Ligand-mediated formation of Cu/metal oxide hybrid nanocrystals with tunable number of interfaces

Combining domains of different chemical nature within the same hybrid material through the formation of heterojunctions provides the opportunity to exploit the properties of each individual component within the same nano-object; furthermore, new synergistic properties will often arise as a result of unique interface interactions. However, synthetic strategies enabling precise control over the final architecture of multicomponent objects still remain scarce for certain classes of materials. Herein, we report on the formation of Cu/MO_x (M = Ce, Zn and Zr) hybrid nanocrystals with a tunable number of interfaces between the two domains. We demonstrate that the organic ligands employed during the synthesis play a key role in regulating the final configuration. Finally, we show that the synthesized nanocrystals serve as materials platforms to investigate the impact of the Cu/metal oxide interfaces in applications by focusing on the electrochemical CO₂ reduction reaction as one representative example.

We report on the formation of Cu/metal oxide hybrid nanocrystals with a tunable number of interfaces between the two domains. We demonstrate that the organic ligands employed during the synthesis play a key role in regulating the final configuration.     

A Mössbauer spectroscopic study of the magnetocrystalline anisotropy inα-FeOOH

Mössbauer spectra are obtained for a single crystal of -FeOOH, with a magnetic field of up to 10T applied along the c axis. No spin reorientation is observed, indicating a lower limit of 6 × 10⁴ J/m³ for the anisotropy constant K. A theoretical estimate gives K > 1.1 × 10⁶ J/m³.     

Polymer Lamellae as Reaction Intermediates in the Formation of Copper Nanospheres as Evidenced by In Situ X-ray Studies

The classical nucleation theory (CNT) is the most common theoretical framework used to explain particle formation. However, nucleation is a complex process with reaction pathways which are often not covered by the CNT. Herein, we study the formation mechanism of copper nanospheres using in situ X-ray absorption and scattering measurements. We reveal that their nucleation involves coordination polymer lamellae as pre-nucleation structures occupying a local minimum in the reaction energy landscape. Having learned this, we achieved a superior monodispersity for Cu nanospheres of different sizes. This report exemplifies the importance of developing a more realistic picture of the mechanism involved in the formation of inorganic nanoparticles to develop a rational approach to their synthesis.     

Elucidating the structure-dependent selectivity of CuZn towards methane and ethanol in CO2 electroreduction using tailored Cu/ZnO precatalysts

Understanding the catalyst compositional and structural features that control selectivity is of uttermost importance to target desired products in chemical reactions. In this joint experimental–computational work, we leverage tailored Cu/ZnO precatalysts as a material platform to identify the intrinsic features of methane-producing and ethanol-producing CuZn catalysts in the electrochemical CO₂ reduction reaction (CO₂RR). Specifically, we find that Cu@ZnO nanocrystals, where a central Cu domain is decorated with ZnO domains, and ZnO@Cu nanocrystals, where a central ZnO domain is decorated with Cu domains, evolve into Cu@CuZn core@shell catalysts that are selective for methane (∼52%) and ethanol (∼39%), respectively. Operando X-ray absorption spectroscopy and various microscopy methods evidence that a higher degree of surface alloying along with a higher concentration of metallic Zn improve the ethanol selectivity. Density functional theory explains that the combination of electronic and tandem effects accounts for such selectivity. These findings mark a step ahead towards understanding structure–property relationships in bimetallic catalysts for the CO₂RR and their rational tuning to increase selectivity towards target products, especially alcohols.

A higher degree of surface alloying and Zn concentration boosts the selectivity towards ethanol of CuZn catalysts in CO₂ electroreduction.     

Thermal Treatment of Iron-Copper Metastable Alloys

Mechanical alloying is a versatile technique for the solid state synthesis of many materials, including alloys such as iron-copper where the elements are immiscible under equilibrium conditions. The structural and magnetic state of these alloys, and their thermal stability, have been investigated by means of thermomagnetometry, DSC, X-ray diffraction and Mössbauer spectroscopy. Comparison of the thermomagnetometry curves for the various alloys together with analysis of intermediate reaction products enabled the individual thermal processes to be identified. The Curie temperature of the alloys was measured, and it was found that on heating the metastable alloys underwent phase segregation between 300-400°C.     

The magnetism of fine particle iron oxides and oxyhydroxides in applied fields

The magnetic properties of a series of fine particle iron oxides, oxyhydroxides and hydrated oxyhydroxides are discussed with reference to the data obtained from low-temperature, high-field Mössbauer spectroscopy experiments, using a two-sublattice atomic spin Hamiltonian model to help in the interpretation of the results.     

Magnetic ordering below 10K in the high-Tc superconductor YBa2(Cu0.985Fe0.015)3O7−σ

The high-temperature superconductor with the nominal composition YBa₂Cu₃O_7?σ has been doped with iron 93% enriched in⁵⁷Fe. When 1.5 at % Fe substitutes for Cu, the transition temperature is reduced by about 30° K with full ac shielding (X′=?1/4π) achieved by ≈40 K. At room temperature the Mössbauer spectrum consists of three overlapping doublets. Below 10 K, hyperfine-field splitting is observed; relaxation still takes place at T=1.8 K.     

Metal–ligand bond strength determines the fate of organic ligands on the catalyst surface during the electrochemical CO2 reduction reaction

Colloidally synthesised nanocrystals (NCs) are increasingly utilised as catalysts to drive both thermal and electrocatalytic reactions. Their well-defined size and shape, controlled by organic ligands, are ideal to identify the parameters relevant to the activity, selectivity and stability in catalysis. However, the impact of the native surface ligands during catalysis still remains poorly understood, as does their fate. CuNCs are among the state-of-the-art catalysts for the electrochemical CO₂ reduction reaction (CO₂RR). In this work, we study CuNCs that are capped by different organic ligands to investigate their impact on the catalytic properties. We show that the latter desorb from the surface at a cathodic potential that depends on their binding strength with the metal surface, rather than their own electroreduction potentials. By monitoring the evolving surface chemistry in situ, we find that weakly bound ligands desorb very rapidly while strongly bound ligands impact the catalytic performance. This work provides a criterion to select labile ligands versus ligands that will persist on the surface, thus offering opportunity for interface design.

The metal–ligand binding strength is a key parameter in determining the role and fate of the surface ligands on nanoparticle catalysts during the electrochemical CO₂ reduction reaction.     

Radiobiological Implications of Nanoparticles Following Radiation Treatment

Materials with a high atomic number (Z) are shown to cause an increase in the level of cell kill by ionizing radiation when introduced into tumor cells. This study uses in vitro experiments to investigate the differences in radiosensitization between two cell lines (MCF-7 and U87) and three commercially available nanoparticles (gold, gadolinium, and iron oxide) irradiated by 6 MV X-rays. To assess cell survival, clonogenic assays are carried out for all variables considered, with a concentration of 0.5 mg mL⁻¹ for each nanoparticle material used. This study demonstrates differences in cell survival between nanoparticles and cell line. U87 shows the greatest enhancement with gadolinium nanoparticles (2.02 ± 0.36), whereas MCF-7 cells have higher enhancement with gold nanoparticles (1.74 ± 0.08). Mass spectrometry, however, shows highest elemental uptake with iron oxide and U87 cells with 4.95 ± 0.82 pg of iron oxide per cell. A complex relationship between cellular elemental uptake is demonstrated, highlighting an inverse correlation with the enhancement, but a positive relation with DNA damage when comparing the same nanoparticle between the two cell lines.     

Exchange-Driven Magnetic Anomalies in Fe–Zr–B-Based Nanocomposites

Hyperfine Interactions - The oxidation of Fe(II)–Fe(III) hydroxycarbonate green rust GR(CO3 2?) in the presence of phosphate ions known as corrosion inhibitor is monitored by...