Anisotropic Pd Research Articles

Bidirectional anisotropic palladium nanozymes reprogram macrophages to enhance collaborative chemodynamic therapy of colorectal cancer

In the complex tumor microenvironment (TME), tumor-associated macrophages (TAMs) play an important role in immunosuppression and tumor growth; hence, tumor cells are no longer the only target during tumor treatment. However, how to simultaneously target both tumor cells and TAMs to effectively eliminate the tumor remains a challenge. Herein, based on the specific receptors for cancer cells and TAMs, we prepared bidirectional anisotropic palladium nanoclusters (Pd-HA+Pd-M@R NPs) to simultaneously target tumor cells and TAMs for enhancing the therapeutic effect. In these nanoclusters, the Pd-HA part was obtained by modifying hyaluronic acid (HA) on the surface of ultra-small Pd nanozymes that could target CT26 cells. Moreover, with the high peroxidase (POD) and catalase (CAT) activity of Pd nanozymes, Pd-HA NPs directly caused cancer cell death by producing H2O2 and highly toxic reactive oxygen therapy (ROS) through chemodynamic therapy (CDT). The other part of Pd NPs functioned as a carrier that linked mannose (Man) and the imiquimod molecule (R837) to obtain Pd-M@R NPs, which could specifically connect the mannose receptor of TAMs and perform targeted reprogramming of TAMs to M1 phenotype to reverse immunosuppression and further activate immunotherapy to form “double therapy”. Therefore, the strategy of “double therapy” provides new sights for treating malignant tumors. Statement of significanceThe bidirectional anisotropic Pd nanoclusters (Pd-HA+Pd-M@R NPs) that can simultaneously target the tumor cells and TAMs with the modification of HA and mannose, respectively. Under the biodirectional anisotropic effect, the Pd nanozymes in Pd-HA can directly kill CT 26 cells through catalyze producing toxic ROS. The Pd-M@R exhibited effectively delivery the imiquimod molecule (R837) to TAMs and specifically induced it transformed into M1 phenotype to reverse tumor immunosuppression to form the "double therapy".

Plasmon-Mediated Nitrobenzene Hydrogenation with Formate as the Hydrogen Donor Studied at a Single-Particle Level

Hydrogenation of nitroaromatics is typically performed under harsh reaction conditions, which would bring safety issues and energy waste. The key for the hydrogenation reaction is to finely control the product selectivity under mild conditions. Herein, the anisotropic Pd–Au nanorods (NRs) exhibited efficient plasmon-enhanced selective hydrogenation of nitrobenzene to aniline with formate as the hydrogen donor. Under visible-light irradiation, both conversion and selectivity for nitrobenzene hydrogenation can reach nearly 100%. Plasmon-induced interaction between formic acid (FA), nitrobenzene, and plasmonic nanostructures was explored by single-particle photoluminescence (PL) measurement in situ. The complete quenching phenomenon of localized surface plasmon resonance PL for single Pd–Au NR was observed when immersed in FA. In addition, light-induced adsorption enhancement of nitrobenzene was discovered, which is vital for the plasmon-enhanced catalysis. This work provides direct evidence for the carrier transfer from Au–Pd NRs to FA via single-particle PL measurement and will give guidance to the rational design of hybrid plasmonic catalysts to promote eco-friendly organic conversion.

High-Density Pd Nanorod Arrays on Au Nanocrystals for High-Performance Ethanol Electrooxidation.

In the synthesis of Au/Pd bimetallic nanocrystals, a layer-by-layer growth is favored, owing to the low bonding energy between Pd atoms ( EPd-Pd) in comparison with EAu-Pd, resulting in homogeneous core/shell nanostructures. Herein, we demonstrate designed synthetic tactics to unconventional Au/Pd heterostructures through a deposition-dominant growth pathway of the newly reduced Pd atoms, which break the intrinsically favored layer-by-layer growth. Pd thus grows on Au seeds in a heterogeneous nucleation manner. The resulting anisotropic Pd nanorods array on the two basal facets and three side facets of the Au triangular seeds in a high density to form 2D/1D Au/Pd heterostructures. It is noticed that Pd nanorods align in an extremely high order. They grow almost in a row with the base of the rod located overlapped on the Au surface. This versatile approach has been also applied to other Au nanocrystal seeds, involving hexagonal nanoplates, circular nanodisks, nanorods, and nanobipyramids. Furthermore, the 2D/1D Au/Pd heterostructures exhibit an enhanced electrocatalytic performance toward ethanol oxidation in alkaline condition, owing to their unique structure and the exposure of Au. We believe that our synthetic strategy is highly valuable for the construction of multimetallic nanostructures with desired architectures and thus intriguing properties.

Size and Shape Controlled Synthesis of Pd Nanocrystals

Abstract Palladium (Pd) has attracted substantial academic interest due to its remarkable properties and extensive applications in many industrial processes and commercial devices. The development of Pd nanocrystals (NCs) would contribute to reduce overall precious metal loadings, and allow the efficient utilization of energy at lower economic costs. Furthermore, some of the important properties of Pd NCs can be substantially enhanced by rational designing and tight controlling of both size and shape. In this review, we have summarized the state-of-the-art research progress in the shape and size-controlled synthesis of noble-metal Pd NCs, which is based on the wet-chemical synthesis. Pd NCs have been categorized into five types: (1) single-crystalline Pd nano-polyhedra with well-defined low-index facets (e.g. {100}, {111} and {110}); (2) single-crystalline Pd nano polyhedra with well-defined high-index facets, such as Pd tetrahexahedra with {hk0} facets; (3) Pd NCs with cyclic penta-twinned structure, including icosahedra and decahedra; (4) monodisperse spherical Pd nanoparticles; (5) typical anisotropic Pd NCs, such as nanoframes, nanoplate, nanorods/wires. The synthetic approach and growth mechanisms of these types of Pd NCs are highlighted. The key factors that control the structures, including shapes (surface structures), twin structures, single-crystal nanostructures, and sizes are carefully elucidated. We also introduce the detailed characterization tools for analysis of Pd NCs with a specific type. The challenges faced and perspectives on this promising field are also briefly discussed. We believe that the detailed studies on the growth mechanisms of NCs provide a powerful guideline to the rational design and synthesis of noble-metal NCs with enhanced properties. Graphical Abstract:

Reusable and Flexible Heterogeneous Catalyst for Reduction of TNT by Pd Nanocube Decorated ZnO Nanolayers onto Electrospun Polymeric Nanofibers

An effective method for the fabrication of well designed nanocomposite for the catalytic reduction of 2,4,6-trinitrotoluene (TNT) was developed. Here, cubic palladium (Pd) nanoparticles were utilized for enhancing the interface properties, attachment quality, catalytic yield and stability after the catalysis reactions. Ligand controlled facet growth by the Br- anions during thermal decomposition of the palladium-precursor resulted with cubic shaped average ∼13 nm palladium nanocubes (Pd NC). The anisotropic Pd NC were utilized to decorate the surface of the zinc oxide (ZnO) nanolayers deposited by atomic layer deposition (ALD) technique on the electrospun polyacrylonitrile (PAN) nanofibers. Due to the polymeric nature of the electrospun PAN nanofibers, Pd NC decorated nanoweb is highly flexible and has a high surface area. For the sustainable Pd NC decoration on the ZnO surfaces coated on PAN nanofibers, anchor points were formed by the functional thiol groups which can facilitate the Pd NC attachment and stability on the ZnO surface. The -OH and alkyl thiol groups obtained via sol-gel reactions positioned on the ZnO layer providing a better interface between ZnO and Pd NC which cannot be obtained by pristine PAN nanofibers. Additionally, due to the increased surface interaction, geometrical positioning on fibers for a better intermediate complex formation and stability via soft-soft interaction, Pd NC decorated flexible polymeric electrospun nanoweb provided enhanced catalytic reduction of TNT in aqueous medium.

Facile ultrafine copper seed-mediated approach for fabricating quasi-two-dimensional palladium-copper bimetallic trigonal hierarchical nanoframes

Anisotropic Pd nanoparticles with highly branched morphologies are urgently needed as building blocks for nanoscale devices, catalysts, and sensing materials owing to their novel structures and unique physicochemical properties. However, realizing size control and branch manipulation for these materials is very challenging. In this study, we develop a facile ultrafine Cu seed-mediated approach in the aqueous phase to produce novel Pd–Cu trigonal hierarchical nanoframes (THNFs). The main branch of most of the obtained nanocrystals is tripod-like, with advanced branches along the arms as frame units having self-similarity. In this method, the size of the Pd–Cu THNFs can be flexibly controlled by manipulating the nucleation involving the sub-3 nm Cu seeds. These Pd–Cu THNFs outperform Pd black with regard to their ethanol-oxidation performance, having a specific activity and mass activity 9.7 and 6.6 times higher, respectively. This research provides a versatile ultrafine seed-mediated approach for producing size-controlled anisotropic bimetallic nanoframes.

Bromide (Br−) ion-mediated synthesis of anisotropic palladium nanocrystals by laser ablation

Anisotropic growth of Pd nanoparticles in bromine (Br) containing solution has been studied by pulsed laser ablation. For size and shape control different solutions like water, sodium dodecyl sulphate (SDS) (anionic surfactant), and (Br−) ion containing cetyltrimethylammonium bromide (CTAB) (cationic surfactant) and electrolyte (KBr) were used. In laser ablation surrounding liquid plays a dominant role in controlling size and directional growth. Absorption spectra of as-generated Pd nanoparticles undergo modification with time in different solutions due to Br− ion-mediated directional growth. In water and SDS quasi-spherical and spherical Pd nanoparticles with mean size of 14 and 8nm, respectively, and in CTAB decahedron and icosahedron shape Pd nanocrystals with mean size 65nm were observed. When strong Br− ion source KBr was used sharp edged cuboid shaped large Pd nanoparticles were observed. Surface energy modification due to preferential chemisorption of Br− ions onto {100} planes of Pd resulted in formation anisotropic Pd nanostructures enclosed with {100} planes. The nanocubes exhibit broad plasmon resonance around 250–280nm. Further, size of nanocuboids were controlled by using mixed solutions of KBr with SDS and CTAB for tunable plasmon resonance wavelength from 230 to 550nm.

Pd-on-Au Supra-nanostructures Decorated Graphene Oxide: An Advanced Electrocatalyst for Fuel Cell Application

We report a very easy and effective approach for synthesizing unique palladium-on-gold supra-nanostructure (Au@Pd-SprNS)-decorated graphene oxide (GO) nanosheets. The SprNSs comprising Au nanorods as core and a unique close-packed assembly of tiny anisotropic Pd nanoparticles (NPs) as shell were homogeneously distributed on the GO surface via electrostatic self-assembly. Compared with the traditional one-pot method for synthesis of metal NPs on GO sheets, the size and shape of core-shell Au@Pd SprNSs can be finely controlled and uniformly distributed on the GO carrier. Interestingly, this Au@Pd-SprNSs/GO nanocomposite displayed high electrocatalytic activities toward the oxidation of methanol, ethanol, and formic acid, which can be attributed to the abundance of intrinsic active sites including high density of atomic steps, ledges and kinks, Au-Pd heterojunctions and cooperative action of the two metals of the SprNSs. Additionally, uniform dispersion of the SprNSs over the GO nanosheets prevent agglomeration between the SprNSs, which is of great significance to enhance the long-term stability of catalyst. This work will introduce a highly efficient Pd-based nanoelectrocatalyst to be used in fuel cell application.

Refractive index susceptibility of palladium nanoplates with plasmonic resonance in the visible region

We synthesized anisotropic Pd nanoplates for use as a novel refractive index (RI) sensing material in the visible region. The nanoplates showed an extinction peak that was attributed to the excitation of the localized surface plasmon resonance at ~620 nm in the visible region. It was found that the peak was red-shifted with increasing the RI of the surrounding medium. The susceptibility was calculated to be 250 nm per RI unit, comparable to some anisotropic Au nanoparticles that are excellent RI sensing materials.

A Strategy for the Formation of Gold–Palladium Supra-Nanoparticles from Gold Nanoparticles of Various Shapes and Their Application to High-Performance H2O2 Sensing

We present a new approach for the synthesis of gold (Au)–palladium (Pd) bimetallic supra-nanoparticles in which densely packed anisotropic Pd nanostructures surround a central Au nanoparticle (rod, sphere, cubic shape). They were obtained by means of Pd crystal growth on Au nanoparticle surfaces which are modified with a mixture of cetyltrimethylammonium bromide (CTAB) and 5-bromosalicylic acid (5-BrSA). From a comparative study with a Au nanorod (NR) as a seed, the use of the CTAB/5-BrSA mixture plays a pivotal role in obtaining such unique supra-structures; the Au NR capped with only CTAB resulted in Au core–continuous Pd shell nanoparticles instead. The Au–Pd supra-nanoparticles provide active surface area for electrocatalytic activities higher than that of the Au@Pd continuous shell nanoparticles, displaying outstanding performance for mediator-free electrochemical detection of H2O2.

Plasmon-enhanced formic acid dehydrogenation using anisotropic Pd-Au nanorods studied at the single-particle level.

Plasmonic bimetal nanostructures can be used to drive the conventional catalytic reactions efficiently at low temperature with the utilization of solar energy. This work developed Pd-modified Au nanorods, which work as the light absorber and the catalytically active site simultaneously, and exhibit efficient plasmon-enhanced catalytic formic acid dehydrogenation even when below room temperature (5 °C). Plasmon-induced interface interaction and photoreaction dynamics of individual nanorods were investigated by single-particle photoluminescence measurement, and a complete quenching phenomenon at the LSPR region was observed for the first time. More importantly, the spatial distribution of the SPR-induced enhancement, analyzed by the finite difference time domain (FDTD) simulation, shows that only tip-coated Pd can be affected for the occurrence of plasmon resonance energy transfer. This finding provides a route to decrease the amount of Pd species by the selective deposition only at the field-enhanced sites.

A facile approach for morphosynthesis of Pd nanoelectrocatalysts

A facile approach has been developed for synthesis of highly-structured, anisotropic Pd nanostructures. The dendritic Pd nanostructures show superior performance toward oxidation of formic acid and methanol for fuel cell application.

A Rapid Synthesis of Oriented Palladium Nanoparticles by UV Irradiation

Palladium nanoparticles of average size around 8 nm have been synthesized rapidly by UV irradiation of mixture of palladium chloride and potassium oxalate solutions. A rod-shaped palladium oxalate complex has been observed as an intermediate. In the absence of potassium oxalate, no Pd nanoparticles have been observed. The synthesized Pd nanoparticles have been characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), selective area electron diffraction and energy dispersive analysis by X-rays (EDAX) analyses. XRD analysis indicates the preferential orientation of catalytically active {111} planes in Pd nanoparticles. A plausible mechanism has been proposed for the formation of anisotropic Pd nanoparticles.

Preparation of nanostructured Pd particles using a seeding synthesis approach—Application to the selective hydrogenation of buta-1,3-diene

Well-defined nanostructured Pd particles were successfully synthesized in aqueous solution using a seeding-mediated approach with cetyltrimethylammonium bromide (CTAB) acting as both capping and structure-directing agent. Four well-defined nanoobjects were obtained: nanocubes, nanotetrahedra, nanopolyhedra, and nanorods. The anisotropic Pd nanorods exposed preferentially {1 0 0} facets due to the stabilization effect of CTAB. After deposition onto α-Al2O3, these nanostructured Pd particles were tested in the selective hydrogenation of buta-1,3-diene at 298 K under 20 bars of H2. Compared to an isotropic Pd catalyst, anisotropic Pd catalysts were found highly selective for the hydrogenation of buta-1,3-diene into butenes without further hydrogenation into butane. Moreover, on the nanostructured catalysts, further hydrogenation of but-1-ene into butane is reduced while but-2-enes were hardly converted. Finally, an unusual high level of cis but-2-ene isomer was observed. These results suggest a modification of the mechanism usually admitted for Pd catalysts when a well-defined nanomorphology is achieved.

Anisotropic Growth of Metal Chains on Anisotropic Substrate

Based on the exchange mechanism of metal islands growth on anisotropic metal surfaces, the growth processes of anisotropic Cu islands on the anisotropic Pd (110) surface are investigated by Monte Carlo simulations with realistic growth model and physical parameters. The anisotropic diffusion and anisotropic sticking of Cu adatoms are included in the simulation model after being considered the anisotropy of Pd (110) surface and compared to the experiments. It is found that the larger diffusion rate along the [110] channels of Pd (110) surface gives rise to a slower growth rate of Cu island in this direction, unless special effect of the anisotropic sticking is invoked. The simulation results show that the shape anisotropy of Cu islands is mainly due to the sticking anisotropy rather than the diffusion anisotropy.