Au-Pd Alloy Research Articles

Carbonized wood membrane decorated with AuPd alloy nanoparticles as an efficient self-supported electrode for electrocatalytic CO2 reduction

Efficient electrocatalytic reduction of CO2 to value-added chemicals and fuels is a promising technology for mitigating energy shortage and pollution issues yet highly relay on the development of high-performance electrocatalysts. Herein, we develop an effective strategy to fabricate carbonized wood membrane (CW) decorated with AuPd alloy nanoparticles with tunable composition (termed as AuPd@CW) as self-supported electrodes for efficient electrocatalytic CO2 reduction. The uniformly distributed AuPd nanoparticles on wood matrix are first achieved through the in-situ reduction of metal cations by the lignin content in wood. Subsequently, two-step carbonization was employed to promote the alloying of AuPd nanoparticles and the formation of CW. The AuPd@CW membrane electrode features an integrated macroscopic structure with numerous open and aligned channels for rapid electron transfer and mass diffusion and well-dispersed AuPd alloy nanoparticles as active sites for the CO2 reduction. The optimal Au95Pd5@CW electrode affords a high selectivity for CO2 electroreduction with a maximum CO faradaic efficiency (FECO) of 82% at an overpotential of 0.49 V, much higher than those obtained on Au@CW and Pd@CW electrodes. The CO current density and FECO remain relatively stable during a 12 h electrolysis reaction. In addition, density functional theory (DFT) calculations reveal that alloying Au with Pd enables a balance between the formation of intermediate COOH* and the desorption of CO on the surface of AuPd nanoparticles, thus enhancing the selectivity of CO production. This work offers an effective strategy for the fabrication of bimetallic alloys supported on wood-based carbon membrane as a practical electrode for electrochemical energy conversion.

Controllable Synthesis of Supported PdAu Nanoclusters and Their Electronic Structure-Dependent Catalytic Activity in Selective Dehydrogenation of Formic Acid.

We report the design and synthesis of uniform PdAu alloy nanoclusters immobilized on diamine and graphene oxide-functionalized silica nanospheres. The structure-dependent activity for selectively catalytic dehydrogenation of formic acid (FA) has been evaluated and optimized by controlling the Pd/Au mole ratio and the carrier components. The relationship between the catalyst structure and activity has been investigated via both experiments and characterization. High-resolution transmission electron microscopy (TEM) and X-ray diffraction (XRD) proved the formation of PdAu alloy nanoclusters. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS), and X-ray absorption fine structure (XAFS) analyses verified the electron transfer between Au, Pd, and the support. An outstanding turnover frequency (TOF) value of 16 647 h-1 at 323 K, which is among the highest activity for FA dehydrogenation ever reported, can be achieved at optimized conditions and ascribed to the combination of the bimetallic synergistic effect and the carrier effect.

UV-Mediated Photofunctionalization of Indirect Restorative Materials Enhances Bonding to a Resin-Based Luting Agent.

Purpose The potential of UV-mediated photofunctionalization to enhance the resin-based luting agent bonding performance to aged materials was investigated. Methods Sixty samples of each material were prepared. Yttria-stabilized zirconia (YZr) and Pd-Au alloy (Pd-Au) plates were fabricated and sandblasted. Lithium disilicate glass-ceramic (LDS) was CAD-CAM prepared and ground with #800 SiC paper. Half of the specimens were immersed in machine oil for 24 h to simulate the carbon adsorption. Then, all of the specimens (noncarbon- and carbon-adsorbed) were submitted to UV-mediated photofunctionalization with a 15 W UV-LED (265 nm, 300 mA, 7692 μW/cm2) for 0 (control groups), 5, and 15 min and subjected to contact angle (Ɵ) measurement and bonded using a resin cement (Panavia™ V5, Kuraray Noritake, Japan). The tensile bond strength (TBS) test was performed after 24 h. The Ɵ (°) and TBS (MPa) data were statistically analyzed using two-way ANOVA and Bonferroni correction tests (α = 0.05). Results In the carbon-adsorbed groups, UV-mediated photofunctionalization for 5 min significantly decreased Ɵ of all materials and increased TBS of YZr, and UV for 15 min significantly increased the TBS of LDS and Pd-Au. In noncarbon-adsorbed groups, UV-photofunctionalization did not significantly change the Ɵ or TBS except YZr specimens UV-photofunctionalized for 15 min. Conclusion UV-mediated photofunctionalization might have removed the adsorbed hydrocarbon molecules from the materials' surfaces and enhanced bond strengths of Panavia™ V5 to YZr, LDS, and Pd-Au. Additionally, UV-mediated photofunctionalization improved the overall TBS of YZr. Further investigation on the optimum conditions of UV photofunctionalization on indirect restorative materials should be conducted.

The mechanism of the water dissociation and dehydrogenation of glycerol on Au (111) and PdAu alloy catalyst surfaces

Hydrogen is an energy carrier found from renewable sources such as biomass, geothermal, solar, or wind. Water splitting and dehydrogenation of glycerol is a sustainable process of H2 production from renewables because water is abundant, and the glycerol is formed from the biomass-derived compounds. However, finding a suitable and best catalyst for these processes is challenging. Thus, this paper proposed a theoretical study to find the mechanism of the dissociation of water and dehydrogenation of glycerol using Au metal and PdAu alloy catalysts using the density functional theory (DFT) method. Four PdAu alloys have been constructed with different atomic compositions ranging from 1 to 3 of Pd metal to Au metal. The result showed strong adsorption on the Pd1Au3 catalyst surface, and the water splitting is best on the Pd3Au1 catalyst surface. Simultaneously, the glycerol adsorption on catalyst surfaces is tested before proceeding for the complete dehydrogenation mechanism of glycerol. Strong adsorption was found at the Pd1Au3 catalyst compared to other catalyst surfaces on the glycerol adsorption. The dehydrogenation mechanism was found toward a downhill reaction and removed eight hydrogens from the glycerol compared to Au metal, referring to easy dehydrogenation of glycerol using the alloy PdAu. The final species that adsorbed on the Pd1Au3 surface is the carbon monoxide will be turned later into carbon dioxide.

Surface segregation of PdM (M=Cu, Ag, Au) alloys and its implication to acetylene hydrogenation, DFT-based Monte Carlo simulations

The surface composition and atomic arrangement of heterogeneous catalysts determine the surface chemistry and are necessary information for understanding surface catalytic reactions. Compared with monometallic catalysts, alloy catalysts are more complicated because of possible surface segregation or adsorption-induced segregation which may change under different reaction atmosphere. Construction of reasonable slab models to study reactions on alloy surfaces is of importance. Here we proposed a density functional theory based Monte Carlo method (DFT-MC) and used it to investigate the surface composition and atomic arrangement of the (111) surfaces of 1:1 PdAg, PdAu and PdCu alloys in vacuum and under the acetylene partial hydrogenation conditions modeled by co-adsorption of H and acetylene and of H and ethylene. Our DFT-MC simulations indicate that Au and Ag segregate on the PdAu(111) and PdAg(111) surfaces while Pd is enriched on the PdCu(111) surface under vacuum conditions. The surface Pd contents of PdAg and PdAu tend to increase under partial hydrogenation conditions. Analyses reveal that the co-adsorption energies on the ideal (bulk-cut) surfaces correlate linearly with the values on the segregated surfaces and there is also a linear relationship for the d-band centers between the ideal and segregated surfaces. The present study provides a way to construct more realistic models for studying reactions on alloy surfaces.

Importance of Pd Distribution to Au–Pd Nanocrystals with High Refractive Index Sensitivity

Plasmonic metal nanoparticles (NPs) show promise in a variety of applications, ranging from theranostics to chemical sensing, with chemical sensing made possible by the sensitivity of the localized surface plasmon resonance (LSPR) to the surrounding dielectric environment. Au NPs have been the standard for LSPR sensing applications due to their narrow plasmon band, tunable LSPR maximum, and relative chemical stability; however, the comparatively low refractive index sensitivity (RIS) and morphological instability of Au nanostructures are limiting factors. Recent research has found that incorporating Pd into Au systems can increase RIS and impart multifunctionality, but how the distribution of Pd within Au-based nanostructures affects LSPR sensing is unclear. Here, Au–Pd heterostructures with different Au–Pd distributions were prepared to systematically study the effect of Pd distribution on RIS. Specifically, symmetrically branched Au nanocrystals with Oₕ symmetry (i.e., octopods) were selected as building blocks as their branch tips concentrate E-fields locally. Using these nanocrystals as seeds, Pd-tipped Au octopods and core@shell Au@Pd octopods were synthesized for comparison to alloy Au–Pd octopods and all-Au octopods. Through experiment and simulation, we show that RIS depends both on Pd loading and location in Au–Pd heterostructures, with the Pd-tipped Au octopods displaying the highest RIS while maintaining a moderate figure of merit. This systematic analysis highlights that localization of Pd at LSPR hotspots is critical to achieving the highest RIS, with this insight intended to guide design of future LSPR sensors that move beyond the all-Au standard.

Shape Changes in AuPd Alloy Nanoparticles Controlled by Anisotropic Surface Stress Relaxation.

The shape of AuPd nanoparticles is engineered by surface stress relaxation, achieved by varying the Au content in nanoparticles of Pd-rich compositions. AuPd nanoparticles are grown in the gas phase for several compositions and growth conditions. Their structure is atomically resolved by HRTEM/STEM and EDX. In pure Pd distributions the dominant structures are FCC truncated octahedra (TO), while increasing the Au content there is a transition to icosahedral (Ih) structures in which Au atoms are preferentially placed at the nanoparticle surface. The transition is sharper for growth conditions closer to equilibrium. The physical origin of the transition is determined with the aid of computer simulations. Global optimization searches and free energy calculations confirm that Ih become the equilibrium structure for increasing the Au content. Atomic stress calculations demonstrate that the TO → Ih shape change is caused by a better relaxation of anisotropic surface stress in icosahedra.

PdAu and PdAuAg composite membranes with reduced film thickness using YSZ as a stainless-steel support modifier

PdAu and PdAuAg alloy membranes were synthesized on top of YSZ-modified planar porous stainless steel supports by electroless deposition. A uniform, continuous and smooth coverage was observed after three YSZ deposition calcination cycles, with neither uncovered zones nor detachment after calcination at 673 K. Through this modification procedure, we could obtain thinner and more robust PdAu and PdAuAg alloy membranes. These membranes showed higher hydrogen permeance during the evaluations (623–723 K) and high thermal stability during the long-term stability test. The PdAu and PdAuAg membranes exhibited a good performance during the exposure to CO/H2O steam mixture. Contrary to the PdAu membrane, where no significant change on the atomic surface composition was observed, silver segregation was evidenced on the PdAuAg membrane after exposure to CO/H2O steam mixture.

Sulfur spillover driven by charge transfer between AuPd alloys and SnO2 allows high selectivity for dimethyl disulfide gas sensing

• Ultrafine AuPd alloys modified SnO 2 materials are fabricated by a co-reduction way. • SnO 2 /AuPd materials show superior sensing signals to dimethyl disulfide at 135 °C. • SnO 2 /AuPd sensors show high response value and selectivity to dimethyl disulfide. • The sensing process is probed by combining DFT calculations and in-situ techniques. Monometallic-catalyst modification is a popular means for boosting sensing performances of gas sensors based on semiconductor metal oxides, but it is restricted to the single-type of catalytic activity, hardly insuring high-level regulation of sensor performances. Herein, through combining density functional theory (DFT) calculations and in-situ testing technologies, we presented the modulation of both electronic structure and reaction kinetic process of the sensing surfaces by introducing bimetal alloy catalysts. When used AuPd alloys to modify SnO 2 surfaces, it appeared obviously discriminative sensing behaviors, possessing high response signal (R air /R gas = 36.6) and ultra-high selectivity to 10 ppm dimethyl disulfide (DMDS) gas at 135 °C, which is considerably different from pure SnO 2 , monometallic Au or Pd doped SnO 2 . DFT calculations confirmed the occurrence of the charge transfer that was from AuPd alloys to SnO 2 and the reinforce of surface adsorption strength for DMDS, which may be a major reason for a high gas response to DMDS. In-situ diffuse scattering Fourier transform infrared spectra and quasi in-situ XPS test demonstrated that the surface reaction site for DMDS molecules was mainly located on surfaces of AuPd alloys, and the “sulfur spillover” that generated from alloys surfaces to SnO 2 played a crucial role during DMDS-sensing process, which was further validated by kinetic reaction-pathway calculations. This work will enrich basic research of catalytic electronics in sensor field.

PdAu alloy nano wires for the elevated alcohol electro-oxidation reaction

In the search of a satisfactory electrocatalyst for fuel cells, herein, we are reporting Au rich PdAu nano wires with excellent electro-catalytic activity towards methanol and ethanol oxidation. Ultrathin one-dimensional PdAu nanowires were prepared rapidly through a simple one step process. Among the prepared catalysts, the 10% Pd incorporated PdAu nano wire catalyst imparted greater catalytic activity, which exhibited ten times enhancement higher activity towards methanol as well as six times higher activity towards ethanol than that of the pure Pd catalyst. Eventually, the amount of Pd metal reduced to 90% without compromising its catalytic efficiency. Distinctive properties of one-dimensional Au were attributed to the improved catalytic activity.

Electrochemical impedance spectroscopy study of corrosion characteristics of palladium-silver dental alloys.

Electrochemical impedance spectroscopy (EIS) has been used to obtain insight into corrosion processes for three Pd-Ag alloys, and compare their behavior with an Au-Pd alloy. Five specimens of each alloy received clinically-appropriate simulated porcelain-firing heat treatment. EIS testing was performed at ambient temperature, using 0.09% NaCl, 0.9% NaCl and Fusayama solutions. EIS data are presented as Bode plots. At the open-circuit potential (OCP), the data fit a modified Randles equivalent electrical circuit with a constant phase element (CPE), and the charge-transfer resistance (RCT ) and the two CPE parameters (CPE-T and CPE-P) were determined. The area-normalized capacitance of the double layer (Cdl ) was also calculated. The EIS data at two relevant elevated potentials in the passive range were also found to fit well a modified Randles equivalent circuit with different values for the charge transfer resistance and CPE parameters. At the OCP no significant effect on RCT was found for the alloys and electrolytes, and both alloy and electrolyte significantly affected CPE-P. In vitro corrosion was controlled by charge transfer and charge accumulation processes, and the behavior differed at the elevated potentials compared to the OCP. Significant effects were found for alloy, electrolyte, and alloy/electrolyte interaction on Cdl at the OCP. The EIS parameters at elevated potentials indicate that the Pd-Ag alloys should have satisfactory clinical corrosion resistance. The EIS analyses yielded information about in vitro corrosion of these alloys that cannot be obtained from potentiodynamic polarization testing.

Effective Intratumoral Retention of [103 Pd]AuPd Alloy Nanoparticles Embedded in Gel-Forming Liquids Paves the Way for New Nanobrachytherapy.

Local application of radioactive sources as brachytherapy is well established in oncology. This treatment is highly invasive however, due to the insertion of millimeter sized metal seeds. The authors report the development of a new concept for brachytherapy, based on gold-palladium (AuPd) alloy nanoparticles, intrinsically radiolabeled with 103 Pd. These are formulated in a carbohydrate-ester based liquid, capable of forming biodegradable gel-like implants upon injection. This allows for less invasive administration through small-gauge needles. [103 Pd]AuPd nanoparticles with sizes around 20nm are prepared with radiolabeling efficiencies ranging from 79% to >99%. Coating with the hydrophobic polymer poly(N-isopropylacrylamide) leads to nanoparticle diameters below 40nm. Dispersing the nanoparticles in ethanol with water insoluble carbohydrate esters gives "nanogels", a low viscosity liquid capable of solidifying upon injection into aqueous environments. Both nanoparticles and radioactivity are stably retained in the nanogel over 25 days (>99%) after formation in aqueous buffers. Animals bearing CT26 murine tumors are injected intratumorally with 25 MBq of the 103 Pd-nanogel, and display tumor growth delay and significantly increase median survival times compared with control groups. Excellent retention in the tumor of both the 103 Pd and the nanoparticle matrix itself is observed, demonstrating a potential for replacing currently used brachytherapy seeds.

Ultrasmall PdAu alloy nanoparticles anchored on amine-functionalized hierarchically porous carbon as additive-free catalysts for highly efficient dehydrogenation of formic acid

The role of mass transport for bubble generation reaction as formic acid (FA) dehydrogenation has been overlooked for a long time that the turnover frequency (TOF) values of the majority of the catalysts are limited to less than 1000 h−1. Here, we proposed a design principle of efficient catalyst for this type of reaction that the synergism of highly active catalytic components and developed porous structure of the support required for effective mass transport is indispensable. Based on this cognition, well-dispersed and ultrasmall PdAu alloy nanoparticles (∼2 nm) supported in amine-functionalized hierarchically porous carbon (HPC-NH2) have been prepared via an impregnation-reduction method. Notably, owing to the electronic effect of the PdAu alloy clusters and the introduced basic amine sites, as well as the hierarchically porous structure of the support, the optimal Pd60Au40/HPC-NH2 catalyst exhibits a TOF value up to 3763 h−1 at room temperature and 29,210 h−1 at 323 K.

Efficient electrocatalytic formic acid oxidation over PdAu-manganese oxide/carbon

Developing high efficient Palladium-metal-based electrocatalysts is of great significance for formic acid oxidation (FAO) reaction. Here, we experimentally synthesize PdAu alloy composited with MnOx electrocatalyst (PdAu-MnOx/C) and illustrate its remarkable FAO performance. By virtue of theory studies, we find that Pd-Au bridges have superior adsorption ability towards HCOO* and oxygen vacancies in MnOx make HCOO* formation from HCOOH easier, synergistically lead to the outstanding FAO performance with specific activity and mass activity of 19.0 mA cm−2 and 4539 mA mg−1Pd+Au respectively, which are 2.6 times and 3.5 times higher than commercial Pd/C. This work shed some light toward development of high-performance Pd-based electrocatalysts for FAO.

Towards High Efficacy of Pd-Au/C Catalyst for Tetrachloromethane Hydrodechlorination

We present an efficient strategy for synthesising the PdAu catalysts with a homogeneous PdAu alloy phase for environmentally important hydrodechlorination of tetrachloromethane in the gas phase. The synthesis of carbon-supported catalysts involved two major steps: (i) incorporation of palladium and gold nanoparticles into carbon support and (ii) activation of the catalysts. The critical part of this work was to find the optimal conditions for both steps. Thus, the incorporation of the nanoparticles was carried out in two ways, by impregnation and direct redox reaction method using acetone solutions of metal precursor salts. The activation was performed either by a conventional thermal reduction in hydrogen or flash irradiation in a microwave oven. The homogeneity and structure of the PdAu alloy were found to depend on the catalyst activation method critically. In all cases, we observed better homogeneity for catalysts that were subject to microwave irradiation. Moreover, the flash microwave irradiation of prepared catalysts provided catalysts of better stability and selectivity towards the desired products (hydrocarbons) in the hydrodechlorination of tetrachloromethane as compared to the catalyst obtained by conventional thermal activation in hydrogen.

Bimetallic AuPd Alloy Nanoparticles Decorated on Macroporous WO3 Supports for Selective Detection of Acetone

Three-dimensional ordered macroporous (3DOM) metal-oxide-based materials have received much attention in the field of gas sensing for their potential in breath acetone analysis. The major challenge of metal-oxide-based sensors for analyzing acetone from exhalation is their poor selectivity in the complex mixture of breath. Functionalizing of sensitive materials by noble metal nanoparticles (NPs) is one of the efficient methods to improve gas sensing selectivity, but noble metal NPs are prone to aggregation at the working temperature. To address these issues, we herein have constructed a series of AuPd/WO3 materials by depositing bimetallic AuPd alloy NPs on the surface of 3DOM WO3 supports. The amount of AuPd NP content and Au/Pd molar ratio are optimized on the basis of acetone responses. The sensor based on the optimal AuPd alloy NP-decorated 3DOM WO3 (AuPdW) exhibits high responses to trace acetone with rapid response/recovery speeds. Besides, the AuPdW sensor presents excellent acetone selectivity and good reproducibility. More attractively, the responses of the sensor to acetone exhibit no noticeable decline over 8 weeks, indicating good long-term stability of the synthesized material. We suggest that the improved responses and excellent selectivity to acetone are ascribed to the synergistic effect of electronic sensitization and chemical sensitization of AuPd alloy NPs. The good long-term stability of AuPdW is attributed to the steric hindrance effect of 3DOM structure to AuPd NPs.

Nanoparticle-Catalyzed Green Chemistry Synthesis of Polybenzoxazole.

Enabling catalysts to promote multistep chemical reactions in a tandem fashion is an exciting new direction for the green chemistry synthesis of materials. Nanoparticle (NP) catalysts are particularly well suited for tandem reactions due to the diverse surface-active sites they offer. Here, we report that AuPd alloy NPs, especially 3.7 nm Au42Pd58 NPs, catalyze one-pot reactions of formic acid, diisopropoxy-dinitrobenzene, and terephthalaldehyde, yielding a very pure thermoplastic rigid-rod polymer, polybenzoxazole (PBO), with a molecular weight that is tunable from 5.8 to 19.1 kDa. The PBO films are more resistant to hydrolysis and possess thermal and mechanical properties that are superior to those of commercial PBO, Zylon. Cu NPs are also active in catalyzing tandem reactions to form PBO when formic acid is replaced with ammonia borane. Our work demonstrates a general approach to the green chemistry synthesis of rigid-rod polymers as lightweight structural materials for broad thermomechanical applications.

Cortisol AuPd plasmonic unclad POF biosensor

This paper presents the development and feasibility tests of a cortisol immunosensor. The sensor is based on surface plasmon resonance (SPR) using an unclad plastic optical fiber (POF) in which the SPR is used as sensitivity enhancer, promoted by a gold/palladium (AuPd) alloy coating. The AuPd coated fibers were functionalized with an anti-cortisol antibody and passivated with bovine serum albumin (BSA) to be tested in the presence of cortisol as target analyte. The antibody-antigen binding reaction caused a variation of the refractive index on the surface of the AuPd coating, which leads to a shift of the SPR signature wavelength. The sensor was tested for different cortisol concentrations, ranging from 0.005 to 10 ng/mL. The reported biosensor presented a total wavelength shift of 15 nm for the testing range, putting in evidence a high sensitivity. Control tests for selectivity assessment were also performed. Concentrations as high as 10 ng/mL of cortisol, in a sensor functionalized with anti-hCG antibodies, only resulted in 1 nm variation of the resonance wavelength, 15 times lower than the one functionalized with the anti-cortisol antibodies, which indicates a high selectivity for the proposed approach. For this sensing approach the limit of detection (LOD) was determined to be 1 pg/mL. The proposed SPR based POF sensor has a low-cost interrogation method, high sensitivity and low LOD, straightforward signal processing and find important applications in different biological fields.

Quantifying oxygen induced surface enrichment of a dilute PdAu alloy catalyst

The surface composition of dilute PdAu catalysts is dynamic and difficult to resolve. Using CO pulse titration, we determine that after oxygen treatment a three-fold enrichment of Pd is seen on the surface of a dilute PdAu catalyst.

The effect of curing mode of dual-cure resin cements on bonding performance of universal adhesives to enamel, dentin and various restorative materials.

The effect of curing mode of dual-cure resin cements on the tensile bond strength (TBS) of universal adhesives to enamel, dentin, zirconia, lithium disilicate ceramics (LDS), feldspathic porcelain (FP), and a Pd-Au alloy was evaluated. The substrates were bonded using Tokuyama Universal Bond (TUB) or Scotchbond Universal Adhesive (SBU), followed by luting with Estecem II (ECII) or Rely-X Ultimate (RXU), respectively, which were used either in light-curing or self-curing mode. The TBS test was performed after 24 h or 5,000 thermal cycles. Light-curing significantly improved the 24-h TBS of TUB/ECII to enamel, dentin and FP, as well as the TBS of SBU/RXU to all substrates except LDS. After thermal cycling, light-curing significantly increased the TBS of both adhesives/cements to dentin, but significant differences between curing modes were seldom observed for other substrates. This suggested that light-curing is essential for the hydrophilic dentin, but self-curing might be sufficient for other substrates.