Co₇Se₈ Nanostructures as Catalysts for Oxygen Reduction Reaction with High Methanol Tolerance

Co₇Se₈ nanostructures electrodeposited on glassy carbon (GC) electrodes show high efficiency for oxygen reduction reaction (ORR) with high methanol tolerance as compared to Pt electrocatalysts. In the presence of methanol, the onset potential for the ORR at Pt/GC is shifted from 0.931 V (vs reversible hydrogen electrode (RHE)) to 0.801 V (vs RHE), whereas it remains the same (0.811 V vs RHE) at Co₇Se₈/GC in the presence and absence of methanol in 0.5 M H₂SO₄ solution. The Co₇Se₈/GC electrodes also showed high cyclability in the presence of methanol, with no degradation of catalytic performance. It is also noteworthy that the Co₇Se₈/GC exhibited exclusively a four-electron reduction pathway for ORR and very low H₂O₂ yield in acidic electrolyte. The admirable performance of Co₇Se₈/GC catalyst along with its cost-effective nature holds great potential for application in direct methanol fuel cells

Synthesis of Superconducting Nanocables of FeSe Encapsulated in Carbonaceous Shell

The recent discovery of superconductivity in iron selenide has attracted considerable attention due to the simplicity of composition, unconventional nature of superconductivity, and ease of synthesis. We have synthesized superconducting FeSe nanowires with a simple catalyst-aided vapor transport reaction at 800 °C in an inert atmosphere. The precursors were chosen to be elemental Se and iron acetylacetonate [Fe^III(C₅H₈O₂)₃]. These vaporized very easily, thereby facilitating transport, and also contributed to the formation of a carbonaceous shell encapsulating the FeSe nanowires. The superconductivity of these nanocables was confirmed through magnetic measurements and a <i>T</i>_c of ≈8 K was obtained for an ensemble of nanocables. The length of FeSe filling inside the carbon nanofibers could be varied by controlling the reaction conditions while the diameter of nanowires was dependent on the thickness of Au–Pd coating used as a catalyst. Extensive analysis through high-resolution microscopy revealed that there was considerable lattice contraction of FeSe in the nanocable up to about 3.6% along the <i>c</i>-direction leading to a reduced spacing between the (001) lattice planes. Interestingly, this compression was more pronounced near the catalyst-FeSe interface and was reduced further along the length of the nanocable. The presence of carbon nanofibers as a shell around the FeSe protected the FeSe nanowires from both atmospheric O₂ and moisture attack, as was evident from the very long ambient condition shelf life of these nanocables, and also makes them more stable under e-beam irradiation

Enhancement of Superconducting <i>T</i>_c (33 K) by Entrapment of FeSe in Carbon Coated Au–Pd₁₇Se₁₅ Nanoparticles

FeSe has been an interesting member of the Fe-based superconductor family ever since the discovery of superconductivity in this simple binary chalcogenide. Simplicity of composition and ease of synthesis has made FeSe, in particular, very lucrative as a test system to understand the unconventional nature of superconductivity, especially in low-dimensional models. In this article we report the synthesis of composite nanoparticles containing FeSe nanoislands entrapped within an <i>ent</i>-FeSe-Pd₁₆Se₁₅–Au nanoparticle and sharing an interface with Pd₁₇Se₁₅. This assembly exhibits a significant enhancement in the superconducting <i>T</i>_<i>c</i> (onset at 33 K) accompanied by a noticeable lattice compression of FeSe along the ⟨001⟩ and ⟨101⟩ directions. The <i>T</i>_<i>c</i> in FeSe is very sensitive to application of pressure and it has been shown that with increasing external pressure <i>T</i>_<i>c</i> can be increased almost 4-fold. In these composite nanoparticles reported here, immobilization of FeSe on the Pd₁₇Se₁₅ surface contributes to increasing the effect of interfacial pressure, thereby enhancing the <i>T</i>_<i>c</i>. The effect of interfacial pressure is also manifested in the contraction of the FeSe lattice (up to 3.8% in ⟨001⟩ direction) as observed through extensive high-resolution TEM imaging. The confined FeSe in these nanoparticles occupied a region of approximately 15–25 nm, where lattice compression was uniform over the entire FeSe region, thereby maximizing its effect in enhancing the <i>T</i>_<i>c</i>. The nanoparticles have been synthesized by a simple catalyst-aided vapor transport reaction at 800 °C where iron acetylacetonate and Se were used as precursors. Morphology and composition of these nanoparticles have been studied in details through extensive electron microscopy

Cobalt Selenide Nanostructures: An Efficient Bifunctional Catalyst with High Current Density at Low Coverage

Electrodeposited Co₇Se₈ nanostructures exhibiting flake-like morphology show bifunctional catalytic activity for oxygen evolution and hydrogen evolution reaction (OER and HER, respectively) in alkaline medium with long-term durability (>12 h) and high Faradaic efficiency (99.62%). In addition to low Tafel slope (32.6 mV per decade), the Co₇Se₈ OER electrocatalyst also exhibited very low overpotential to achieve 10 mA cm^–2 (0.26 V) which is lower than other transition metal chalcogenide based OER electrocatalysts reported in the literature and significantly lower than the state-of-the-art precious metal oxides. A low Tafel slope (59.1 mV per decade) was also obtained for the HER catalytic activity in alkaline electrolyte. The OER catalytic activity could be further improved by creating arrays of 3-dimensional rod-like and tubular structures of Co₇Se₈ through confined electrodeposition on lithographically patterned nanoelectrodes. Such arrays of patterned nanostructures produced exceptionally high mass activity and gravimetric current density (∼68 000 A g^–1) compared to the planar thin films (∼220 A g^–1). Such high mass activity of the catalysts underlines reduction in usage of the active material without compromising efficiency and their practical applicability. The catalyst layer could be electrodeposited on different substrates, and an effect of the substrate surface on the catalytic activity was also investigated. The Co₇Se₈ bifunctional catalyst enabled water electrolysis in alkaline solution at a cell voltage of 1.6 V. The electrodeposition works with exceptional reproducibility on any conducting substrate and shows unprecedented catalytic performance especially with the patterned growth of catalyst rods and tubes

Excellent Bifunctional Oxygen Evolution and Reduction Electrocatalysts (5A_1/5)Co₂O₄ and Their Tunability

Hastening the progress of rechargeable metal–air batteries and hydrogen fuel cells necessitates the advancement of economically feasible, earth-abundant, inexpensive, and efficient electrocatalysts facilitating both the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Herein, a recently reported family of nano (5A1/5)Co2O4 (A = combinations of transition metals, Mg, Mn, Fe, Ni, Cu, and Zn) compositionally complex oxides (CCOs) [Wang et al., Chemistry of Materials, 2023, 35 (17), 7283–7291.] are studied as bifunctional OER and ORR electrocatalysts. Among the different low-temperature soft-templating samples, those subjected to 600 °C postannealing heat treatment exhibit superior performance in alkaline media. One specific composition (Mn0.2Fe0.2Ni0.2Cu0.2Zn0.2)Co2O4 exhibited an exceptional overpotential (260 mV at 10 mA cm–2) for the OER, a favorable Tafel slope of 68 mV dec–1, excellent onset potential (0.9 V) for the ORR, and lower than 6% H2O2 yields over a potential range of 0.2 to 0.8 V vs the reversible hydrogen electrode. Furthermore, this catalyst displayed stability over a 22 h chronoamperometry measurement, as confirmed by X-ray photoelectron spectroscopy analysis. Considering the outstanding performance, the low cost and scalability of the synthesis method, and the demonstrated tunability through chemical substitutions and processing variables, CCO ACo2O4 spinel oxides are highly promising candidates for future sustainable electrocatalytic applications

Soft-Chemical Synthetic Route to Superparamagnetic FeAs@C Core–Shell Nanoparticles Exhibiting High Blocking Temperature

Superparamagnetic FeAs nanoparticles with a fairly high blocking temperature (<i>T</i>_B) have been synthesized through a hot injection precipitation technique. The synthesis involved usage of triphenylarsine (TPA) as the As precursor, which reacts with Fe­(CO)₅ by ligand displacement at moderate temperatures (300 °C). Addition of a surfactant, hexadecylamine (HDA), assists in the formation of the nanoparticles, due to its coordinating ability and low melting point which provides a molten flux like condition making this synthesis a solventless method. Decomposition of the carbonaceous precursors, HDA, TPA and Fe­(CO)₅, also produces the carbonaceous shell coating the FeAs nanoparticles. Magnetic characterization of these nanoparticles revealed the superparamagnetic nature of these nanoparticles with a perfect anhysteretic nature of the isothermal magnetization above <i>T</i>_B. The <i>T</i>_B observed in this system was indeed high (240 K) when compared with other superparamagnetic systems conventionally utilized for magnetic storage devices. It could be further increased by decreasing the strength of the applied magnetic field. The narrow hysteresis with low magnitude of coercivity at 5 K suggested soft ferromagnetic ordering in these nanoparticle ensembles. Mössbauer and XPS studies indicated that the Fe was present in +3 oxidation state and there was no signature of Fe(0) that could have been responsible for the increased magnetic moment and superparamagnetism. Typically for superparamagnetic nanoparticle ensemble, the need for isolation of the superparamagnetic domains (thereby inhibiting particle aggregation and enhancing the <i>T</i>_B) has been in constant limelight. Carbonaceous coating on these as-synthesized nanoparticles formed <i>in situ</i> provided the physical nonmagnetic barrier needed for such isolation. The high <i>T</i>_B and room temperature magnetic moment of these FeAs@C nanoparticles also make them potentially useful for applications in ferrofluids and magnetic refrigeration. In principle this method can be used as a general route toward synthesis of other arsenide nanostructures including the transition metal arsenide which show interesting magnetic and electronic properties (e.g., CoAs, MnAs) with finer control over morphology, composition and structure

Mesoporous RE_0.5Ce_0.5O_2–<i>x</i> Fluorite Electrocatalysts for the Oxygen Evolution Reaction

Developing highly active and stable electrocatalysts for the oxygen evolution reaction (OER) is key to improving the efficiency and practical application of various sustainable energy technologies including water electrolysis, CO2 reduction, and metal air batteries. Here, we use evaporation-induced self-assembly (EISA) to synthesize highly porous fluorite nanocatalysts with a high surface area. In this study, we demonstrate that a 50% rare-earth cation substitution for Ce in the CeO2 fluorite lattice improves the OER activity and stability by introducing oxygen vacancies into the host lattice, which results in a decrease in the adsorption energy of the OH* intermediate in the OER. Among the binary fluorite compositions investigated, Nd2Ce2O7 is shown to display the lowest OER overpotential of 243 mV, achieved at a current density of 10 mA cm–2, and excellent cycling stability in an alkaline medium. Importantly, we demonstrate that rare-earth oxide OER electrocatalysts with high activity and stability can be achieved using the EISA synthesis route without the incorporation of transition and noble metals