A simple method for the preparation of a nickel selenide and cobalt selenide mixed catalyst to enhance bifunctional oxygen activity for Zn–air batteries

Developing a low-cost, simple, and efficient method to prepare excellent bifunctional electrocatalysts toward the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is critical in rechargeable zinc–air batteries. Non-stoichiometric M_0.85Se (M = Ni or Co) nanoparticles are synthesized and modified on nitrogen-doped hollow carbon sphere (NHCS). The NHCS loaded Ni_0.85Se (Ni_0.85Se-NHCS) with rich Ni³⁺ presents higher OER activity, whereas the NHCS-loaded Co_0.85Se (Co_0.85Se-NHCS) with abundant Co²⁺ displays better ORR activity, respectively. When Co_0.85Se-NHCS is mixed with Ni_0.85Se-NHCS in a mass ratio of 1 : 1, the resulting mixture (Ni_0.85Se/Co_0.85Se-NHCS-2) shows better ORR and OER dual catalytic functions than a single selenide. Moreover, zinc–air batteries equipped with Ni_0.85Se/Co_0.85Se-NHCS-2 as the oxygen electrode catalyst exhibit excellent charge and discharge performance as well as improved stability over precious metals. This work has developed a simple and effective method to prepare excellent bifunctional electrocatalysts for ORR and OER, which is beneficial for the practical large-scale application of zinc–air batteries.

The mixture Ni_0.85Se/Co_0.85Se-NHCS-2 displayed superior electrocatalytic performance to that of Ni_0.85Se-NHCS or Co_0.85Se-NHCS alone. This provided a simple approach to develop ORR/OER bifunctional electrocatalysts for zinc–air batteries.     

N-doped mixed Co,Ni-oxides with petal structure as effective catalysts for hydrogen and oxygen evolution by water splitting

Developing electrocatalytic nanomaterials for green H₂ energy is inseparable from the exploration of novel materials and internal mechanisms for catalytic enhancement. In this work, nano-petal N-doped bi-metal (Ni, Co) and bi-valence (+2, +3) (Ni_1−xCo_x)²⁺Co₂³⁺O₄ compounds have been in situ grown on the surface of Ni foam. The N³⁻ atoms originate from the amino group in urea and doped in the compound during annealing. The as-synthesized N-doped (Ni_1−xCo_x)²⁺Co₂³⁺O₄ nano-petals demonstrate commendable hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) bi-functional catalytic efficiency and stability. Electrochemical measurements confirm that the nitrogen doping significantly improves the catalytic kinetics and the surface area. Density functional theory calculations reveal that the improved HER and OER kinetics is not only due to the synergistic effect of bi-metal and bi-valence, as well as the introduction of defects such as oxygen vacancies, but also it more depends on the shortened bond length between the nitrogen N³⁻ atoms and the metal atoms, and the increased electron density of the metal atoms attached to the N³⁻ atoms. In other words, the change of lattice parameters caused by nitrogen doping is more conducive to the catalytic enhancement than the synergistic effect brought by bi-metal. This study provides an experimental and theoretical reference for the design of bi-functional electrocatalytic nanomaterials.

Developing electrocatalytic nanomaterials for green H₂ energy is inseparable from the exploration of novel materials and internal mechanisms for catalytic enhancement.     

Ni stabilized rock-salt structured CoO; Co1−xNixO: tuning of eg electrons to develop a novel OER catalyst

The oxygen evolution reaction (OER) is a key half-reaction in hydrogen–oxygen electrolysers that is very important for efficient electrochemical energy generation, storage and fuel production that offers a clean alternative to fissile fuel combustion based energy systems. Several transition metal containing perovskites were recently explored for the development of superior OER catalysts, and their activity was correlated with the applied potentials at a specific current density to e_g electron density present in the materials. The rock salt structure is envisaged here as a model host structure similar to perovskite to tune the e_g electrons to obtain superior electro-catalytic activity. Incorporation of Ni into CoO lattices helps to stabilize the rock salt structure and modulate the e_g electrons to develop superior OER and ORR electrocatalysts. Nickel doped rock salt structured CoO, Ni_xCo_1−xO (0 ≤ x ≤ 0.5), were synthesized by employing a solid state metathesis synthesis route. The compounds were characterised by powder X-ray diffraction (XRD), TGA, FT-IR and X-ray Photoelectron Spectroscopy (XPS). Ni_0.3Co_0.7O with 1.3 e_g electrons showed superior electrocatalytic activity for the oxygen evolution reaction. The overpotential for the Ni_0.3Co_0.7O sample was also found to be ∼0.450 V for 1 M and about ∼0.389 V at 5 M concentration of the KOH electrolyte.

Incorporation of Ni into CoO lattices helps to stabilize the rock salt structure and modulate the e_g electrons to develop superior OER and ORR electrocatalysts.     

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.     

Hydrogen-etched CoS2 to produce a Co9S8@CoS2 heterostructure electrocatalyst for highly efficient oxygen evolution reaction

There is a pressing requirement for developing high-efficiency non-noble metal electrocatalysts in oxygen evolution reactions (OER), where transition metal sulfides are considered to be promising electrocatalysts for the OER in alkaline medium. Herein, we report the outstanding OER performance of Co₉S₈@CoS₂ heterojunctions synthesized by hydrogen etched CoS₂, where the optimized heterojunction shows a low η₅₀ of 396 mV and a small Tafel slope of 181.61 mV dec⁻¹. The excellent electrocatalytic performance of this heterostructure is attributed to the interface electronic effect. Importantly, the post-stage characterization results indicate that the Co₉S₈@CoS₂ heterostructure exhibits a dynamic reconfiguration during the OER with the formation of CoOOH in situ, and thus exhibits a superior electrocatalytic performance.

Herein, we report the outstanding OER performance of Co₉S₈@CoS₂ heterojunctions synthesized by hydrogen etched CoS₂, where the optimized heterojunction shows a low η₅₀ of 396 mV and a small Tafel slope of 181.61 mV dec⁻¹.     

Solventless synthesis of nanospinel Ni1−xCoxFe2O4 (0 ≤ x ≤ 1) solid solutions for efficient electrochemical water splitting and supercapacitance

The formation of solid solutions represents a robust strategy for modulating the electronic properties and improving the electrochemical performance of spinel ferrites. However, solid solutions have been predominantly prepared via wet chemical routes, which involve the use of harmful and/or expensive chemicals. In the present study, a facile, inexpensive and environmentally benign solventless route is employed for the composition-controlled synthesis of nanoscopic Ni_1−xCo_xFe₂O₄ (0 ≤ x ≤ 1) solid solutions. The physicochemical characterization of the samples was performed by p-XRD, SEM, EDX, XPS, TEM, HRTEM and UV-Vis techniques. A systematic investigation was also carried out to elucidate the electrochemical performance of the prepared nanospinels towards energy generation and storage. Based on the results of CV, GCD, and stability tests, the Ni_0.4Co_0.6Fe₂O₄ electrode showed the highest performance for the supercapacitor electrode exhibiting a specific capacitance of 237 F g⁻¹, superior energy density of 10.3 W h kg⁻¹ and a high power density with a peak value of 4208 W kg⁻¹, and 100% of its charge storage capacity was retained after 4000 cycles with 97% coulombic efficiency. For HER, the Ni_0.6Co_0.4Fe₂O₄ and CoFe₂O₄ electrodes showed low overpotentials of 168 and 169 mV, respectively, indicating better catalytic activity. For OER, the Ni_0.8Co_0.2Fe₂O₄ electrode exhibited a lower overpotential of 320 mV at a current density of 10 mA cm⁻², with a Tafel slope of 79 mV dec⁻¹, demonstrating a fast and efficient process. These results indicated that nanospinel ferrite solid solutions could be employed as promising electrode materials for supercapacitor and water splitting applications.

The formation of solid solutions represents a robust strategy for modulating the electronic properties and improving the electrochemical performance of spinel ferrites.     

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.     

Ultrafine Co3O4 nanolayer-shelled CoWP nanowire array: a bifunctional electrocatalyst for overall water splitting

The development of bifunctional electrocatalysts based on highly efficient non-noble metals is pivotal for overall water splitting. Here, a composite electrode of Co₃O₄@CoWP is synthesized, where an ultrathin layer composed of Co₃O₄ nanoparticles is grown on CoWP nanowires supported on a carbon cloth (CC). The Co₃O₄@CoWP/CC electrode exhibits excellent electrocatalytic activity and improved kinetics towards both the oxygen and hydrogen evolution reactions (OER and HER). The Co₃O₄@CoWP/CC electrode achieves a current density of 10 mA cm⁻² at a low overpotential of 269 mV for the OER and −10 mA cm⁻² at 118 mV for the HER in 1.0 M KOH solution. The voltage applied to a two-electrode water electrolyzer for overall water splitting, while employing the Co₃O₄@CoWP/CC electrode as both an anode and a cathode, in order to reach a current density of 10 mA cm⁻², is 1.61 V, which is better than that for the majority of reported non-noble electrocatalysts. Moreover, the Co₃O₄@CoWP/CC electrode exhibits good stability over 24 h with slight attenuation. The electrode benefits from the enhanced adsorption of oxygen intermediates on Co₃O₄ during the OER, the increased ability for water dissociation and the optimized H adsorption/desorption ability of CoWP nanowires during the HER. This study provides a feasible approach for cost-effective and high-performance non-noble metal bifunctional catalysts for overall water electrolysis.

A hierarchical 3D self-supporting CoWP nanowire array shelled with an ultrathin Co₃O₄ nanolayer on carbon cloth (Co₃O₄@CoWP/CC) exhibits superior overall water electrolysis capability.     

Nanostructured RuO2–Co3O4@RuCo-EO with low Ru loading as a high-efficiency electrochemical oxygen evolution catalyst

Electrochemical water splitting technology is considered to be the most reliable method for converting renewable energy such as wind and solar energy into hydrogen. Here, a nanostructured RuO₂/Co₃O₄–RuCo-EO electrode is designed via magnetron sputtering combined with electrochemical oxidation for the oxygen evolution reaction (OER) in an alkaline medium. The optimized RuO₂/Co₃O₄–RuCo-EO electrode with a Ru loading of 0.064 mg cm⁻² exhibits excellent electrocatalytic performance with a low overpotential of 220 mV at the current density of 10 mA cm⁻² and a low Tafel slope of 59.9 mV dec⁻¹ for the OER. Compared with RuO₂ prepared by thermal decomposition, its overpotential is reduced by 82 mV. Meanwhile, compared with RuO₂ prepared by magnetron sputtering, the overpotential is also reduced by 74 mV. Furthermore, compared with the RuO₂/Ru with core–shell structure (η = 244 mV), the overpotential is still decreased by 24 mV. Therefore, the RuO₂/Co₃O₄–RuCo-EO electrode has excellent OER activity. There are two reasons for the improvement of the OER activity. On the one hand, the core–shell structure is conducive to electron transport, and on the other hand, the addition of Co adjusts the electronic structure of Ru.

The optimized RuO₂/Co₃O₄–RuCo-EO electrode with Ru loading of 0.064 mg cm⁻² exhibits the excellent oxygen evolution activity with an overpotential of 220 mV at the current density of 10 mA cm⁻² and a Tafel slope of 59.9 mV dec⁻¹.     

Enhancing oxygen and hydrogen evolution activities of perovskite oxide LaCoO3via effective doping of platinum

In this study, a series of perovskite oxides LaCo_1−xPt_xO_3−δ (x = 0, 0.02, 0.04, 0.06, and 0.08) were prepared by the citric acid–ethylenediaminetetraacetic acid (CA–EDTA) complexing sol–gel method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Then, the samples were investigated as OER and HER bifunctional electrocatalysts in alkaline media. Compared with other catalysts, LaCo_0.94Pt_0.06O_3−δ had good stability and presented more activity at a lower overpotential of 454 mV (at 10 mA cm⁻²), a lower Tafel slope value of 86 mV dec⁻¹ and a higher mass activity of 44.4 A g⁻¹ for OER; it displayed a lower overpotential of 294 mV (at −10 mA cm⁻²), a lower Tafel slope value of 148 mV dec⁻¹ and a higher mass activity of −34.5 A g⁻¹ for HER. The improved performance might depend on a larger ECSA, faster charge transfer rate and higher ratio of the highly oxidative oxygen species (O₂²⁻/O⁻). Furthermore, the e_g orbital filling of Co approaching 1.2 in the B site might play a leading role.

Among the perovskite LaCo_1−xPt_xO_3−δ catalysts, LaCo_0.94Pt_0.06O_3−δ proved best for catalyzing OER/HER, with η = 454/294 mV, which might be attributed to LCP6 having the e_g orbital filling of Co closest to 1.2.     

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.     

Nickel foam and stainless steel mesh as electrocatalysts for hydrogen evolution reaction,oxygen evolution reaction and overall water splitting in alkaline media

In this work, several commonly used conductive substrates as electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) under alkaline conditions were studied, including nickel foam (Ni foam), copper foam (Cu foam), nickel mesh (Ni mesh) and stainless steel mesh (SS mesh). Ni foam and SS mesh are demonstrated as high-performance and stable electrocatalysts for HER and OER, respectively. For HER, Ni foam exhibited an overpotential of 0.217 V at a current density of 10 mA cm⁻² with a Tafel slope of 130 mV dec⁻¹, which were larger than that of the commercial Pt/C catalyst, but smaller than that of the other conductive substrates. Meanwhile, the SS mesh showed the best electrocatalytic performance for OER with an overpotential of 0.277 V at a current density of 10 mA cm⁻² and a Tafel slope of 51 mV dec⁻¹. Its electrocatalytic performance not only exceeded those of the other conductive substrates but also the commercial RuO₂ catalyst. Moreover, both Ni foam and SS mesh exhibited high stability during HER and OER, respectively. Furthermore, in the two-electrode system with Ni foam used as the cathode and SS mesh used as the anode, they enable a current density of 10 mA cm⁻² at a small cell voltage of 1.74 V. This value is comparable to or exceeding the values of previously reported electrocatalysts for overall water splitting. In addition, NiO on the surface of Ni foam may be the real active species for HER, NiO and FeO_x on the surface of SS mesh may be the active species for OER. The abundant and commercial availability, long-term stability and low-cost property of nickel foam and stainless steel mesh enable their large-scale practical application in water splitting.

Efficient electrocatalytic overall water splitting is achieved with commercially-available and low-cost nickel foam and stainless steel mesh as cathode and anode electrodes.     

Characterization of NaxLi0.67+yNi0.33Mn0.67O2 as a positive electrode material for lithium-ion batteries

The relationship between the charge–discharge properties and crystal structure of Na_xLi_0.67+yNi_0.33Mn_0.67O₂ (0.010 ≤ x ≤ 0.013, 0.16 ≤ y ≤ 0.20) has been investigated. Li/Na_xLi_0.67+yNi_0.33Mn_0.67O₂ cells exhibit gradually sloping initial charge and discharge voltage–capacity curves. The initial charge capacity increased from 171 mA h g⁻¹ for thermally-treated Na_0.15Li_0.51Ni_0.33Mn_0.67O₂ to 226 mA h g⁻¹ for Na_0.010Li_0.83Ni_0.33Mn_0.67O₂ with an increase in the Li content. The initial maximum discharge capacity was 252 mA h g⁻¹ in the case of Na_0.010Li_0.83Ni_0.33Mn_0.67O₂ between 4.8 and 2.0 V at a fixed current density of 15 mA g⁻¹ (0.06C) at 25 °C. The predominance of the spinel phase leads to the high initial discharge capacity of Na_0.010Li_0.83Ni_0.33Mn_0.67O₂. This study shows that chemical lithiation using LiI is effective to improve the electrochemical properties.

The relationship between the charge–discharge properties and crystal structure of Na_xLi_0.67+yNi_0.33Mn_0.67O₂ (0.010 ≤ x ≤ 0.013, 0.16 ≤ y ≤ 0.20) has been investigated.     

Comparison of electrochemical performance of LiNi1−xCoxO2 cathode materials synthesized from coated (1−x)Ni(OH)2@xCo(OH)2 and doped Ni1−xCox(OH)2 precursors

LiNi_1−xCo_xO₂ cathode materials were successfully synthesized from coated (1−x)Ni(OH)₂@xCo(OH)₂ and doped Ni_1−xCo_x(OH)₂ precursors, and the effects of the Co site and content in the precursor and final cathode material on the structure, morphology, and electrochemical performance of the cathodes were investigated using X-ray diffraction, scanning electron microscopy, and charge–discharge tests. The electrochemical performance of the materials prepared from the coated precursor was generally better than that of the materials prepared from the doped precursor. However, with increasing Co content, the performance difference gradually decreased. Among the as-prepared samples, the sample coated with 12 mol% Co delivered an excellent reversible capacity of 213.8 mA h g⁻¹ at 0.1C and the highest capacity retention of 88.5% after 100 cycles at 0.2C in the voltage range of 2.75–4.3 V. High-performance LiNi_1−xCo_xO₂ materials were successfully synthesized, and our findings clearly reveal the differences in the electrochemical properties of the materials prepared from the two different precursors with increasing Co content, thereby providing a valuable reference for the synthesis of high-performance Ni-rich layered cathode materials for Li-ion batteries.

The effects of Co site and content on electrochemical performance of LiNi_1−xCo_xO₂ cathodes materials were investigated.     

Preparation,characterization and application in cobalt ion adsorption using nanoparticle films of hybrid copper–nickel hexacyanoferrate

Different mole ratios (n_Cu : n_Ni = x : y) of hybrid copper–nickel metal hexacyanoferrates (Cu_xNi_yHCFs) were prepared to explore their morphologies, structure, electrochemical properties and the feasibility of electrochemical adsorption of cobalt ions. Cyclic voltammetry (CV), field emission scanning electron microscopy (FE-SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) indicated that the x : y ratio of Cu_xNi_yHCF nanoparticles can be easily controlled as designed using a wet chemical coprecipitation method. The crystallite size and formal potential of Cu_xNi_yHCF films showed an insignificant change when 0 ≤ x : y < 0.3. Given the shape of the CV curves, this might be due to Cu²⁺ ions being inserted into the NiHCF framework as countercations to maintain the electrical neutrality of the structure. On the other hand, crystallite size depended linearly on the x : y ratio when x : y > 0.3. This is because Cu tended to replace Ni sites in the lattice structure at higher molar ratios of x : y. Cu_xNi_yHCF films inherited good electrochemical reversibility from the CuHCFs, in view of the cyclic voltammograms; in particular, Cu₁Ni₂HCF exhibited long-term cycling stability and high surface coverage. The adsorption of Co²⁺ fitted the Langmuir isotherm model well, and the kinetic data can be well described by a pseudo-second order model, which may imply that Co²⁺ adsorption is controlled by chemical adsorption. The diffusion process was dominated by both intraparticle diffusion and surface diffusion.

Cu_xNi_yHCF films with appropriate Cu/Ni ratios are expected to be prepared as designed for the recovery of Co²⁺ from spent LIBs.     

Chemical stability of Ca3Co4−xO9+δ/CaMnO3−δ p–n junction for oxide-based thermoelectric generators

An all-oxide thermoelectric generator for high-temperature operation depends on a low electrical resistance of the direct p–n junction. Ca₃Co_4−xO_9+δ and CaMnO_3−δ exhibit p-type and n-type electronic conductivity, respectively, and the interface between these compounds is the material system investigated here. The effect of heat treatment (at 900 °C for 10 h in air) on the phase and element distribution within this p–n junction was characterized using advanced transmission electron microscopy combined with X-ray diffraction. The heat treatment resulted in counter diffusion of Ca, Mn and Co cations across the junction, and subsequent formation of a Ca₃Co_1+yMn_1−yO₆ interlayer, in addition to precipitation of Co-oxide, and accompanying diffusion and redistribution of Ca across the junction. The Co/Mn ratio in Ca₃Co_1+yMn_1−yO₆ varies and is close to 1 (y = 0) at the Ca₃Co_1+yMn_1−yO₆–CaMnO_3−δ boundary. The existence of a wide homogeneity range of 0 ≤ y ≤ 1 for Ca₃Co_1+yMn_1−yO₆ is corroborated with density functional theory (DFT) calculations showing a small negative mixing energy in the whole range.

The heat treatment beneficially affects the performance of an all-oxide thermoelectric generator through phase and element distribution within this p–n junction.     

Ultradispersed IrxNi clusters as bifunctional electrocatalysts for high-efficiency water splitting in acid electrolytes

Design and synthesis of electrocatalysts with high activity and low cost is an important challenge for water splitting. We report a rapid and facile synthetic route to obtain Ir_xNi clusters via polyol reduction. The Ir_xNi clusters show excellent activity for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in acidic electrolytes. The optimized Ir₂Ni/C clusters exhibit an electrochemical active area of 18.27 mF cm⁻², with the overpotential of OER being 292 mV and HER being 30 mV at 10 mA cm⁻², respectively. In addition, the Ir₂Ni/C used as the cathode and anode for the H-type hydrolysis tank only needs 1.597 V cell voltages. The excellent electrocatalytic performance is mainly attributed to the synergistic effect between the metals and the ultra-fine particle size. This study provides a novel strategy that has a broad application for water splitting.

A method of preparing Ir_xNi/C clusters by polyol reduction using a XC-72R support was proposed. Due to the 2 nm size of the catalyst particles, more active sites are exposed. This is a promising route for the development of efficient water splitting electrocatalysts.     

Interior engineering of seaweed-derived N-doped versatile carbonaceous beads with CoxOy for universal organic pollutant degradation

The rational optimization of catalytic composites with excellent catalytic activities and long-term cycling stabilities for environmental remediation is still maintained as highly desired but is an ongoing challenge. Here, seaweed-derived N-doped versatile carbonaceous beads with Co_xO_y (Co-NC-0.25-700 °C) are employed as a novel catalyst to activate peroxymonosulfate (PMS) for methylene blue (MB) degradation. Profiting from the improved structure–activity relationship and the synergistic effects between the “egg-box” structure and the Co_xO_y loaded on the N-doped carbonaceous beads, Co-NC-0.25-700 °C exhibited relatively high performance and comparative long-term stability. The universal applicability of Co-NC-0.25-700 °C was investigated by degrading other types of organic pollutants in various systems. For this type of newly fabricated high-performance versatile composites, structure–property relationships were plausibly proposed. Notably, the degradation efficiency and the catalyst structure could be tailored by the amount of polyethyleneimine (PEI) introduced in the preparation process and by the pyrolysis temperature. More favorably, the coupling of the magnetic properties and bead-like shape endows the resultant composites with remarkable reusability and recyclability, as compared to powder state materials. Another interesting finding is that MB degradation over Co-NC-0.25-700 °C is minimally affected by common ions (Cl⁻, NO₃⁻, SO₄²⁻, etc.), and holds a certain catalytic activity under the background conditions of two simulated real water conditions (running water and seawater). Of particular interest, a microreactor filled with Co-NC-0.25-700 °C was utilized as a verification model for practical applications of the reaction in continuous-flow. More far-reaching, the simulations of actual water conditions and the design of a continuous-flow reactor represent a giant step towards universal applications for organic pollution treatment.

Interior engineering of seaweed-derived N-doped versatile carbonaceous beads with Co_xO_y formed by simple co-crosslinking and pyrolysis procedures are utilized for the degradation of various organic pollutants via peroxymonosulfate (PMS) activation.     

Ultrathin sulfate-intercalated NiFe-layered double hydroxide nanosheets for efficient electrocatalytic oxygen evolution

As an important two-dimensional material, layered double hydroxides (LDHs) show considerable potential in electrocatalytic reactions. However, the great thickness of the bulk LDH materials significantly limits their catalytic activity. In this work, we report ultrathin NiFe-LDH nanosheets with sulfate interlayer anions (Ni₆Fe₂(SO₄)(OH)₁₆·7H₂O) (U-LDH(SO₄²⁻)), which can be synthesized in gram-scale by a simple solvothermal method. The U-LDH(SO₄²⁻) shows excellent stability and great electrocatalytic performance in OER with a current density of 10 mA cm⁻² at a low overpotential of 212 mV and a small Tafel slope of 65.2 mV dec⁻¹, exhibiting its great potential for a highly efficient OER electrocatalyst.

Ultrathin NiFe-LDH nanosheets with sulfate interlayer anions prepared in gram-scale via one-pot solvothermal method exhibited excellent OER activity.