Supported Pd-Cu bimetallic nanoparticles that have high activity for the electrochemical oxidation of methanol

Monodisperse bimetallic Pd-Cu nanoparticles with controllable size and composition were synthesized by a one-step multiphase ethylene glycol (EG) method. Adjusting the stoichiometric ratio of the Pd and Cu precursors afforded nanoparticles with different compositions, such as Pd(85)-Cu(15), Pd(56)-Cu(44), and Pd(39)-Cu(61). The nanoparticles were separated from the solution mixture by extraction with non-polar solvents, such as n-hexane. Monodisperse bimetallic Pd-Cu nanoparticles with narrow size-distribution were obtained without the need for a size-selection process. Capping ligands that were bound to the surface of the particles were removed through heat treatment when the as-prepared nanoparticles were loaded onto a Vulcan XC-72 carbon support. Supported bimetallic Pd-Cu nanoparticles showed enhanced electrocatalytic activity towards methanol oxidation compared with supported Pd nanoparticles that were fabricated according to the same EG method. For a bimetallic Pd-Cu catalyst that contained 15?% Cu, the activity was even comparable to the state-of-the-art commercially available Pt/C catalysts. A STEM-HAADF study indicated that the formation of random solid-solution alloy structures in the bimetallic Pd(85)-Cu(15)/C catalysts played a key role in improving the electrochemical activity.     

Highly Selective Pd–Cu/α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalysts for Liquid-Phase Hydrogenation: The Influence of the Pd: Cu Ratio on the Structure and Catalytic Characteristics

The structure and catalytic characteristics of a series of Pd–Cu/α-Al₂O₃ catalysts with Pd: Cu ratio varied from Pd₁–Cu_0.5 to Pd₁–Cu₄ were studied. The use of α-Al₂O₃ with a small surface area (S_sp = 8 m²/g) as a support made it possible to minimize the effect of diffusion on the catalytic characteristics and to study the structure of Pd–Cu nanoparticles by X-ray diffraction (XRD) analysis. The XRD analysis and transmission electron microscopy (TEM) data indicated the formation of uniform bimetallic Pd–Cu nanoparticles (d = 20–60 nm), whose composition corresponded to a ratio between the metals in the catalyst, and also the absence of monometallic Pd⁰ and Cu⁰ nanoparticles. The study of catalytic properties in the liquid-phase hydrogenation of diphenylacetylene (DPA) showed that the activity of the catalysts rapidly decreased with the Cu content increase; however, in this case, the yield of a desired alkene compound significantly increased. The selectivity of alkene formation on the catalysts with the ratios Pd: Cu = 1: 3 and 1: 4 was superior to the commercial Lindlar catalyst.     

Pd‐Cu alloy nanoparticle supported on amine‐terminated ionic liquid functional 3D graphene and its application on Suzuki cross‐coupling reaction

Well distributed Pd‐Cu bimetallic alloy nanoparticles supported on amine‐terminated ionic liquid functional three‐dimensional graphene (3D IL‐rGO/Pd‐Cu) as an efficient catalyst for Suzuki cross‐coupling reaction has been prepared via a facile synthetic method. The introduction of IL‐NH₂ cations on the surface of graphene sheets can effectively avoid the re‐deposition of graphene sheets, allowing the catalyst to be reused up to 10 cycles. The addition of Cu not only saves cost but also ensures high catalytic efficiency. It is worthy to note that the catalyst 3D IL‐rGO/Pd_2.5Cu_2.5 can efficiently catalyze the Suzuki cross‐coupling reaction with the yield up to 100% in 0.25 h, almost one‐fold higher than that by the pristine IL‐rGO/Pd_2.5 catalyst (52%). The Powder X‐Ray Diffraction (XRD), combining energy dispersive X‐ray spectroscopy (EDS) mapping results confirm the existence and distribution of Pd and Cu in the bimetallic nanoparticles. The transmission electron microscopy (TEM) reveals the nanoparticle size with an average diameter of 3.0 ± 0.5 nm. X‐ray photoelectron spectroscopy (XPS) analysis proved the presence of electron transfer from Cu to Pd upon alloying. Such alloying‐induced electronic modification of Pd‐Cu alloy and 3D ionic liquid functional graphene with large specific surface area both accounted for the catalytic enhancement.     

Catalytic dehydrogenation of natural terpenes via CuPd alloy nanoparticles generated on mesoporous graphitic carbon nitride

A facile wet-chemical protocol for the synthesis of bimetallic CuPd alloy nanoparticles (NPs) anchored on mesoporous graphitic carbon nitride (m-gCN), serving as both stabilizer and support material, was presented herein. The presented protocol allowed to synthesize nearly monodisperse CuPd alloy NPs with an average particle size of 3.9 ± 0.9 nm without use of any additional surfactants and to prepare CuPd/m-gCN nanocatalysts with different Cu/Pd compositions (Cu₂₅Pd₇₅/m-gCN, Cu₃₅Pd₆₅/m-gCN, Cu₁₆Pd₇₄/m-gCN, Cu₃₂Pd₆₈/m-gCN, Cu₁₀Pd₉₀/m-gCN, and Cu₅₀Pd₅₀/m-gCN). After the detailed characterization of CuPd/m-gCN nanocatalysts, they were utilized as catalysts in the dehydrogenation of terpenes. Among all tested nanocatalysts, Cu₅₀Pd₅₀/m-gCN showed the highest activity in terms of the product yields within the same reaction time. Various parameters influencing the catalytic activity of Cu₅₀Pd₅₀/m-gCN were studied using himachalene as a model substrate and the optimum conditions were determined. Under the optimized reaction conditions, the catalytic application of Cu₅₀Pd₅₀/m-gCN nanocatalysts was extended to nine different terpenes and the corresponding products were obtained in high conversion yields (>90%) under mild conditions. A reusability test showed that Cu₅₀Pd₅₀/m-gCN nanocatalysts can be re-used up to four cycles without significant loss in their initial activity.     

A Facile Strategy to PdCu Bimetallic Alloy Nanosponges with Highly Porous Features as a High‐Performance Electrocatalytic Activity for Ethanol Electrooxidation in an Alkaline Medium

Well‐defined three‐dimensional (3D) PdCu bimetallic alloy nanosponges (BANs) with highly porous structure was reported through a rapid and general strategy. Significantly, the as‐prepared PdCu BANs exhibited greatly enhanced activity and stability than commercial Pd/C catalyst towards ethanol electrooxidation in an alkaline medium. Pd₁Cu₁ shows higher active area and better electrocatalytic activity than Pd₁Cu₂ and Pd₂Cu₁. This result demonstrates the potential of applying these PdCu BANs as effective electrocatalysts for direct alcohol fuel cells (DAFCs).     

Mild and Selective Catalytic Hydrogenation of the C=C Bond in α,β‐Unsaturated Carbonyl Compounds Using Supported Palladium Nanoparticles

Chemoselective reduction of the C=C bond in a variety of α,β‐unsaturated carbonyl compounds using supported palladium nanoparticles is reported. Three different heterogeneous catalysts were compared using 1 atm of H₂: 1) nano‐Pd on a metal–organic framework (MOF: Pd⁰‐MIL‐101‐NH₂(Cr)), 2) nano‐Pd on a siliceous mesocellular foam (MCF: Pd⁰‐AmP‐MCF), and 3) commercially available palladium on carbon (Pd/C). Initial studies showed that the Pd@MOF and Pd@MCF nanocatalysts were superior in activity and selectivity compared to commercial Pd/C. Both Pd⁰‐MIL‐101‐NH₂(Cr) and Pd⁰‐AmP‐MCF were capable of delivering the desired products in very short reaction times (10–90 min) with low loadings of Pd (0.5–1 mol %). Additionally, the two catalytic systems exhibited high recyclability and very low levels of metal leaching.     

Preparation,characterization and catalytic application of PdPt bimetallic nanoparticles stabilized by 15‐membered triolefinic macrocycle‐terminated poly(propylene imine) dendrimer

PdPt bimetallic nanoparticles stabilized by 15‐membered triolefinic macrocycle‐stabilized poly(propylene imine) dendrimer (G3‐M(Pd_x Pt_10−x ) DSNs) have been prepared via synthesis of a 15‐membered triolefinic macrocycle‐modified third‐generation poly(propylene imine) dendrimer (G3‐M) and then synchronous ligand exchange with Pd(PPh₃)₄/Pt(PPh₃)₄ complexes. The structure and catalytic activity of the DSNs were characterized using Fourier transform infrared, ¹H NMR, transmission electron microscopy, energy‐dispersive X‐ray and X‐ray photoelectron analyses. As a novel catalyst system, it can be concluded that the composition of the bimetallic nanoparticles has an influence on the catalytic activity of the hydrogenation reaction of acrylonitrile–butadiene rubber, which can be related to synergistic effect. Furthermore, the selectivity and recyclability of G3‐M(Pd_x Pt_10−x ) DSN catalyst are also discussed.     

Oxidation of ethanol on carbon-supported oxide-rich Pd–W bimetallic nanoparticles in alkaline media

Carbon-supported oxide-rich Pd–W bimetallic nanoparticles were prepared by chemical reduction methods. The existence of oxides in the electrocatalysts is confirmed by X-ray photoelectron spectrum (XPS) and high resolution transmission electron microscopy. XPS analysis indicates that the oxygen atoms account for about 50% of all the atoms in Pd–W bimetallic nanoparticles. Compared to Pd/C catalyst, the carbon-supported oxide-rich Pd–W bimetallic nanoparticles exhibit a better catalytic activity for the anode oxidation of ethanol in alkaline media. The onset potential of the as prepared oxide-rich Pd_0.8W_0.2/C catalyst (Pd: W = 8: 2, metal atom ratio) for ethanol oxidation is negative shifted about 90 mV comparing to Pd/C catalyst. The oxide-rich Pd–W/C electrocatalysts provide a new model of noble-metal/promoter system as an extreme case of making the promoter (WO₃) closely adjacent to the noble metal (Pd) by fabricating nanoparticles containing both atom-clusters of oxides and the noble metal atoms.

     

Bismuth modified Pd/C as catalysts for hydrogen related reactions

The electrocatalytic activity of bimetallic BiPd catalysts supported on Sibunit carbon towards hydrogen oxidation/evolution reactions (HOR/HER) was studied in a gas diffusion electrode (GDE) setup. Catalysts were synthesized by deposition of Pd on the carbon support, followed by impregnation of Pd/C precursor with Bi(NO₃)₃ solution and reduction in hydrogen. Transmission electron microscopy and local EDX elemental analysis revealed that BiPd/C catalysts contain bimetallic particles with narrow size distribution with maxima at 3.2–4.1 nm. X-ray diffraction evidenced that bimetallic particles are constituted by Pd–Bi solid solution. It was shown that modification of Pd/C by bismuth increases the specific activity of palladium towards HOR/HER by a factor of 3.     

Pd/Co双金属纳米颗粒的制备及催化制氢性能

采用聚乙烯吡咯烷酮(PVP)保护的化学共还原法制备了Pd/Co双金属纳米颗粒, 研究了PVP及还原剂(NaBH₄)的用量、金属盐浓度、金属比例等对Pd/Co双金属纳米颗粒催化NaBH₄制氢性能的影响. 透射电子显微镜(TEM)的结果表明, 所制备的Pd/Co双金属纳米颗粒的平均粒径在1.5-2.8 nm之间. Pd/Co双金属纳米颗粒(BNPs)的催化活性远高于Pd与Co单金属纳米颗粒的活性; 当Pd/Co的理论原子比为1/9时, 双金属纳米颗粒的催化活性最高可达15570 mol·mol^-1·h^-1 (文中纳米颗粒的催化活性均为每摩尔Pd的活性). 密度泛函理论(DFT)的计算结果表明, Pd原子与Co原子之间发生电荷转移, 使得Pd原子带负电而Co原子带正电, 荷电的Pd和Co原子进而成为催化反应的活性中心. 所制备的Pd/Co双金属纳米颗粒具有很好的催化耐久性, 即使重复使用5次后, 该催化剂仍具有较高的催化活性, 且使用后的纳米颗粒催化剂也没有出现团聚现象. 双金属纳米颗粒催化NaBH₄水解反应的活化能约为54 kJ·mol^-1.     

Catalytic conversion of cellulose into polyols using carbon-nanotube-supported monometallic Pd and bimetallic Pd–Fe catalysts

A series of carbon nanotube (CNT)-supported monometallic Pd and bimetallic Pd–Fe catalysts were synthesized and employed for catalytic hydrogenolysis of cellulose into polyols, including hexitol, ethylene glycol (EG), 1,2-propanediol (1,2-PG), and glycerol (Gly). The physicochemical properties of the catalysts were characterized by nitrogen physical adsorption measurements, X-ray diffraction analysis, transmission electron microscopy, and X-ray photoelectron spectroscopy. The total yield of hexitol, EG, 1,2-PG, and Gly in hydrolytic hydrogenation of cellulose was 37, 55, and 53% for Pd/CNTs, Pd–Fe/CNTs (Pd:Fe = 1:1), and Pd–Fe/CNTs (Pd:Fe = 1:2), respectively. Addition of Fe to Pd significantly modified the physicochemical properties of the nanoparticles and their catalytic performance, especially regarding hexitol selectivity. The promoting effect of Fe, especially for hexitol selectivity, compared with the monometallic catalyst is due to the fact that incorporation of Fe may stabilize Pd⁰ nanoparticles and lead to downshift of the d-band center of Pd metal nanoparticles by charge transfer from Fe to Pd. Recycling experimental results showed that leaching of Fe resulted in a significant decrease in the hexitol yield obtained using the Pd–Fe/CNTs after the first recycle, further demonstrating that Fe element plays a promoting role for hexitol formation.     

Nanostructured PdRu/C catalysts for formic acid oxidation

Pd and bimetallic PdRu nanoparticles supported on Vulcan XC-72 carbon prepared by the microwave-assisted polyol process are examined as electrocatalysts for the electrooxidation of formic acid. The catalysts are characterized by transmission electron microscopy and X-ray diffraction. The Pd and PdRu nanoparticles with sizes of <10 nm display the characteristic diffraction peaks of a Pd face-centered cubic (fcc) crystal structure. It is found that the addition of Ru to Pd/C can decrease the lattice parameter of Pd (fcc) crystal. The electrocatalytic activities of the catalysts are evaluated in sulfuric acid solution containing 1 M formic acid using linear sweeping voltammetry and chronoamperometry. The results show that Pd₅Ru₁/C displays the best electrocatalytic performance among all catalysts for formic acid electrooxidation.     

Fabrication of Ultrafine Palladium Phosphide Nanoparticles as Highly Active Catalyst for Chemoselective Hydrogenation of Alkynes

Monodisperse palladium phosphide nanoparticles (Pd–P NPs) with a smallest size ever reported of 3.9 nm were fabricated using cheap and stable triphenylphosphine as phosphorous source. After the deposition and calcination at 300 °C and 400 °C, the resulting Pd–P NPs increased in size to 4.0 nm and 4.8 nm, respectively. Notably, the latter NPs probably crystallized with a single phase of Pd₃P_0.95, which acted as a highly active catalyst in semi‐ and stereoselective hydrogenation of alkynes. X‐ray photoelectron spectroscopy analysis determined a positive shift of binding energy for Pd(3d) in Pd–P NPs compared to that in Pd on carbon. It indicated the electron flow from metal to phosphorus and the larger electron deficiency of Pd in Pd–P NPs, which suppressed palladium hydride formation and subsequently increased the selectivity. Thus, this result may also indicate the applications of Pd–P and other metal–P NPs in various selective hydrogenation reactions.     

Synthesis and characterization of Sibunit-supported Pd–Ga,Pd–Zn,and Pd–Ag catalysts for liquid-phase acetylene hydrogenation

Pd/Sibunit and Pd–M/Sibunit (M = Ga, Zn, or Ag) catalysts have been synthesized, and their catalytic properties in liquid-phase acetylene hydrogenation have been investigated. Doping of the palladium catalyst with a metal M leads to the formation of the Pd₂Ga, PdZn, or Pd_0.46Ag_0.54 bimetallic compound. The bimetallic particles are much smaller (1.6–2.0 nm) than the monometallic palladium particles (4.0 nm). Doping with zinc raises the ethylene selectivity by 25% without affecting the activity of the catalyst. Specific features of the effect of each of the dopants on palladium are reported.     

One Step Preparation of Reduced Graphene Oxide/Pd–Fe3O4@Polypyrrole Composites and Their Application in Catalysis

The simple preparation of catalysts with superior catalytic activity and good reusability is highly desirable. Herein, we report a novel strategy to construct reduced graphene oxide (rGO)/Pd–Fe₃O₄@polypyrrole (PPy) catalysts with Pd and Fe₃O₄ nanoparticles anchored on a rGO nanosheet surface and wrapped in a PPy shell. The synthesis and assembly of both the Pd and Fe₃O₄ nanoparticles, the preparation of the PPy layer, and the reduction of graphene oxide nanosheets were finished in one step. In the system, the PPy layer not only prevented aggregation of Pd and Fe₃O₄ nanoparticles, but also generated a synergistic effect with precursor Pd²⁺ ions, which led to a high dispersity of as‐prepared Pd nanoparticles. Although the procedure was simplified to one step, the catalytic activity and reusability were not sacrificed. In the reduction of 4‐nitrophenol, their catalytic performance was better than that in recent reports. Moreover, the catalysts showed good reusability owing to their magnetic properties.     

Influence of the thermal treatment conditions and composition of bimetallic catalysts Fe—Pd/SiO2 on the catalytic properties in phenylacetylene hydrogenation

The supported bimetallic Fe—Pd/SiO₂ catalysts with the different Fe (0.025—8 mass.%) and Pd (0.05—3.2 mass.%) loadings were synthesized by the incipient wetness impregnation of support. The samples were heat-treated under different conditions (calcination in air at 240—350 °C or reduction in an H₂ flow at 400 °C). The X-ray phase analysis revealed the formation of Pd⁰, α-Fe₂O₃ and Fe₃O₄ phases after calcination of the samples at 240—260 °C. The reduction of the calcined Fe—Pd samples in an H₂ flow at 400 °C enables the formation of Fe⁰ nanoparticles of size 17—20 nm. The synthesized catalytic systems were studied in the selective hydrogenation of phenylacetylene at room temperature and atmospheric pressure in a solvent (ethanol, propanol). The catalytic properties of the Fe—Pd catalysts depend on the nature of solvent, catalyst composition, and thermal treatment conditions. The application of the Fe—Pd bimetallic catalysts with a low Pd loading of 0.05—0.1 mass.% made it possible to reach the high activity and selectivity to styrene (91%) at the complete conversion of phenylacetylene.     

In Situ Generation of ArCu from CuF2 Makes Coupling of Bulky Aryl Silanes Feasible and Highly Efficient

A bimetallic system of Pd/CuF₂, catalytic in Pd and stoichiometric in Cu, is very efficient and selective for the coupling of fairly hindered aryl silanes with aryl, anisyl, phenylaldehyde, p‐cyanophenyl, p‐nitrophenyl, or pyridyl iodides of conventional size. The reaction involves the activation of the silane by Cu^II, followed by disproportionation and transmetalation from the Cu^I(aryl) to Pd^II, upon which coupling takes place. Cu^III formed during disproportionation is reduced to Cu^I(aryl) by excess aryl silane, so that the CuF₂ system is fully converted into Cu^I(aryl) and used in the coupling. Moreover, no extra source of fluoride is needed. Interesting size selectivity towards coupling is found in competitive reactions of hindered aryl silanes. Easily accessible [PdCl₂(IDM)(AsPh₃)] (IDM = 1,3‐dimethylimidazol‐2‐ylidene) is by far the best catalyst, and the isolated products are essentially free from As or Pd (<1 ppm). The mechanistic aspects of the process have been experimentally examined and discussed.     

High Performance Pd,PdNi, PdSn and PdSnNi Nanocatalysts Supported on Carbon Nanotubes for Electrooxidation of C2C4 Alcohols

Nanocatalysts Pd, Pd₈Ni₂, Pd₈Sn₂ and Pd₈Sn₁Ni₁ supported on multi‐walled carbon nanotubes (MWCNTs) were successively synthesized by the chemical reduction method in the glycol‐water mixture solvent. Transmission electron microscopy results show that the prepared Pd, Pd₈Ni₂, Pd₈Sn₂ and Pd₈Sn₁Ni₁ nanoparticles are uniformly dispersed on the surface of MWCNTs. The average particle sizes of the nanocatalysts are 3.5–3.8 nm. Electroactivity of the prepared catalysts towards oxidation of ethanol, 1‐propanol, 2‐propanol, n‐butanol, iso‐butanol and sec‐butanol (C2? C4 alcohols) in alkaline medium was studied by cyclic voltammetry and chronoamperometry. The current density obtained for the electrooxidation of C2? C4 alcohols depends on the catalysts and the various structures of the alcohols. Addition of Sn or/and Ni to Pd nanoparticles enhances the electroactivity of the Pd/MWCNT catalyst. Furthermore, the ternary Pd₈Sn₁Ni₁/MWCNT catalyst presents the highest electroactivity for the oxidation of C2? C4 alcohols among the prepared catalysts. Electrocatalytic activity order among propanol isomers and butanol isomers is as follows respectively: 1‐propanol > 2‐propanol, and n‐butanol > iso‐butanol > sec‐butanol > tert‐butanol. This is consistent with the Mulliken charge value of the carbon atom bonded with hydroxyl group in the corresponding alcohol molecule.     

Highly selective catalysts for liquid-phase hydrogenation of substituted alkynes based on Pd—Cu bimetallic nanoparticles

Catalytic properties of Pd—Cu bimetallic catalysts supported on SiO₂ and Al₂O₃ were studied in a model reaction of selective hydrogenation of diphenylacetylene. Application of PdCu₂(AcO)₆ heterobimetallic acetate complex as a precursor made it possible to obtain homogeneous Pd—Cu bimetallic nanoparticles. This result was supported by the data of IR spectroscopy of adsorbed CO. The Pd-Cu catalysts showed considerably higher selectivity than monometallic samples. Moreover, the introduction of copper decreases the hydrogenation rate of diphenylethylene (DPE) to diphenylethane. As a result, the maximum yield of the target product, DPE, increased from 78 to 93% in the presence of Pd—Cu catalysts.     

Dendrimer Templated Synthesis of Carbon Nanotube Supported PdAu Catalyst and its Application as Hydrogen Peroxide Sensor

At present, CNT supported catalysts were prepared by two different methods as NaBH₄ reduction and dendrimer templated NaBH₄ reduction method to observe the effect of preparation method on the sensitivity and activity of H₂O₂ reduction. Then, CNT supported Pd_xAu_y bimetallic nanocatalysts having various atomic ratio were synthesized via novel dendrimer templated NaBH₄ reduction method. The resulting materials were characterized employing XRD and TEM. Crystallite size of 10 %Pd_0.7Au_0.3/CNT_dendrimer was obtained from XRD 17.1 nm and mean particle size obtained from TEM is about 15 nm. Moreover, the electrochemical behavior of these catalysts was characterized by cyclic voltammetry (CV) and chronoamperometry (CA) techniques. Pd_xAu_y bimetallic nanocatalysts have excellent electrocatalytic properties and great potential for applications in electrochemical detection. The sensitivity and the limit of detection values for the prepared sensor with monometallic 10 % Pd/CNT_dendrimer catalysts are 219.78 μA mM^?1cm^?2 and 2.6 μM, respectively. However, the sensor constructed with 10 %Pd_0.7Au_0.3/CNT_dendrimer modified electrode has a very high sensitivity of 316.89 μA mM^?1 cm^?2 with a quick response time of 2 s and a wide linear range of 0.001–19.0 mM. In addition, the interference experiment indicated that the 10 % Pd_0.7Au_0.3/CNT_dendrimer nanoparticles have good selectivity toward H₂O₂.