-assisted reduction, to obtain a formic acid (FA) decomposition catalyst. This material showed a turnover frequency (TOF) for the heterogeneously-catalyzed decomposition of FA of 8588 h⁻¹ at 60 °C, with 100% H₂ selectivity. This performance is ascribed to the uniform dispersion of smaller palladium nanoparticles and a synergistic effect between the metal NPs and support. Even at 30 °C, the complete decomposition of FA was achievable in FA/SF (SF, sodium formate) solution, with a TOF as high as 1857 h⁻¹.

Pd/ZrO₂@C was prepared employing UiO-66-derived ZrO₂@C as the support and showed high catalytic activity for formic acid decomposition.     

Fabrication of Pd3@Beta for catalytic combustion of VOCs by efficient Pd3 cluster and seed-directed hydrothermal syntheses

Subnanometric Pd clusters confined within zeolite crystals was fabricated using zeolitic seeds with premade [Pd₃Cl(PPh₂)₂(PPh₃)₃]⁺ clusters under hydrothermal conditions. Characterization of the Pd₃@Beta catalysts indicate that the Pd clusters confined in the channels of Beta zeolite exhibit better dispersion and stronger interaction with the zeolite support, leading to stabilized Pd species after heat treatment by high temperature. In the model reaction of toluene combustion, the Pd₃@Beta outperforms both zeolite-supported Pd nanoparticles prepared by conventional impregnation of Pd₃/Beta and Pd/Beta. Temperatures for achieving toluene conversion of 5%, 50% and 98% of Pd₃@Beta are 136, 169 and 187 °C at SV = 60 000 mL g⁻¹ h⁻¹, respectively. Pd₃@Beta could also maintain the catalytic reaction for more than 100 h at 230 °C without losing its activity, an important issue for practical applications. The metal-containing zeolitic seed directed synthesis of metal clusters inside zeolites endows the catalysts with excellent catalytic activity and high metal stability, thus providing potential avenues for the development of metal-encapsulated catalysts for VOCs removal.

Encapsulated Pd₃@Beta was fabricated through a novel Pd₃ cluster and seed-directed method, generating an excellent performance in VOCs catalytic combustion.     

Effect of polyvinylpyrrolidone (PVP) on palladium catalysts for direct synthesis of hydrogen peroxide from hydrogen and oxygen

When synthesizing nanoparticles in the liquid phase, polymeric materials (mainly polyvinylpyrrolidone, PVP) are applied as capping and/or stabilizing agents. The polymer layer on the nanoparticles must likely be removed since it blocks the active sites of the catalyst and inhibits mass transfer of the reactants. However, we have found that the polymer can have a positive effect on the direct synthesis of hydrogen peroxide. By testing Pd/SiO₂ catalysts with different amounts of PVP, it was revealed that an adequate amount of PVP resulted in a higher rate of hydrogen peroxide production (1001 mmol_H2O2 g_Pd⁻¹ h⁻¹) than pristine Pd/SiO₂ did (750 mmol_H2O2 g_Pd⁻¹ h⁻¹), unlike other PVP added Pd/SiO₂ catalysts containing excess PVP (less than 652 mmol_H2O2 g_Pd⁻¹ h⁻¹). The effect of PVP on the catalysts was examined by transmission electron microscopy, Fourier transform infrared spectroscopy, CO chemisorption, thermogravimetric analysis, and X-ray photoelectron spectroscopy. For the catalysts containing PVP, the oxidation state of the palladium 3d shifted to high binding energy due to electron transfer from Pd to the PVP molecules. Consequently, the presence of PVP on the catalysts inhibited oxygen dissociation and decomposition of the produced hydrogen peroxide, resulting in a high selectivity and high production rate of hydrogen peroxide.

Addition of polyvinylpyrrolidone to Pd/SiO₂ catalyst improved H₂O₂ selectivity by adjusting electronic state of palladium active species.     

Synthesis and characterization of nickel-doped ceria nanoparticles with improved surface reducibility

Nickel-doped ceria nanoparticles (Ni_0.1Ce_0.9O_2−x NPs) were fabricated from Schiff-base complexes and characterized by various microscopic and spectroscopic methods. Clear evidence is provided for incorporation of nickel ions in the ceria lattice in the form of Ni³⁺ species which is considered as the hole trapped state of Ni²⁺. The Ni_0.1Ce_0.9O_2−x NPs exhibit enhanced reducibility in H₂ as compared to conventional ceria-supported Ni particles, while in O₂ the dopant nickel cations are oxidized at higher valence than the supported ones.

Nickel-doped ceria nanoparticles (Ni_0.1Ce_0.9O_2−x NPs) were fabricated from Schiff-base complexes and characterized by various microscopic and spectroscopic methods.     

Efficient dehydrogenation of a formic acid–ammonium formate mixture over Au3Pd1 catalyst

A series of AuPd/C catalysts were prepared and tested for the first time for active and stable dehydrogenation of a formic acid–ammonium formate (FA–AF) mixture. The catalysts with different Au-to-Pd molar ratios were prepared using a facile simultaneous reduction method and characterized using transmission electron microscopy (TEM), high-resolution TEM, energy dispersive X-ray spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. It was found that the catalytic activity and stability of the Au₃Pd₁/C catalyst was the best. The initial turnover frequency for the dehydrogenation of the FA–AF mixture over the Au₃Pd₁/C catalyst can reach 407.5 h⁻¹ at 365 K. The reaction order with respect to FA and AF is 0.25 and 0.55, respectively. The apparent activation energy of dehydrogenation is 23.3 ± 1.3 kJ mol⁻¹. The catalytic activity of the Au₃Pd₁/C catalyst remains ca. 88.0% after 4 runs, which is much better than the single Pd/C catalyst. The mechanism for the dehydrogenation is also discussed.

The Au₃Pd₁/C catalyst shows better performance in a formic acid–ammonium formate mixture and the mechanism of dehydrogenation is discussed.     

Synthesis of 2D MoS2(1−x)Se2x semiconductor alloy by chemical vapor deposition

Alloying/doping in two-dimensional (2D) materials is emerging as an increasingly important strategy due to the wide-range bandgap tunability and versatility of these materials. Monolayer 2D transition metal dichalcogenide (TMD) alloy has been investigated both theoretically and experimentally in recent years. Here, we synthesized a bilayer MoS_2(1−x)Se_2x semiconductor alloy via the chemical-vapor deposition technique. The as-grown triangular MoS_2(1−x)Se_2x flakes with size of roughly 10 μm were observed by optical microscope and scanning electron microscope (SEM). The 1.4–1.9 nm thickness of the samples, as measured by AFM, means that bilayer MoS_2(1−x)Se_2x alloys were grown. The characteristic Raman modes related to Mo–S and Mo–Se vibrations were observed in the Raman spectrum. Two emission peaks were respectively found, corresponding to the A and B excitons in the photoluminescence (PL) spectrum. XPS measurements confirmed the Se doping of the alloy. The first-principles calculation results show a contraction of the band gap value with the increase of Se doping in the MoS₂ lattice. Compared with monolayer MoS_2(1−x)Se_2x alloy, the band bending effect is more obvious, and the bilayer MoS_2(1−x)Se_2x alloy still shows the direct band gap luminescence characteristic, which has certain guiding significance for the growth of two-dimensional materials and for device preparation.

Alloying/doping in two-dimensional (2D) materials is emerging as an increasingly important strategy due to the wide-range bandgap tunability and versatility of these materials.     

Reusable magnetic PdxCoy nanoalloys confined in mesoporous carbons for green Suzuki–Miyaura reactions

We report herein Pd_xCo_y nanoalloys confined in mesoporous carbons (Pd_x–Co_y@MC) prepared by an eco-friendly one-pot approach consisting in the co-assembly of readily available and non-toxic carbon precursors (phloroglucinol, glyoxal) with a porogen template (pluronic F-127) and metallic salts (H₂PdCl₄ and Co(NO₃)₂·6H₂O) followed by thermal annealing. Three Pd_xCo_y@MC materials with different alloy compositions were prepared (C1: x/y = 90/10; C2: x/y = 75/25; C3 and C4: x/y = 50/50). The nanoalloys were uniformly distributed in the carbon framework and the particle sizes depended on the alloy composition. These composites were then used for Suzuki–Miyaura reactions using either H₂O or a 1 : 1 H₂O/EtOH mixture as solvent. The Pd₅₀Co₅₀@MC catalyst C3 proved to be the most efficient catalyst (in terms of efficiency and magnetic recovery) affording the coupling products in good to excellent yields. After reaction, C3 was recovered quantitatively by simple magnetic separation and reused up to six times without loss of efficiency. The amount of palladium lost in the reaction mixture after magnetic separation was very low (ca. 0.1 % wt of the amount initially used).

(Pd_x–Co_y)@MC were prepared in one-pot via an eco-friendly route and used many times for Suzuki reactions in H₂O or H₂O/EtOH mixture.     

Pt–Nix alloy nanoparticles: a new strategy for cocatalyst design on a CdS surface for photo-catalytic hydrogen generation

Solar photocatalytic water splitting for the production of hydrogen has been a core aspect for decades. A highly active and durable photocatalyst is crucial for the success of the renewable hydrogen economy. To date, the development of highly effective photocatalysts has been seen by the contemporary research community as a grand challenge. Thus, herein we put forward a sincere attempt to use a Pt–Ni_x alloy nanoparticle (NP) cocatalyst loaded CdS photocatalyst ((Pt–Ni_x)/CdS) for photocatalytic hydrogen production under visible light. The Pt–Ni_x alloy NP cocatalyst was synthesized using a one-pot solvothermal method. The cocatalyst nanoparticles were deposited onto the surface of CdS, forming a Pt–Ni_x/CdS photocatalyst. Photocatalytic hydrogen production was carried out using a 300 W Xe light equipped with a 420 nm cut-off filter. The H₂ evolution rate of the Pt–Ni₃/CdS photocatalyst can reach a value as high as 48.96 mmol h⁻¹ g⁻¹ catalyst, with a quantum efficiency of 44.0% at 420 nm. The experimental results indicate that this Pt–Ni₃/CdS photocatalyst is a prospective candidate for solar hydrogen generation from water-splitting.

In this report, PtNi_x alloy NPs coupled with a CdS photocatalyst for photocatalytic hydrogen generation under visible light have been explored.     

Preparation and catalytic properties of poly(methyl methacrylate)-supported Pd0 obtained from room-temperature,dark reduction of ionic aggregates of the unstable Pd2+ solution ionomer

A poly(methyl methacrylate)-supported Pd⁰ nanocatalyst was successfully prepared from solution reaction of Pd(CH₃COO)₂ with a copolymer acid, poly(methyl methacrylate-ran-methacrylic acid) (MMA–MAA). The reaction was carried out in a benzene/methanol mixed solvent in the dark at room temperature (∼25 °C) in the absence of a typical chemical reductant. There was coordination between the Pd⁰ nanoclusters and MMA–MAA, resulting in Pd⁰ nanoclusters being stably and uniformly dispersed in the MMA–MAA matrix, with an average particle size of ∼2.5 ± 0.5 nm. Mechanistically, it can tentatively be proposed that PMMA-ionomerization of the Pd²⁺ ions produces intramolecular –2COO⁻–Pd²⁺ aggregate cross-links in the solution. On swelling of the chain-segments that are covalently bound via multiple C–C bonds, the resultant elastic forces cause instantaneous dissociation at the O–Pd coordination bonds to give transient bare (i.e., uncoordinated), highly-oxidative Pd²⁺ ions and H⁺-associative carboxylate groups, both of which rapidly scavenge electrons and protons, respectively, of the active α-H atoms abstracted from the methanol molecules of the solvent to make Pd⁰ nanoclusters supported by the re-formed MMA–MAA. The MMA–MAA acid copolymer, without itself undergoing any permanent chemical change, serves as a mechanical activator or catalyst for the mechanochemical reduction of Pd(CH₃COO)₂ under mild conditions. Compared with traditional Pd/C catalysts, this Pd⁰ nanocatalyst exhibited more excellent catalytic efficiency and reusability in the Heck reaction between iodobenzene and styrene, and it could be easily separated. The supported Pd⁰ nanocatalyst prepared using this novel and simple preparation method may display high-efficiency catalytic properties for other cross coupling reactions.

A polymer-supported Pd⁰ nanocatalyst is prepared by using mechanochemical reduction as the driving force for the reaction.     

Catalysis with magnetically retrievable and recyclable nanoparticles layered with Pd(0) for C–C/C–O coupling in water

Nanoparticles layered with palladium(0) were prepared from nano-sized magnetic Fe₃O₄ by coating it with silica and then reacting sequentially with phenylselenyl chloride under an N₂ atmosphere and palladium(ii) chloride in water. The resulting Fe₃O₄@SiO₂@SePh@Pd(0) NPs are magnetically retrievable and the first example of NPs in which the outermost layer of Pd(0) is mainly held by selenium. The weight percentage of Pd in the NPs was found to be 1.96 by ICP-AES. The NPs were authenticated via TEM, SEM-EDX, XPS, and powder XRD and found to be efficient as catalysts for the C–O and C–C (Suzuki–Miyaura) coupling reactions of ArBr/Cl in water. The oxidation state of Pd in the NPs having size distribution from ∼12 to 18 nm was inferred as zero by XPS. They can be recycled more than seven times. The main features of the proposed protocols are their mild reaction conditions, simplicity, and efficiency as the catalyst can be separated easily from the reaction mixture by an external magnet and reused for a new reaction cycle. The optimum loading (in mol% of Pd) was found to be 0.1–1.0 and 0.01–1.0 for O-arylation and Suzuki–Miyaura coupling, respectively. For ArCl, the required amount of NPs was more as compared to that needed for ArBr. The nature of catalysis is largely heterogeneous.

Fe₃O₄@SiO₂@SePh@Pd(0) (Pd, 1.96%) as the first example of NPs having a Pd(0) layer held by selenium can execute C–C/C–O coupling in 2–6 h (80 °C).     

Perovskite lattice oxygen contributes to low-temperature catalysis for exhaust gas cleaning

A Pd catalyst supported on Ba-substituted LaAlO₃ perovskite (Pd/La_0.9Ba_0.1AlO_3−δ) was investigated for NO reduction at low temperature by propylene, which revealed that Pd/La_0.9Ba_0.1AlO_3−δ has remarkably higher activity than other Pd catalysts at low temperatures (≤573 K) for NO reduction by propylene. To elucidate the surface reaction pathway, transient response tests were conducted using ¹⁸O₂. Also, X-ray photoelectron spectroscopy (XPS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements were conducted. Comparison with a Ba-impregnated catalyst (Pd/Ba/LaAlO₃) demonstrated that Pd/La_0.9Ba_0.1AlO_3−δ shows higher activity for the formation of oxygenated species (C_xH_yO_z) as an intermediate for NO reduction because the surface lattice oxygen has improved mobility via Ba²⁺ substitution in LaAlO₃. Therefore, Pd/La_0.9Ba_0.1AlO_3−δ have high activity for NO reduction, even at low temperatures in a humid condition.

A Pd catalyst supported on Ba-substituted LaAlO₃ perovskite (Pd/La_0.9Ba_0.1AlO_3−δ) has remarkably higher activity than other Pd catalysts at low temperatures (≤573 K) for NO reduction by propylene.     

Enhanced thermoelectric properties of hydrothermally synthesized Bi0.88−xZnxSb0.12 nanoalloys below the semiconductor–semimetal transition temperature

Bi_0.88−xZn_xSb_0.12 alloys with x = 0.00, 0.05, 0.10, and 0.15 were prepared using hydrothermal synthesis in combination with evacuating-and-encapsulating sintering. The effects of partial Zn substitution for Bi and different sintering temperatures on the thermoelectric properties of Bi_0.88−xZn_xSb_0.12 alloys were investigated between 25 K and 425 K. Both the electrical conductivity and absolute thermopower are enhanced for the set of alloys sintered at 250 °C. The maximum power factor of 57.60 μW cm⁻¹ K⁻² is attained for the x = 0.05 alloy sintered at 250 °C. As compared with Zn-free Bi_0.88Sb_0.12, both the total thermal conductivity and lattice component are reduced upon Zn doping. Bipolar conduction is observed in both electronic and thermal transport. The maximum zT of 0.47 is attained at 275 K for the x = 0.05 alloy sintered at 250 °C.

The peak zT is attained for hydrothermally synthesized Bi_0.83Zn_0.05Sb_0.12 nanoalloy due to the significantly enhanced thermoelectric power factor and relatively low thermal conductivity.