Search Results (16)

Hollow flower-like multi-metallic nanocrystals have attracted significant research attention due to their exceptional catalytic properties, which stem from their high surface area-to-volume ratio and abundant active sites. Nevertheless, conventional synthesis methods for noble metal nanocrystals typically involve complex procedures or require harsh reaction conditions. In this work, we developed a facile and environmentally benign strategy for fabricating hollow flower-shaped trimetallic nanocrystals at ambient temperature. Our approach employs AgCl nanocubes, derived from AgNO₃ and HAuCl₄, as self-sacrificing templates. Through ascorbic acid-mediated reduction of metal precursors, we successfully synthesized three distinct types of hollow flower-like nanocrystals: AuAgCu, AuAgPt, and AuAgPd. Comprehensive characterization confirmed the well-defined morphology and precise composition control of the as-prepared nanocrystals. The catalytic performance was systematically evaluated through in situ UV–vis spectroscopy monitoring of 4-nitrophenylthiophenol reduction, revealing the following activity trend: AuAgCu > AuAgPt > AuAgPd. This study not only provides a versatile platform for constructing sophisticated multi-metallic nanostructures but also offers valuable insights into the structure–activity relationship of complex catalysts. Full article

This research presents a novel, cost-effective, and scalable approach for the direct detection of myoglobin (Myo) in point-of-care (PoC) applications. In this strategy, redox-active Prussian Blue nanocubes (PBNCs) are applied to a disposable platinum screen-printed electrode (Pt-SPE). Subsequently, a biomimetic sensing layer is generated by electropolymerization of ortho-phenylenediamine (o-PD) in the presence of Myo, which forms molecularly imprinted polymer (MIP) sites by cyclic voltammetry (CV). The electropolymerization process takes place in a potential range of −0.2 V to +0.8 V, for five cycles at a scan rate of 50 mV/s, in a 10 mmol/L o-PD solution. After polymerization, the electrode is incubated in trypsin for 2 h to create Myo-specifically imprinted cavities. The structural and morphological properties of the biomimetic layer were analyzed by Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The direct detection of Myo was analyzed by differential pulse voltammetry (DPV). The results showed a linear response to Myo concentrations ranging from 1.0 ag/mL to 10 ng/mL, a limit of detection (LOD) of 0.76 ag/mL, and a R² value of 0.9775. The absence of an external liquid redox probe simplifies the sensor design, improves portability, and reduces the complexity of the assay, making it more suitable for PoC. Full article

A series of bimetallic Pd/Pt truncated nanocube catalysts with similar morphologies and particle sizes but different platinum contents were successfully synthesized using a colloidal method without using any capping agents. Their hydrogenation properties were systematically studied and compared with their monometallic Pd or Pt nanocrystal counterparts. The results of EDX-mapping and line scanning show that platinum was relatively uniformly distributed on the surface of the Pd/Pt bimetallic nanocrystals and was not selectively deposited at the corners of the nanocrystals. The results of the selective hydrogenation of acetophenone demonstrate that the hydrogenation rate and the carbonyl selectivity of bimetallic Pd/Pt truncated nanocube catalysts are generally much higher than those of their monometallic Pd or Pt nanocrystal counterparts. It was found that the electronic interaction between palladium and platinum in the bimetallic Pd/Pt truncated nanocube catalysts and the corresponding hydrogenation activity in the selective hydrogenation of acetophenone are closely related to the molar ratio between platinum and palladium and the thickness of the platinum layer in the bimetallic Pd/Pt truncated nanocube catalyst. With an increase in the Pt/Pd molar ratio in the bimetallic Pd/Pt truncated nanocube catalysts, the activity and carbonyl selectivity in the acetophenone hydrogenation reaction increase first, reach a maximum when the molar ratio of Pt/Pd is 0.02 and the theoretical thickness of Pt is 1.3 atomic layers, and then decrease with a further increase in the Pt/Pd ratio. The hydrogenation rate of acetophenone on the Pd/Pt_0.02 catalyst reaches 1.07 × 10³ mmol·h⁻¹·g_cat.⁻¹, which is 79 and 75 times larger than that of the monometallic Pd and Pt nanocrystal catalysts, respectively. The maximum yield of the target product 1-phenylethanol on the Pd/Pt_0.02 truncated nanocube catalyst reaches 97.2%, which is 6.6% and 16.7% higher than that of the monometallic Pd and Pt nanocrystal catalysts, respectively. Full article

Palladium (Pd) nanocubes, a type of metallic nanostructure, have demonstrated remarkable optoelectronic properties, garnering significant attention. However, their nonlinear optical characteristics and related device applications remain underexplored. In this study, we report the fabrication of a novel saturable absorber (SA) by depositing Pd nanocubes onto a D-shaped fiber (DF). The Pd nanocubes, with an average size of 12 nm, were synthesized and integrated with a DF, resulting in a highly robust SA with broadband saturable absorption characteristics. When incorporated into Er³⁺-doped laser cavities, the Pd-DF SA enabled the generation of ultrafast pulses with a central wavelength of 1560 nm, a corresponding repetition rate of 26.7 MHz, and a temporal width of 1.85 ps. Our findings highlight the strong potential of the Pd-DF device as a versatile SA for constructing high-energy ultrafast fiber lasers. Full article

Tailoring the shape of Pd nanocrystals is one of the main ways to enhance catalytic activity; however, the effect of shapes and electrolyte pH on carbon monoxide oxidation (CO_Oxid) is not highlighted enough. This article presents the controlled fabrication of Pd nanocrystals in different morphologies, including Pd nanosponge via the ice-cooling reduction of the Pd precursor using NaBH₄ solution and Pd nanocube via ascorbic acid reduction at 25 °C. Both Pd nanosponge and Pd nanocube are self-standing and have a high surface area, uniform distribution, and clean surface. The electrocatalytic CO oxidation activity and durability of the Pd nanocube were significantly superior to those of Pd nanosponge and commercial Pd/C in only acidic (H₂SO₄) medium and the best among the three media, due to the multiple adsorption active sites, uniform distribution, and high surface area of the nanocube structure. However, Pd nanosponge had enhanced CO_Oxid activity and stability in both alkaline (KOH) and neutral (NaHCO₃) electrolytes than Pd nanocube and Pd/C, attributable to its low Pd-Pd interatomic distance and cleaner surface. The self-standing Pd nanosponge and Pd nanocube were more active than Pd/C in all electrolytes. Mainly, the CO_Oxid current density of Pd nanocube in H₂SO₄ (5.92 mA/cm²) was nearly 3.6 times that in KOH (1.63 mA/cm²) and 10.3 times that in NaHCO₃ (0.578 mA/cm²), owing to the greater charge mobility and better electrolyte–electrode interaction, as evidenced by electrochemical impedance spectroscopy (EIS) analysis. Notably, this study confirmed that acidic electrolytes and Pd nanocube are highly preferred for promoting CO_Oxid and may open new avenues for precluding CO poisoning in alcohol-based fuel cells. Full article

The rational regulation of catalyst active sites at atomic scale is a key approach to unveil the relationship between structure and catalytic performance. Herein, we reported a strategy for the controllable deposition of Bi on Pd nanocubes (Pd NCs) in the priority order from corners to edges and then to facets (Pd NCs@Bi). The spherical aberration-corrected scanning transmission electron microscopy (ac-STEM) results indicated that Bi₂O₃ with an amorphous structure covers the specific sites of Pd NCs. When only the corners and edges of the Pd NCs were covered, the supported Pd NCs@Bi catalyst exhibited an optimal trade-off between high conversion and selectivity in the hydrogenation of acetylene to ethylene under ethylene-rich conditions (99.7% C₂H₂ conversion and 94.3% C₂H₄ selectivity at 170 °C) with remarkable long-term stability. According to the H₂-TPR and C₂H₄-TPD measurements, the moderate hydrogen dissociation and the weak ethylene adsorption are responsible for this excellent catalytic performance. Following these results, the selectively Bi-deposited Pd nanoparticle catalysts showed incredible acetylene hydrogenation performance, which provides a feasible perspective to design and develop highly selective hydrogenation catalysts for industrial applications. Full article

The design and synthesis of ultra-small-sized Pt-based catalyst with specific effects for enhancing the oxygen reduction reaction (ORR) is an effective way to improve the utilization of Pt. Herein, Pt-Pd-Ni octahedra nanoparticles characterized by the ultra-small size of 4.71 nm were synthesized by a Pd seed-inducing-growth route. Initially, Pd nanocubes were synthesized under solvothermal conditions; subsequently, Pt-Ni was deposited in the Pd seed solution. The Pd seeds were oxidized into Pd²⁺ and combined with Pt²⁺ and Ni²⁺ in the solution and finally formed the ternary alloy small-sized octahedra. In the synthesis process of the ultra-small Pt-Pd-Ni octahedra, Pd nanocube seed played an important role. In addition, the size of the Pt-Pd-Ni octahedra could be regulated by adjusting the concentration rate of Pt-Ni. The ultra-small Pt-Pd-Ni octahedra formation by depositing Pt-Ni with a feeding ratio of 2:1 showed good ORR activity, and the high half-wave potential was 0.933 V. In addition, the Pt-Pd-Ni octahedra showed an enhanced mass activity of 0.93 A mg⁻¹ _Pt+Pd in ORR, which was 5.81 times higher than commercial Pt/C. The theoretical calculation shows that compared to Pt/C, the small-sized ternary alloy octahedra had an obvious contraction strain effect (contraction rate: 3.49%). The alloying effect affected the d-band center of the Pt negative shift. In the four-electron reaction, Pt-Pd-Ni ultra-small octahedra exhibited the lowest overpotential, resulting in the adsorption performance to become optimized. Therefore, the Pd seed-inducing-growth route provides a new idea for exploring the synthesis of small-sized nanoparticle catalysts. Full article

Eliminating clogging in capillary tube reactors is critical but challenging for enabling continuous-flow microfluidic synthesis of nanoparticles. Creating immiscible segments in a microfluidic flow is a promising approach to maintaining a continuous flow in the microfluidic channel because the segments with low surface energy do not adsorb onto the internal wall of the microchannel. Herein we report the spontaneous self-agglomeration of reduced graphene oxide (rGO) nanosheets in polyol flow, which arises because the reduction of graphene oxide (GO) nanosheets by hot polyol changes the nanosheets from hydrophilic to hydrophobic. The agglomerated rGO nanosheets form immiscible solid segments in the polyol flow, realizing the liquid–solid segmented flow to enable clogging aversion in continuous-flow microfluidic synthesis. Simultaneous reduction of precursor species in hot polyol deposits nanocrystals uniformly dispersed on the rGO nanosheets even without surfactant. Cuprous oxide (Cu₂O) nanocubes of varying edge lengths and ultrafine metal nanoparticles of platinum (Pt) and palladium (Pd) dispersed on rGO nanosheets have been continuously synthesized using the liquid–solid segmented flow microfluidic method, shedding light on the promise of microfluidic reactors in synthesizing functional nanomaterials. Full article

Colorimetric enzyme-linked immunosorbent assay (ELISA) has been widely applied as the gold-standard method for cytokine detection for decades. However, it has become a critical challenge to further improve the detection sensitivity of ELISA, as it is limited by the catalytic activity of enzymes. Herein, we report an enhanced colorimetric ELISA for ultrasensitive detection of interleukin-6 (IL-6, as a model cytokine for demonstration) using Pd@Pt core@shell nanodendrites (Pd@Pt NDs) as peroxidase nanomimics (named “Pd@Pt ND ELISA”), pushing the sensitivity up to femtomolar level. Specifically, the Pd@Pt NDs are rationally engineered by depositing Pt atoms on Pd nanocubes (NCs) to generate rough dendrite-like Pt skins on the Pd surfaces via Volmer–Weber growth mode. They can be produced on a large scale with highly uniform size, shape, composition, and structure. They exhibit significantly enhanced peroxidase-like catalytic activity with catalytic constants (Kcat) more than 2000-fold higher than those of horseradish peroxidase (HRP, an enzyme commonly used in ELISA). Using Pd@Pt NDs as the signal labels, the Pd@Pt ND ELISA presents strong colorimetric signals for the quantitative determination of IL-6 with a wide dynamic range of 0.05–100 pg mL⁻¹ and an ultralow detection limit of 0.044 pg mL⁻¹ (1.7 fM). This detection limit is 21-fold lower than that of conventional HRP-based ELISA. The reproducibility and specificity of the Pd@Pt ND ELISA are excellent. More significantly, the Pd@Pt ND ELISA was validated for analyzing IL-6 in human serum samples with high accuracy and reliability through recovery tests. Our results demonstrate that the colorimetric Pd@Pt ND ELISA is a promising biosensing tool for ultrasensitive determination of cytokines and thus is expected to be applied in a variety of clinical diagnoses and fundamental biomedical studies. Full article

The synthesis of Pd@Pt core–shell nanocubes was achieved through a direct seed-mediated growth method. This process represents a simple and cost-effective way to produce core–shell nanocubes. The morphology of the Pd@Pt core–shell nanocubes varied from simple cubic to concave cubic, depending on the reducing agent and the Pt content. The selection of the reducing agent is important because the reduction rate is directly related to the shell growth. The catalytic activity and stability of the Pd@Pt core–shell nanocubes in the methanol oxidation reaction were different for the nanocubes with partial and full Pt shells. Full article

The formation of palladium hydrides is a well-known phenomenon, observed for both bulk and nanosized samples. The kinetics of hydrogen adsorption/desorption strongly depends on the particle size and shape, as well as the type of support and/or coating of the particles. In addition, the structural properties of hydride phases and their distribution also depend on the particle size. In this work, we report on the in situ characterization of palladium nanocubes coated with HKUST-1 metal-organic framework (Pd@HKUST-1) during desorption of hydrogen by means of synchrotron-based time-resolved X-ray powder diffraction. A slower hydrogen desorption, compared to smaller sized Pd nanoparticles was observed. Rietveld refinement of the time-resolved data revealed the remarkable stability of the lattice parameters of α- and β-hydride phases of palladium during the α- to β- phase transition, denoting the behavior more similar to the bulk materials than nanoparticles. The stability in the crystal sizes for both α- and β-hydride phases during the phase transition indicates that no sub-domains are formed within a single particle during the phase transition. Full article

The selective enhancement of catalytic activity is a challenging task, as catalyst modification is generally accompanied by both desirable and undesirable properties. For example, in the case of the direct synthesis of hydrogen peroxide, Pt on Pd improves hydrogen conversion, but lowers hydrogen peroxide selectivity, whereas Au on Pd enhances hydrogen peroxide selectivity but decreases hydrogen conversion. Toward an ideal catalytic property, the development of a catalyst that is capable of improving H-H dissociation for increasing H₂ conversion, whilst suppressing O-O dissociation for high H₂O₂ selectivity would be highly beneficial. Pd-core AuPt-bimetallic shell nanoparticles with a nano-sized bimetallic layer composed of Au-rich or Pt-rich content with Pd cubes were readily prepared via the direct seed-mediated growth method. In the Pd-core AuPt-bimetallic shell nanoparticles, Au was predominantly located on the {100} facets of the Pd nanocubes, whereas Pt was deposited on the corners of the Pd nanocubes. The evaluation of Pd-core AuPt-bimetallic shell nanoparticles with varying Au and Pt contents revealed that Pd-core AuPt-bimetallic shell that was composed of 2.5 mol% Au and 5 mol% Pt, in relation to Pd, exhibited the highest H₂O₂ production rate (914 mmol H₂O₂ g_metal⁻¹ h⁻¹), due to the improvement of both H₂O₂ selectivity and H₂ conversion. Full article

The atomic disorder and the vibrational properties of Pd nanocubes have been studied through a combined use of X-ray diffraction and molecular dynamics simulations. The latter show that the trend of the mean square relative displacement as a function of the radius of the coordination shells is characteristic of the nanoparticle shape and can be described by a combined model: A correlated Debye model for the thermal displacement and a parametric expression for the static disorder. This combined model, supplemented by results of line profile analysis of the diffraction patterns collected at different temperatures (100, 200, and 300 K) can explain the observed increase in the Debye–Waller coefficient, and shed light on the effect of the finite domain size and of the atomic disorder on the vibrational properties of metal nanocrystals. Full article

This article presents a facile, one-pot method using the aqueous phase for the synthesis of high-quality Pd nanocubes. In this study, Pd chloride was used as the precursor, sodium iodide as capping agent, and poly(vinylpyrrolidone) as surfactant and reducing agent. The effects of different halogens on the morphology of Pd nanocrystals were investigated. The results showed that, in this synthesis system, the selection and proper amount of sodium iodide was essential to the preparation of high-quality Pd nanocubes. When iodide was replaced by other halogens (such as bromide and chloride), Pd nanocrystals with cubic morphology could not be obtained. In addition, we have found that NaBH₄ can be used to efficiently remove inorganic covers, such as iodide, from the surface of Pd nanoparticles as synthesized. The Pd nanoparticles obtained were employed as electro-catalysts for formic acid oxidation, and they exhibited excellent catalytic activity and good stability towards this reaction. Full article

In the present work, centrifugal deposited Au-Pd core-shell nanoparticle (NP) film was proposed for the room-temperature optical detection of hydrogen gas. The size dimension of 44, 48, 54, and 62 nm Au-Pd core-shell nanocubes with 40 nm Au core were synthesized following a solution-based seed-mediated growth method. Compared to a pure Pd NP, this core-shell structure with an inert Au core could decrease the H diffusion length in the Pd shell. Through a modified centrifugal deposition process, continues film samples with different core-shell NPs were deposited on 10 mm diameter quartz substrates. Under various hydrogen concentration conditions, the optical response properties of these samples were characterized by an intensity-based optical fiber bundle sensor. Experimental results show that the continues film that was composed of 62 nm Au-Pd core-shell NPs has achieved a stable and repeatable reflectance response with low zero drift in the range of 4 to 0.1% hydrogen after a stress relaxation mechanism at first few loading/unloading cycles. Because of the short H diffusion length due to the thinner Pd shell, the film sample composed of 44 nm Au-Pd NPs has achieved a dramatically decreased response/recovery time to 4 s/30 s. The experiments present the promising prospect of this simple method to fabricate optical hydrogen sensors with controllable high sensitivity and response rate at low cost. Full article