Solution combustion synthesis of Ni-based hybrid metal oxides for oxygen evolution reaction in alkaline medium

Oxygen evolution reaction (OER) has arisen as an outstanding technology for energy generation, conversion, and storage. Herein, we investigated the synthesis of nickel-based hybrid metal oxides (Ni_xM_1−xO_y) and their catalytic performance towards OER. Ni_xM_1−xO_y catalysts were synthesized by solution combustion synthesis (SCS) using the metal nitrates as oxidizer and glycine as fuel. Scanning electron microscope (SEM) micrographs display a porous morphology for the hybrid binary Ni_xM_1−xO_y, the common feature of combusted materials. X-ray diffraction (XRD) of Ni_xM_1−xO_y depicted well-defined diffraction peaks, which confirms the crystalline nature of synthesized catalysts. The particle size of as-synthesized materials ranges between 20 and 30 nm with a mesoporous nature as revealed by N₂-physisorption. The electrocatalytic performance of the as-prepared materials was evaluated towards OER in alkaline medium. Among them, Ni_xCo_1−xO_y showed the best catalytic performance. For instance, it exhibited the lowest overpotential at a current density of 10 mA cm⁻² (404 mV), onset potential (1.605 V), and Tafel slope (52.7 mV dec⁻¹). The enhanced electrocatalytic performance of Ni_xCo_1−xO_y was attributed to the synergism between cobalt and nickel and the alteration of the electronic structure of nickel. Also, Ni_xCo_1−xO_y afforded the highest Ni³⁺/Ni²⁺ when compared to other electrocatalysts. This leads to higher oxidation states of Ni species, which promote and improve the electrocatalytic activity.

Ni-based mixed transition metal oxides (MTMO) (Ni_xM_1−xO_y) were synthesized using the solution combustion synthesis (SCS), and investigated as electrocatalysts towards oxygen evolution reaction (OER) in alkaline medium.     

High-temperature thermoelectric properties of Na- and W-Doped Ca3Co4O9 system

The detailed crystal structures and high temperature thermoelectric properties of polycrystalline Ca_3−2xNa_2xCo_4−xW_xO₉ (0 ≤ x ≤ 0.075) samples have been investigated. Powder X-ray diffraction data show that all samples are phase pure, with no detectable traces of impurity. The diffraction peaks shift to lower angle values with increase in doping (x), which is consistent with larger ionic radii of Na⁺ and W⁶⁺ ions. X-ray photoelectron spectroscopy data reveal that a mixture of Co²⁺, Co³⁺ and Co⁴⁺ valence states are present in all samples. It has been observed that electrical resistivity (ρ), Seebeck coefficient (S) and thermal conductivity (κ) are all improved with dual doping of Na and W in Ca₃Co₄O₉ system. A maximum power factor (PF) of 2.71 × 10⁻⁴ W m⁻¹ K⁻² has been obtained for x = 0.025 sample at 1000 K. The corresponding thermoelectric figure of merit (zT) for x = 0.025 sample is calculated to be 0.21 at 1000 K, which is ∼2.3 times higher than zT value of the undoped sample. These results suggest that Na and W dual doping is a promising approach for improving thermoelectric properties of Ca₃Co₄O₉ system.

The detailed crystal structures and high temperature thermoelectric properties of polycrystalline Ca_3−2xNa_2xCo_4−xW_xO₉ (0 ≤ x ≤ 0.075) samples have been investigated.     

Effects of A-site composition of perovskite (Sr1−xBaxZrO3) oxides on H atom adsorption,migration, and reaction

Hydrogen (H) atomic migration over a metal oxide is an important surface process in various catalytic reactions. Control of the interaction between H atoms and the oxide surfaces is therefore important for better catalytic performance. For this investigation, we evaluated the adsorption energies of the H atoms over perovskite-type oxides (Sr_1−xBa_xZrO₃; 0.00 ≤ x ≤ 0.50) using DFT (Density Functional Theory) calculations, then clarified the effects of cation-substitution in the A-site of perovskite oxides on H atom adsorption, migration, and reaction. Results indicated local distortion at the oxide surface as a key factor governing H atom adsorption. Subtle Ba²⁺ substitution for Sr²⁺ sites provoked local distortion at the Sr_1−xBa_xZrO₃ oxide surface, which led to a decrement in the H atom adsorption energy. Furthermore, the effect of Sr²⁺/Ba²⁺ ratio on the H atoms'' reactivities was examined experimentally using a catalytic reaction, which was promoted by activated surface H atoms. Results show that the surface H atoms activated by the substitution of Sr²⁺ sites with a small amount of Ba²⁺ (x = 0.125) contributed to enhancement of ammonia synthesis rate in an electric field, which showed good agreement with predictions made using DFT calculations.

H atom adsorption over perovskite (Sr_1−xBa_xZrO₃) was governed by local lattice distortion, which can be tuned by the A-site cation-doping ratio.     

Atmosphere-sensitive photoluminescence of CoxFe3−xO4 metal oxide nanoparticles

In this work the photoluminescence (PL) of Co_xFe_3−xO₄ spinel oxide nanoparticles under pulsed UV laser irradiation (λ_exc = 270 nm) is investigated for varying Co/Fe ratios (x = 0.4_⋯2.5). A broad emission in the green spectral range is observed, exhibiting two maxima at around 506 nm, which is dominant for Fe-rich nanoparticles (x = 0.4, 0.9), and at around 530 nm, that is more pronounced for Co-rich nanoparticles (x > 1.6). As examinations in different atmospheres show that the observed emission reacts sensitively to the presence of water, it is proposed that the emission is mainly caused by OH groups with terminal or bridging metal–O bonds on the Co_xFe_3−xO₄ surface. Raman spectroscopy supports that the emission maximum at 506 nm corresponds to terminal OH groups bound to metal cations on tetrahedral sites (i.e., Fe³⁺), while the maximum around 530 nm corresponds to terminal OH groups bound to metal cations on octahedral sites (i.e., Co³⁺). Photoinduced dehydroxylation shows that OH groups can be removed on Fe-rich nanoparticles more easily, leading to a conversion process and the formation of new OH groups with different bonds to the surface. As such behavior is not observed for Co_xFe_3−xO₄ with x > 1.6, we conclude that the OH groups are more stable against dehydroxylation on Co-rich nanoparticles. The higher OH stability is expected to lead to a higher catalytic activity of Co-rich cobalt ferrites in the electrochemical generation of oxygen.

Co_xFe_3−xO₄ (0.4 < x < 2.5) nanoparticles show a broad green emission induced by surface OH-groups with a lower stability regarding UV-photoinduced dehydroxylation on Fe-rich (x ≤ 1.6) nanoparticles.     

Synthesis and characterisation of Ba(Zn1−xCox)2Si2O7 (0 ≤ x ≤ 0.50) for blue-violet inorganic pigments

Ba(Zn_1−xCo_x)₂Si₂O₇ (0 ≤ x ≤ 0.50) solid solutions were synthesized as novel blue-violet inorganic pigments by a conventional solid-state reaction method. The crystal structure, optical properties, and colour of the pigments were characterized. All the pigments were obtained in a single-phase form. The pigments strongly absorbed visible light at wavelengths from 550 to 650 nm, corresponding to the range of green to orange light. This optical absorption was caused by the d–d transition of the tetrahedrally coordinated Co²⁺ (⁴A₂(F) → ⁴T₁(P)), which was the origin of the blue-violet colour of the pigments. The most intense colour was obtained for Ba(Zn_0.85Co_0.15)₂Si₂O₇, where a* = +52.2 and b* = −65.5 in the CIE (Commission Internationale de l''Éclairage) L*a*b* system. These absolute values were significantly larger than those of commercial violet pigments such as Co₃(PO₄)₂ (a* = +33 and b* = −32) and NH₄MnP₂O₇ (a* = +39 and b* = −21). Therefore, the Ba(Zn_0.85Co_0.15)₂Si₂O₇ pigment could be a novel blue-violet inorganic pigment.

Ba(Zn_1−xCo_x)₂Si₂O₇ (0 ≤ x ≤ 0.50) solid solutions were synthesized as blue-violet inorganic pigments and the colour gradually changed from pale blue-violet to deep blue-violet with increasing the Co²⁺ concentration.     

Mixed metal CoII1−xZnIIx–organic frameworks based on chains with mixed carboxylate and azide bridges: magnetic coupling and slow relaxation

A series of isomorphous three-dimensional metal–organic frameworks [Co^II_1−xZn^II_x(L)(N₃)]·H₂O (x = 0.26, 0.56 and 0.85) based on bimetallic Co^II_1−xZn^II_x (x = 0.26, 0.56 and 0.85) chains with random metal sites have been synthesized and magnetically characterized. The Co^II_1−xZn^II_x series, which intrinsically feature random anisotropic/diamagnetic sites, shows complex magnetic interactions. By gradually introducing the diamagnetic Zn^II ions into the pure anisotropic Co^II single-chain magnets system, the ferromagnetic interactions between Co^II ions are gradually diluted. Moreover, the slow magnetic relaxation behaviour of the mixed metal Co^II_1−xZn^II_x systems also changes. In this bimetallic series Co^II_1−xZn^II_x, the Co-rich materials exhibit slow relaxation processes that may arise from SCM mechanism, while the Zn^II-rich materials show significantly low slow magnetic relaxation. A general trend is that the activation energy and the blocking temperature decrease with the increase in diamagnetic Zn^II content, emphasizing the importance of anisotropy for slow relaxation of magnetization.

A series of mixed-metal systems consisting of Co^II_1−xZn^II_x chains with (μ-COO)₂(μ-EO-N₃) bridges were prepared, exhibiting interesting magnetic coupling and slow magnetic relaxation.     

Tuning the microstructural and magnetic properties of CoFe2O4/SiO2 nanocomposites by Cu2+ doping

Co–Cu ferrite is a promising functional material in many practical applications, and its physical properties can be tailored by changing its composition. In this work, Co_1−xCu_xFe₂O₄ (0 ≤ x ≤ 0.3) nanoparticles (NPs) embedded in a SiO₂ matrix were prepared by a sol–gel method. The effect of a small Cu²⁺ doping content on their microstructure and magnetic properties was studied using XRD, TEM, Mössbauer spectroscopy, and VSM. It was found that single cubic Co_1−xCu_xFe₂O₄ ferrite was formed in amorphous SiO₂ matrix. The average crystallite size of Co_1−xCu_xFe₂O₄ increased from 18 to 36 nm as Cu²⁺ doping content x increased from 0 to 0.3. Mössbauer spectroscopy indicated that the occupancy of Cu²⁺ ions at the octahedral B sites led to a slight deformation of octahedral symmetry, and Cu²⁺doping resulted in cation migration between octahedral A and tetrahedral B sites. With Cu²⁺ content increasing, the saturation magnetization (M_s) first increased, then tended to decrease, while the coercivity (H_c) decreased continuously, which was associated with the cation migration. The results suggest that the Cu²⁺ doping content in Co_1−xCu_xFe₂O₄ NPs plays an important role in its magnetic properties.

The Cu²⁺ doping content in Co_1−xCu_xFe₂O₄/SiO₂ plays an important role in tuning hyperfine interaction and magnetic properties.     

Tuning composition of CuCo2S4–NiCo2S4 solid solutions via solvent-less pyrolysis of molecular precursors for efficient supercapacitance and water splitting

Mixed metal sulfides are increasingly being investigated because of their prospective applications for electrochemical energy storage and conversion. Their high electronic conductivity and high density of redox sites result in significant improvement of their electrochemical properties. Herein, the composition-dependent supercapacitive and water splitting performance of a series of Ni_(1−x)Cu_xCo₂S₄ (0.2 ≤ x ≤ 0.8) solid solutions prepared via solvent-less pyrolysis of a mixture of respective metal ethyl xanthate precursors is reported. The use of xanthate precursors resulted in the formation of surface clean nanomaterials at low-temperature. Their structural, compositional, and morphological features were examined by p-XRD, SEM, and EDX analyses. Both supercapacitive and electrocatalytic (HER, OER) properties of the synthesized materials significantly vary with composition (Ni/Cu molar content). However, the optimal composition depends on the application. The highest specific capacitance of 770 F g⁻¹ at a current density of 1 A g⁻¹ was achieved for Ni_0.6Cu_0.4Co₂S₄ (NCCS-2). This electrode exhibits capacitance retention (C_R) of 67% at 30 A g⁻¹, which is higher than that observed for pristine NiCo₂S₄ (838 F g⁻¹ at 1 A g⁻¹, 47% C_R at 30 A g⁻¹). On the contrary, Ni_0.4Cu_0.6Co₂S₄ (NCCS-3) exhibits the lowest overpotential of 124 mV to deliver a current density of 10 mA cm⁻². Finally, the best OER activity with an overpotential of 268 mV at 10 mA cm⁻² was displayed by Ni_0.8Cu_0.2Co₂S₄ (NCCS-1). The prepared electrodes exhibit high stability, as well as durability.

A multi-component CuCo₂S₄ and NiCo₂S₄ thiospinel solid solution is prepared over an entire range by a low-temperature solvent-less route. The synergistic effect from both thiospinels on water splitting and capacitance is studied.     

The synthesis of CoxNi1−xFe2O4/multi-walled carbon nanotube nanocomposites and their photocatalytic performance

A series of Co_xNi_1−xFe₂O₄/multi-walled carbon nanotube (Co_xNi_1−xFe₂O₄/MWCNTs) nanocomposites as photocatalysts were successfully synthesized, where Co_xNi_1−xFe₂O₄ was synthesized via a one-step hydrothermal approach. Simultaneously, methylene blue (MB) was used as the research object to investigate the catalytic effect of the catalyst in the presence of hydrogen peroxide (H₂O₂). The results showed that all the photocatalysts exhibited enhanced catalytic activity compared to pure ferrite. In addition, compared with the other photocatalysts, the reaction time was greatly shortened a significantly higher removal rate was achieved using 3-CNF/MWCNTs. There was no significant decrease in photodegradation efficiency after three catalytic cycles, suggesting that Co_xNi_1−xFe₂O₄/MWCNTs are recyclable photocatalysts for wastewater treatment. Our results indicate that the Co_xNi_1−xFe₂O₄/MWCNT composite can be effectively applied for the removal of organic pollutants as a novel photocatalyst.

A series of Co_xNi_1−xFe₂O₄/multi-walled carbon nanotube (Co_xNi_1−xFe₂O₄/MWCNTs) nanocomposites as photocatalysts were successfully synthesized. The results implied that this composites can be effectively applied for the removal of organic pollutant as novel photocatalysts.     

In-plasma-catalysis for NOx degradation by Ti3+ self-doped TiO2−x/γ-Al2O3 catalyst and nonthermal plasma

In an attempt to realize the efficient treatment of NO_x, a mixed catalyst of Ti³⁺ self-doped TiO_2−x and γ-Al₂O₃ was constructed by reducing commercial TiO₂. The degradation effect on NO_x was evaluated by introducing the mixed catalyst into a coaxial dual-dielectric barrier reactor. It was found that the synthesized TiO_2−x could achieve considerable degradation effects (84.84%, SIE = 401.27 J L⁻¹) in a plasma catalytic system under oxygen-rich conditions, which were better than those of TiO₂ (73.99%) or a single plasma degradation process (26.00%). The presence of Ti³⁺ and oxygen vacancies in TiO_2−x resulted in a relatively narrow band gap, which contributed to catalyzing deeply the oxidation of NO_x to NO₂⁻ and NO₃⁻ during the plasma-induced “pseudo-photocatalysis” process. Meanwhile, the TiO_2−x showed an improved discharge current and promoted discharge efficiency, explaining its significant activation effect in the reaction. Reduced TiO_2−x could achieve an impressive degradation effect in a long-time plasma-catalysis process, and still maintained its intrinsic crystal structure and morphology. This work provides a facile synthesis procedure for preparing Ti³⁺ self-doped TiO_2−x with practical and scalable production potential; moreover, the novel combination with plasma also provides new insights into the low-temperature degradation of NO_x.

TiO_2−x has a smaller forbidden band width, more abundant Ti³⁺ and oxygen vacancies, so as to obtain a better and more stable degradation effect of NO_x in plasma-catalysis process.     

NiO/NixCo3−xO4 porous ultrathin nanosheet/nanowire composite structures as high-performance supercapacitor electrodes

The demand for a new generation of high-safety, long-lifespan, and high-capacity power sources increases rapidly with the growth of energy consumption in the world. Here we report a facile method for preparing architecture materials made of NiO/Ni_xCo_3−xO₄ porous nanosheets coupled with NiO/Ni_xCo_3−xO₄ porous nanowires grown in situ on nickel foams using a hydrothermal method without any binder followed by a heat treatment process. The nanosheet-shaped NiO/Ni_xCo_3−xO₄ species in the nanosheet matrix function well as a scaffold and support for the dispersion of the Ni_xCo_3−xO₄ nanowires, resulting in a relatively loose and open structure within the electrode matrix. Among all composite electrodes prepared, the one annealed in air at 300 °C displays the best electrochemical behavior, achieving a specific capacitance of 270 mF cm⁻² at 5 mA cm⁻² while maintaining excellent stability (retaining ≈ 89% of the max capacitance after 20 000 cycles), demonstrating its potential for practical application in power storage devices.

Porous ultrathin nanosheet/nanowire composite structures are prepared as high-performance supercapacitor electrodes which exhibit excellent stability.     

N-doped TiO2 nanotube arrays with uniformly embedded CoxP nanoparticles for high-efficiency hydrogen evolution reaction

Efficient and stable non-precious metal based electrocatalysts are crucial to the hydrogen evolution reaction (HER) in renewable energy conversion. Herein, Co_xP nanoparticles (NPs) are uniformly embedded in N-doped TiO₂ nanotube arrays (Co_xP/N-TiO₂ NTAs) by low-temperature phosphorization of the precursor of metallic cobalt NPs embedded in N-doped TiO₂ NTAs (Co/N-TiO₂ NTAs) which were fabricated by phase separation of CoTiO₃ NTAs in ammonia. Owing to the abundant exposed surface active sites of Co_xP NPs, tight contact between the Co_xP NPs and TiO₂ NTAs, fast electron transfer in N-doped TiO₂, and channels for effective diffusion of ions and H₂ bubbles in the tubular structure, the Co_xP/N-TiO₂ NTAs have excellent electrocatalytic activity in HER exemplified by a low overpotential of 180 mV at 10 mA cm⁻² and small Tafel slope of 51 mV dec⁻¹ in 0.5 M H₂SO₄. The catalyst also shows long-term cycling stability and is a promising non-precious metal catalyst for HER.

Co_xP NPs embedded in N-doped TiO₂ NTAs was fabricated by phase separation of CoTiO₃ and delivers high efficient and stable HER performance in acid solution.     

Structural growth pattern of neutral and negatively charged yttrium-doped silicon clusters YSin0/− (n=6–20): from linked to encapsulated structures

A global search for the low energy of neutral and anionic doped Si clusters YSi_n^0/− (n = 6–20) was performed using the ABCluster global search technique coupled with a hybrid density functional method (mPW2PLYP). In light of the calculated energies and the measured photoelectron spectroscopy values, the true minima of the most stable structures were confirmed. It is shown that the structural growth pattern of YSi_n⁻ (n = 6–20) is from Y-linked two subcluster structure to a Y-encapsulated structure in Si cages, while that of YSi_n (n = 6–20) is from substitutional to linked structures, and as the number of Si atoms increases, it evolves toward the encapsulated structure. Superatom YSi₂₀⁻ with a high-symmetry endohedral I_h structure has an ideal thermodynamic stability and chemical reactivity, making it the most suitable building block for novel optical, optoelectronic photosensitive or catalytic nanomaterials.

Superatom YSi₂₀⁻, with an ideal thermodynamic stability and chemical reactivity, is the most suitable building block for novel optical, optoelectronic photosensitive or catalytic nanomaterials.     

Co2+ substituted for Bi3+ in BiVO4 and its enhanced photocatalytic activity under visible LED light irradiation

We investigated the fabrication of Co-doped BiVO₄ (Bi_1−xCo_xVO_4+δ, 0.05 < x < 0.5) by the substitution of Co ions for Bi sites in BiVO₄. The X-ray diffraction (XRD), Raman, and X-ray photoelectron spectroscopy (XPS) results indicated that the substitution of Co²⁺ ions for Bi³⁺ sites in BiVO₄ was successful, although a change in the crystal phase of BiVO₄ did not occur. UV-vis DRS and PL results suggested that the Co-incorporation could slightly improve the visible light absorption of BiVO₄ and induce the separation of photoinduced electron–hole pairs; therefore, a significant enhancement of photocatalytic performance was achieved. The Bi_0.8Co_0.2VO_4+δ sample showed superior photocatalytic activity in comparison with other samples, achieving 96.78% methylene blue (MB) removal within 180 min. In addition, the proposed mechanism of improved photocatalytic activities and the stability of the catalyst were also investigated.

We investigated the fabrication of Co-doped BiVO₄ (Bi_1−xCo_xVO_4+δ, 0.05 < x < 0.5) by the substitution of Co ions for Bi sites in BiVO₄.     

Structural,magnetic and hyperthermia properties and their correlation in cobalt-doped magnetite nanoparticles

Cobalt doped magnetite nanoparticles (Co_xFe_3−xO₄ NPs) are investigated extensively because of their potential hyperthermia application. However, the complex interrelation among chemical compositions and particle size means their correlation with the magnetic and heating properties is not trivial to predict. Here, we prepared Co_xFe_3−xO₄ NPs (0 ≤ x ≤ 1) to investigate the effects of cobalt content and particle size on their magnetic and heating properties. A detailed analysis of the structural features indicated the similarity between the crystallite and particle sizes as well as their non-monotonic change with the increase of Co content. Magnetic measurements for the Co_xFe_3−xO₄ NPs (0 ≤ x ≤ 1) showed that the blocking temperature, the saturation magnetization, the coercivity, and the anisotropy constant followed a similar trend with a maximum at x = 0.7. Moreover, ⁵⁷Fe Mössbauer spectroscopy adequately explained the magnetic behaviour, the anisotropy constant, and saturation magnetization of low Co content samples. Finally, our study shows that the relaxation loss is a primary contributor to the SAR in Co_xFe_3−xO₄ NPs with low Co contents as well as their potential application in magnetic hyperthermia.

The interrelation among chemical compositions, structure, and heating properties of cobalt doped magnetite nanoparticles (Co_xFe_3−xO₄ NPs) for their potential hyperthermia application.     

α(β)-PbO2 doped with Co3O4 and CNT porous composite materials with enhanced electrocatalytic activity for zinc electrowinning

The high energy consumption during zinc electrowinning is mainly caused by the high overpotential of the oxygen evolution for Pb–Ag alloys with strong polarization. The preparation of new active energy-saving materials has become a very active research field, depending on the synergistic effects of active particles and active oxides. In this research, a composite material, α(β)-PbO₂, doped with Co₃O₄ and CNTs on the porous Ti substrate was prepared via one-step electrochemical deposition and the corresponding electrochemical performance was investigated in simulated zinc electrowinning solution. The composite material showed a porous structure, finer grain size and larger electrochemical surface area (ECSA), which indicated excellent electrocatalytic activity. Compared with the Pb–0.76 wt% Ag alloy, the overpotential of oxygen evolution for the 3D-Ti/PbO₂/Co₃O₄–CNTs composite material was decreased by about 452 mV under the current density of 500 A m⁻² in the simulated zinc electrowinning solution. The decrease in the overpotential of oxygen evolution was mainly ascribed to the higher ECSA and lower charger transfer resistance. Moreover, it showed the lowest self-corrosion current density of 1.156 × 10⁻⁴ A cm⁻² and may be an ideal material for use in zinc electrowinning.

3D-Ti/PbO₂–Co₃O₄–CNTs composite electrode was fabricated through galvanostatic electrodepositon, which shows outstanding electrocatalytic activity to OER in harsh media (50 g L⁻¹ Zn²⁺ + 150 g L⁻¹ H₂SO₄).     

Magnetic properties,magnetocaloric effect,and critical behaviors in Co1−xCrxFe2O4

This research work focuses on the magnetic properties, nature of the magnetic phase transition, magnetocaloric effect, and critical scaling of magnetization of various Co_1−xCr_xFe₂O₄ (x = 0, 0.125, 0.25, 0.375, and 0.5). The tunability of the magnetic moment, exchange interactions, magnetocrystalline anisotropy constant, and microwave frequency using Cr³⁺ content has been found. The nature of the magnetic phase transitions for all the Cr³⁺ concentrations exhibits as second order which has been confirmed from the analysis of critical scaling, universal curve scaling, and scaling analysis of the magnetocaloric effect. The critical exponent analysis for all samples was performed from the modified Arrott-, and Kouvel–Fisher-plots. These critical analyses suggest that x = 0.125, 0.250, and 0.375 samples show reliable results in the magnetocaloric effect with relative cooling power (RCP) values in the range of 128–145 J kg⁻¹. On the other hand, x = 0.00, and 0.500 samples exhibit inconsistent RCP values. The universal curve scaling also confirms the reliability of the magnetocaloric effect of the investigated samples.

Magnetic entropy change as a function of temperature for various Co_1−xCr_xFe₂O₄ at an applied magnetic field of 5 T.     

Electrical,magnetic and magnetotransport properties of Na and Mo doped Ca3Co4O9 materials

We report the electrical, magnetic and magnetotransport properties of Na and Mo dual doped Ca_3−2xNa_2xCo_4−xMo_xO₉ (0 ≤ x ≤ 0.15) polycrystalline samples. The results indicate that the strength of ferrimagnetic interaction decreases with increase in doping, as is evident from the observed decrease in Curie temperatures (T_C). The substitution of non-magnetic Mo⁶⁺ ions (4d⁰) in CoO₂ layers and the presence of oxygen vacancies are responsible for decrease in ligand field strength, which results in an enhanced magnetization in the low doped x = 0.025 sample due to a change from the low spin to partial high spin electron configuration. The electrical resistivity of samples exhibits a semiconducting-like behavior in the low temperature range, a strongly correlated Fermi liquid-like behavior in the intermediate temperature range, and an incoherent metal-like behavior in the temperature range 210–300 K. All the samples show a large negative magnetoresistance (MR) at low temperature with a maximum MR value of −59% for the x = 0.025 sample at 2 K and 16 T applied field. The MR values follow the observed trend in magnetization at 5 K and sharply increase below the Curie temperatures of the samples, suggesting that the ferrimagnetic interactions are mainly responsible for the decrease in electrical resistivity under an applied magnetic field.

We report the electrical, magnetic and magnetotransport properties of Na and Mo dual doped Ca_3−2xNa_2xCo_4−xMo_xO₉ (0 ≤ x ≤ 0.15) polycrystalline samples.     

Comparison of electrocatalytic activity of Pt1−xPdx/C catalysts for ethanol electro-oxidation in acidic and alkaline media

In this paper, a comparision of Pt_1−xPd_x/C catalysts for ethanol-oxidation in acidic and alkaline media has been investigated. We prepared Pt_1−xPd_x/C catalysts with different ratios of Pt/Pd (x at% = 0, 27, 53, 77 and 100) by the formic acid reduction method. The obtained Pt_1−xPd_x/C catalysts were characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), induced coupled plasma-atomic emission spectroscopy (ICP-AES), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Structural and morphological investigations of the as-prepared catalysts revealed that the metallic particle size increases with increasing Pd content in the catalyst. The electrocatalytic performances and stabilities of Pt_1−xPd_x/C catalysts were tested by cyclic voltammetry (CV), linear sweep voltammetry (LSV) and chronoamperometry (CA) measurements for ethanol oxidation in acidic and alkaline media. The electrochemical measurements demonstrate that Pt_1−xPd_x/C catalysts exhibit much higher electrocatalytic activity for alcohol oxidation in alkaline media than that in acidic media. The composition of Pt/Pd has a significant impact on the ethanol-oxidation in both acidic and alkaline media. The Pt₂₃Pd₇₇/C catalyst shows the highest electrocatalytic performance with a mass specific peak current of 2453.7 mA mg_PtPd⁻¹ in alkaline media, which is higher than the Pt₇₇Pd₂₃/C with the maximum of peak current of 339.7 mA mg_PtPd⁻¹ in acidic media. Meanwhile, the effect of electrolyte, CH₃CH₂OH concentrations and scan rates was also studied for ethanol-oxidation in acidic and alkaline media.

The Pt_1−xPd_x/C catalysts exhibit much higher electrocatalytic activity in alkaline media than in acid media.     

RuxSe@MoS2 hybrid as a highly efficient electrocatalyst toward hydrogen evolution reaction

Alkaline hydrogen evolution reaction (HER) requires highly efficient and stable catalytic materials, the engineering of which needs overall consideration of the water dissociation process as well as the intermediate hydrogen adsorption process. Herein, a Ru_xSe@MoS₂ hybrid catalyst was synthesized by the decoration of MoS₂ with Ru_xSe nanoparticles through a two-step hydrothermal reaction. Due to the bifunctionality mechanism in which Ru promotes the water dissociation and the nearby Se atoms, unsaturated Mo and/or S atoms act as active sites for the intermediate hydrogen adsorption, the hybrid catalyst exhibits an exceptional HER performance in basic media with a rather low overpotential of 45 mV at a current density of 10 mA cm⁻² and a small Tafel slope of 42.9 mV dec⁻¹. The synergetic effect between Ru_xSe and MoS₂ not only enables more catalytically active sites, but also increases the inherent conductivity of the hybrid catalyst, leading to more favorable HER kinetics under both alkaline and acidic conditions. As a result, Ru_xSe@MoS₂ also demonstrates an enhanced catalytic activity toward HER in 0.5 M H₂SO₄ in comparison with pure Ru_xSe and MoS₂, which requires an overpotential of 120 mV to deliver a 10 mA cm⁻² current density and gives a Tafel slope of 72.2 mV dec⁻¹. In addition, the hybrid electrocatalyst also exhibits superior electrochemical stability during the long-term HER process in both acidic media and alkaline media.

The bifunctionality mechanism of Ru_xSe@MoS₂ greatly enhances the alkaline HER performance, in which Ru promotes water dissociation and the nearby Se atoms, unsaturated Mo and/or S atoms act as active sites for the intermediate hydrogen adsorption.