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High-throughput flame spray pyrolysis directly affords a low-loading Pt catalyst supported on cerium oxide, which is an excellent material for selective semihydrogenation of C2H2at 180 °C, exhibiting nearly complete conversion of C2H2(98.2%) with high selectivity towards C2H4(87.1%). Pt in this catalyst is atomically dispersed within cerium oxide, and this structural feature restricts C2H4adsorption as π-bonded, known to promote C2H4selectivity.

The surface chemistry of the activated carbon supporting material was tailored to investigate the influence of O and N groups as well as O-free Lewis basic sites on the performance of Ni-based catalysts for CO2methanation. Catalytic experiments demonstrated that 15% Ni on carbon with O-free Lewis basic sites showed the best performance (XCO2= 76%, SCH4= 97%, T= 450 °C, P= 1 bar), suggesting that the methanation reaction is highly dependent on the basicity of the support. Promotion with 5% Fe enabled the decrease of the optimal reaction temperature while improving the stability of the catalyst. Microstructural and compositional studies of the catalyst after a prolonged time on stream experiment suggested that the slight but gradual catalyst deactivation during methanation is associated with the sintering of Ni nanoparticles and the development of a distinct Ni@NiO core–shell nanostructure.

The deployment of water electrolysis as a major contributor to global hydrogen production requires the elimination of catalysts based on scarce and expensive precious metals, and amongst the most promising alternatives are first-row transition metal phosphides. This study presents the synthesis, characterisation, electrochemical testing and performance rationalisation of cobalt phosphide modified with aluminium as an improved catalyst for alkaline oxygen evolution. The electrodes were prepared by gas phase phosphorisation of Al-sputtered Co foam, and characterised by SEM, EDX, XRD, XPS, HAADF-STEM and Raman spectroscopy. Al modification enhances the oxygen evolution performance of the anodes, with a current density of 200 mA cm−2reached at an overpotential of 360 mV, representing a 50 mV improvement compared to the Al-free sample. Double layer capacitance measurements indicate that the performance enhancement results from an approximately four-fold increase in relative electrochemically active surface area (ECSA) in the Al-modified sample. In situRaman spectroscopy rationalises this ECSA increase on the grounds of an Al-induced preference for a spinel phase Co/Al oxide on the catalyst surface upon exposure to electrolyte solution, the compact crystal structure of which causes shrinkage and surface cracking. This contrasts with previous observations on Al-doped nickel phosphides, where an increase in surface area was attributed to Al dissolution. These results present a route for achieving high current density oxygen evolution without the need to alter the catalyst active species, as well as demonstrate the importance of in situtechniques for rationalising performance improvements resulting from subtle differences in surface chemistry.

Chalcogenide semiconducting nanoparticles are promising building blocks for solution-processed fabrication of optoelectronic devices. In this work, we report a new large-scale colloidal synthesis of metastable CuInSe2nanoparticles with hexagonal plate-like morphology. Powder X-ray diffraction analysis of the nanoparticles showed that the structure of the nanoparticles is not simple hexagonal wurtzite-type CuInSe2(space group P63mc), indicating the formation of an ordered superstructure. Detailed insight into this structural aspect was explored by high-resolution electron microscopy, and the results evidence an unreported chemical ordering within the synthesized CuInSe2nanoparticles. Specifically, while the Se sublattice is arranged in perfect wurtzite subcell, Cu and In are segregated over distinct framework positions, forming domains with lower symmetry. The arrangement of these domains within the hexagonal Se substructure proceeds through the formation of a number of planar defects, mainly twins and antiphase boundaries. As a semiconductor, the synthesized material exhibits a direct optical transition at 0.95 eV, which correlates well with its electronic structure assessed by density functional theory calculations. Overall, these findings may inspire the design and synthesis of other nanoparticles featuring unique chemical ordering; thus, providing an additional possibility of tuning intrinsic transport properties.

To investigate magnetostructural relationships in colloidal magnetite (Fe3O4) nanoparticles (NPs) at high temperature (300–900 K), we measured the temperature dependence of magnetization (M) of oleate-capped magnetite NPs ca. 20 nm in size. Magnetometry revealed an unusual irreversible high-temperature dependence of Mfor these NPs, with dip and loop features observed during heating–cooling cycles. Detailed characterizations of as-synthesized and annealed Fe3O4NPs as well as reference ligand-free Fe3O4NPs indicate that both types of features in M(T) are related to thermal decomposition of the capping ligands. The ligand decomposition upon the initial heating induces a reduction of Fe3+to Fe2+and the associated dip in M, leading to more structurally and compositionally uniform magnetite NPs. Having lost the protective ligands, the NPs continually sinter during subsequent heating cycles, resulting in divergent Mcurves featuring loops. The increase in Mwith sintering proceeds not only through elimination of a magnetically dead layer on the particle surface, as a result of a decrease in specific surface area with increasing size, but also through an uncommonly invoked effect resulting from a significant change in Fe3+/Fe2+ratio with heat treatment. The interpretation of irreversible features in M(T) indicates that reversible M(T) behavior, conversely, can be expected only for ligand-free, structurally and compositionally uniform magnetite NPs, suggesting a general applicability of high-temperature M(T) measurements as an analytical method for probing the structure and composition of magnetic nanomaterials.

Exceptional magnetic properties of magnetite, Fe3O4, nanoparticles make them one of the most intensively studied inorganic nanomaterials for biomedical applications. We report successful gram-scale syntheses, via hydrothermal route or controlled coprecipitation in an automated reactor, of colloidal Fe3O4nanoparticles with sizes of 12.9 ± 5.9, 17.9 ± 4.4, and 19.8 ± 3.2 nm. To investigate structure–property relationships as a function of the synthetic procedure, we used multiple techniques to characterize the structure, phase composition, and magnetic behavior of these nanoparticles. For the iron oxide cores of these nanoparticles, powder X-ray diffraction and electron microscopy both confirm single-phase Fe3O4composition. In addition to the core composition, the magnetic performance of nanoparticles in the 13–20 nm size range can be strongly influenced by the surface properties, which we analyzed by three complementary techniques. Raman scattering and X-ray photoelectron spectroscopy (XPS) measurements indicate overoxidation of nanoparticle surfaces, while transmission electron microscopy (TEM) shows no distinct core–shell structure. Considered together, Raman, XPS, and TEM observations suggest that our nanoparticles have a gradually varying nonstoichiometric Fe3O4+δcomposition, which could be attributed to the formation of Fe3O4–γ-Fe2O3solid solutions at their outermost surface. Detailed analyses by TEM reveal that the hydrothermally produced samples include single-domain nanocrystals coexisting with defective twinned and dimer nanoparticles, which form as a result of oriented-attachment crystal growth. All our nanoparticles exhibit superparamagnetic-like behavior with a characteristic blocking temperature above room temperature. We attribute the estimated saturation magnetization values up to 84.01 ± 0.25 emu/g at 300 K to the relatively large size of the nanoparticles (13–20 nm) coupled with the syntheses under elevated temperature; alternative explanations, such as surface-mediated effects, are not supported by our spectroscopy or microscopy measurements. For these colloids, the heating efficiency in magnetic hyperthermia correlates with their saturation magnetization, making them appealing for therapeutic and other biomedical applications that rely on high-performance nanoparticle-mediated hyperthermia.

In this work, “breathing-caloric” effect is introduced as a new term to define very large thermal changes that arise from the combination of structural changes and gas adsorption processes occurring during breathing transitions. In regard to cooling and heating applications, this innovative caloric effect appears under very low working pressures and in a wide operating temperature range. This phenomenon, whose origin is analyzed in depth, is observed and reported here for the first time in the porous hybrid organic–inorganic MIL-53(Al) material. This MOF compound exhibits colossal thermal changes of ΔS∼ 311 J K–1kg–1and ΔH∼ 93 kJ kg–1at room temperature (298 K) and under only 16 bar, pressure which is similar to that of common gas refrigerants at the same operating temperature (for instance, p(CO2) ∼ 64 bar and p(R134a) ∼ 6 bar) and noticeably lower than p> 1000 bar of most solid barocaloric materials. Furthermore, MIL-53(Al) can operate in a very wide temperature range from 333 K down to 254 K, matching the operating requirements of most HVAC systems. Therefore, these findings offer new eco-friendly alternatives to the current refrigeration systems that can be easily adapted to existing technologies and open the door to the innovation of future cooling systems yet to be developed.

We investigate LaCo2P2as an electrocatalytic material for oxygen evolution reaction (OER) under alkaline and acidic conditions. This layered intermetallic material was prepared viaSn-flux high-temperature annealing. The electrocatalytic ink, prepared with the ball-milled LaCo2P2catalyst at the mass loading of 0.25 mg/cm2, shows OER activity at pH = 14, reaching current densities of 10, 50, and 100 mA/cm2under the overpotential of 400, 440, and 460 mV, respectively. Remarkably, the electrocatalytic performance remains constant for at least 4 days. Transmission electron microscopy reveals the formation of a catalytically active CoOxshell around the pre-catalyst LaCo2P2core during the alkaline OER. The core serves as a robust support for the in situ-formed electrocatalytic system. Similar studies under pH = 0 reveal the rapid deterioration of LaCo2P2, with the formation of LaPO4and amorphous cobalt oxide. This study shows the viability of layered intermetallics as stable OER electrocatalysts, although further developments are required to improve the electrocatalytic performance and increase the stability at lower pH values.