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Palladium absorbs large volumetric quantities of hydrogen at room temperature and ambient pressure, making the palladium hydride system a promising candidate for hydrogen storage. Here, we use Bragg coherent diffraction imaging to map the strain associated with defects in three dimensions before and during the hydride phase transformation of an individual octahedral palladium nanoparticle, synthesized using a seed-mediated approach. The displacement distribution imaging unveils the location of the seed nanoparticle in the final nanocrystal. By comparing our experimental results with a finite-element model, we verify that the seed nanoparticle causes a characteristic displacement distribution of the larger nanocrystal. During the hydrogen exposure, the hydride phase is predominantly formed on one tip of the octahedra, where there is a high number of lower coordinated Pd atoms. Our experimental and theoretical results provide an unambiguous method for future structure optimization of seed-mediated nanoparticle growth and in the design of palladium-based hydrogen storage systems. Palladium can absorb high volumes of hydrogen, but the morphology and 3D displacements occurring during palladium hydride phase formation are not fully characterized in the literature. Here, the authors use Bragg coherent diffraction imaging to map the strain within an individual palladium nanoparticle before and during hydride phase transformation, identifying a characteristic displacement caused by the seed particle in the nanocrystal.

Modulation of bimetallic nanocatalysts with atomic precision would allow for significant increases in catalyst activity through the optimization of heteroatomic interplay. In practice, this level o...

Flexible and free-standing thin films were fabricated and employed directly as working electrodes for the electrochemical reduction of CO2 in 0.5 N KHCO3 at 25 °C, in which, various sizes of Cu2O nanocubes (~ 27 ± 2, 37 ± 3, 62 ± 4 and 207 ± 3 nm) with different extent of surface oxidation (13, 20, 66, and 64% of Cu(II)) were reinforced on to polyvinyl alcohol/reduced graphene oxide matrix (PVA/rGO/(Cu2O/CuO_X, where, X = without halide, Cl, Br and I). The size of Cu2O nanocubes and their surface oxidation were systematically altered by the addition of 1 mL of 10 mM sodium halides (NaCl, NaBr, and NaI) during the synthesis. Energy-dispersive X-ray spectroscopy mapping displayed the specific adsorption of Cl− ions over the Cu2O surface, whereas Br− and I− ions did not show such behaviour. PVA/rGO/(Cu2O/CuO_Cl) thin film exhibited a low overpotential of 20 mV for CO2 reduction reaction and, ~ 60 and ~ 7 times higher current density at − 0.80 V vs. RHE compared to that of the PVA/rGO/(Cu2O/CuO), PVA/rGO/(Cu2O/CuO_Br) ≈ PVA/rGO/(Cu2O/CuO_I), respectively. Gas chromatography and 1H-NMR analyses confirmed methanol as the single liquid product, with a faradaic efficiency of 63% at − 0.75 V vs. RHE on PVA/rGO/(Cu2O/CuO_Cl) thin film.

Palladium absorbs large volumetric quantities of hydrogen at room temperature and ambient pressure, making the Pd-H system a promising candidate for hydrogen storage. Here, we use Bragg coherent diffraction imaging to map the strain associated with defects in three dimensions before and during the hydride phase transformation of an individual octahedral palladium nanoparticle, synthesized by using the seed-mediated approach. The displacement distribution imaging unveils the location of the seed nanoparticle in the final nanocrystal. By comparing our experimental results with a finite-element model, we verify that the seed nanoparticle causes a characteristic displacement distribution of the larger nanocrystal. During the hydrogen exposure, the hydride phase is predominantly formed on one tip of the octahedra, where there is a high number of lower coordinated Pd atoms. Our experimental and theoretical results provide an unambiguous method for future structure optimization of seed-mediated nanoparticles growth and in the design of palladium-based hydrogen storage systems.

We investigated lattice strain on alloyed surfaces using ∼10 nm core–shell nanoparticles with controlled size, shape, and composition. We developed a wet-chemistry method for synthesizing small octahedral PdPt alloy nanoparticles and Au@PdPt core–shell nanoparticles with Pd–Pt alloy shells and Au cores. Upon introduction of the Au core, the size and shape of the overall nanostructure and the composition of the alloyed PdPt were maintained, enabling the use of the electrooxidation of formic acid as a probe to compare the surface structures with different lattice strain. We have found that the structure of the alloyed surface is indeed impacted by the lattice strain generated by the Au core. To further reveal the impact of lattice strain, we fine-tuned the shell thickness. Then, we used synchrotron-based X-ray diffraction to investigate the degree of lattice strain and compared the observations with the results of the formic acid electrooxidation, suggesting that there is an optimal intermediate shell thickness for high catalytic activity.

Control of morphology in the synthesis of Rh nanocrystals can be used to precisely tailor the electronic surface structure; this in turn directly influences their performance in catalysis applications. Many works bring attention to the development of Rh nanostructures with low-index surfaces, but limited effort has been placed on the study of high-index and surface-defect-enriched nanocrystals as they are not favored by thermodynamics due to the involvement of high-energy surfaces and increased surface-to-volume ratios. In this work, we demonstrate an aqueous synthesis of concave Rh nanotetrahedra (CTDs) serving as efficient catalysts for energy conversion reactions. CTDs are surface-defect-rich structures that form through a slow growth rate and follow the four-step model of metallic nanoparticle growth. By tuning the surfactant concentration, the morphology of Rh CTDs evolved into highly excavated nanotetrahedra (HETDs) and twinned nanoparticles (TWs). Unlike the CTD surfaces with abundant adatoms and v...

Controlling the surface composition of shaped bimetallic nanoparticles could offer precise tunability of geometric and electronic surface structure for new nanocatalysts. To achieve this goal, a platform for studying the intermixing process in a shaped nanoparticle was designed, using multilayered Pd-Ni-Pt core-shell nanocubes as precursors. Under mild conditions, the intermixing between Ni and Pt could be tuned by changing layer thickness and number, triggering intermixing while preserving nanoparticle shape. Intermixing of the two metals is monitored using transmission electron microscopy. The surface structure evolution is characterized using electrochemical methanol oxidation. DFT calculations suggest that the low-temperature mixing is enhanced by shorter diffusion lengths and strain introduced by the layered structure. The platform and insights presented are an advance toward the realization of shape-controlled multimetallic nanoparticles tailored to each potential application.

In this study, CuFeO2 and Mg-doped CuFeO2 powders are synthesized by using a novel chemical solution route under an ambient atmosphere. By regulating the pH of the reaction solution, on the basis of Pourbaix diagrams, and the stoichiometric ratio of copper to iron ions, delafossite CuFeO2 powders are formed at 363 K in an aqueous solution. Mg-doped CuFeO2 powders are also synthesized by using the same chemical route with the trace addition of Mg(II) ions. From the powder X-ray diffraction results, all diffraction peaks are of the delafossite structure with dominated 3R phase and few 2H phase. X-ray photoelectron spectroscopy measurements show that the chemical environments of the Cu and Fe ions are consistent with the binding energies of Cu(I) and Fe(III) in the delafossite structure of CuFeO2. The UV–vis spectra show that the CuFeO2 and Mg-doped CuFeO2 powders are both able to absorb light with wavelengths ranging from 300 to 700 nm. The calculated optical band gaps of the CuFeO2 and Mg-doped CuFeO2 powders are 1.35 and 1.5 eV, respectively. With regard to the application of the powders in the photodegradation of 50 ppm methylene blue, the results suggest that at an incident light irradiation of AM 1.5G, the photodegradation efficiency of the Mg-doped CuFeO2 powder is remarkably better than that of the CuFeO2 powder, which can be attributed to its higher carrier concentration. Furthermore, at an external bias of −1.2 V, these delafossite catalysts are able to convert CO2 to ethylene glycol through an electrocatalytic reaction.

Au-Pd nanocrystals are an intriguing system to study the integrated functions of localized surface plasmon resonance (LSPR) and heterogeneous catalysis. Gold is both durable and can harness incident light energy to enhance the catalytic activity of another metal, such as Pd, via the SPR effect in bimetallic nanocrystals. Despite the superior catalytic performance of icosahedral (IH) nanocrystals compared to alternate morphologies, the controlled synthesis of alloy and core-shell IH is still greatly challenged by the disparate reduction rates of metal precursors and lack of continuous epigrowth on multiply twinned boundaries of such surfaces. Herein, we demonstrate a one-step strategy for the controlled growth of monodisperse Au-Pd alloy and core-shell IH with terraced shells by turning an ionic switch between [Br(-)]/[Cl(-)] in the coreduction process. The core-shell IH nanocrystals contain AuPd alloy cores and ultrathin Pd shells (2 nm). They not only display more than double the activity of the commercial Pd catalysts in ethanol electrooxidation attributed to monatomic step terraces but also show SPR-enhanced conversion of 4-nitrophenol. This strategy holds promise toward the development of alternate bimetallic IH nanocrystals for electrochemical and plasmon-enhanced catalysis.

Sub-1 nm PtSn nanosheets of 0.6–0.9 nm in thickness were synthesized via a solution colloidal method and were applied as electrooxidation catalysts for methanol oxidation reaction (MOR) and ethanol oxidation (EOR) in alkaline and acid environments. Owing to the specific structural and compositional characteristics, the as-prepared PtSn nanosheets exhibits superior activity and durability relative to commercial Pt black and Pt/carbon catalysts. PtSn nanosheets not only exhibit an outstanding mass activity in MOR (871.6 mA mg Pt−1), which is 2.3 times (371 mA mg Pt−1) and 10.1 times (86.1 mA mg Pt−1) higher than that of commercial Pt/carbon and Pt black respectively, but also display an mass activity in EOR (673.6 mA mg Pt−1) with 5.3 times higher commercial Pt black (127.7 mA mg Pt−1) and 2.3 times higher than commercial Pt/C catalyst (295 mA mgPt−1). The reported value is the highest activity in both MOR and EOR examinations compared to the reported PtSn-based electrocatalysts,. The improved performance may be due to the highly-reactive exposed (1 1 1) facet sites resulted from its sub-1 nm 2D sheet like morphology.

We probe the acoustic vibrations of silver nanoprisms and gold nano-octahedrons in aqueous solution with four-wave mixing. The nonlinear optical response shows two acoustic vibrational modes: an in-plane mode of nanoprisms with vertexial expansion and contraction; an extensional mode of nano-octahedrons with longitudinal expansion and transverse contraction. The particles were also analyzed with electron microscopy and the acoustic resonance frequencies were then calculated by the finite element analysis, showing good agreement with experimental observations. The experimental mode frequencies also fit with theoretical approximations, which show an inverse dependence of the mode frequency on the edge length, for both nanoprisms and nano-octahedrons. This technique is promising for in situ monitoring of colloidal growth.

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