Core–shell structured Li–Fe electrode for high energy and stable thermal battery

The thermal battery, a key source for powering defensive power systems, employs Li alloy-based anodes. However, the alloying increases the reduction potential of Li which lowers the overall working voltage and energy output. To overcome these issues, Li alloy must be replaced with pure Li. Utilizing pure Li requires a structure that can hold liquefied Li because the working temperature for the thermal battery exceeds the melting point of Li. The liquefied Li can leak out of the anode, causing short-circuit. A Li–Fe electrode (LiFE) in which Fe powder holds liquefied Li has been developed. In LiFE, higher Li content can lead to higher energy output but increases the risk of Li leakage. Thus, Li content in the LiFE has been limited. Here, we demonstrate a novel core–shell electrode structure to achieve a higher energy output. The proposed core–shell LiFE incorporates a high Li content core and a low Li content shell; high energy comes from the core and the shell prevents the Li from leakage. The fabricated core–shell structured electrode demonstrates the high energy of 9074 W s, an increase by 1.66 times compared to the low Li content LiFE with the conventionally used Li content (5509 W s).

In LiFE, higher Li content can lead to higher energy output but increases the risk of Li leakage. Here, we demonstrate a novel core–shell electrode structure to achieve a higher energy output and prevent the Li from leakage.     

Fabrication of double core–shell Si-based anode materials with nanostructure for lithium-ion battery

Yolk–shell structure is considered to be a well-designed structure of silicon-based anode. However, there is only one point (point-to-point contact) in the contact region between the silicon core and the shell in this structure, which severely limits the ion transport ability of the electrode. In order to solve this problem, it is important that the core and shell of the core–shell structure are closely linked (face-to-face contact), which ensures good ion diffusion ability. Herein, a double core–shell nanostructure (Si@C@SiO₂) was designed for the first time to improve the cycling performance of the electrode by utilising the unique advantages of the SiO₂ layer and the closely contacted carbon layer. The improved cycling performance was evidenced by comparing the cycling properties of similar yolk–shell structures (Si@void@SiO₂) with equal size of the intermediate shell. Based on the comparison and analysis of the experimental data, Si@C@SiO₂ had more stable cycling performance and exceeded that of Si@void@SiO₂ after the 276^th cycle. More interestingly, the electron/ion transport ability of electrode was further improved by combination of Si@C@SiO₂ with reduced graphene oxide (RGO). Clearly, at a current density of 500 mA g⁻¹, the reversible capacity was 753.8 mA h g⁻¹ after 500 cycles, which was 91% of the specific capacity of the first cycle at this current density.

Double core shell structure can not only improve the efficiency of lithium transport, but also effectively alleviate volume expansion.     

Control of cyclic stability and volume expansion on graphite–SiOx–C hierarchical structure for Li-ion battery anodes

To increase the energy density of today''s batteries, studies on adding Si-based materials to graphite have been widely conducted. However, adding a Si-based material in the slurry mixing step suffers from low distribution due to the self-aggregation property of the Si-based material. Herein, a hierarchical structure is proposed to increase the integrity by using APS to provide a bonding effect between graphite and SiO_x. Additionally, to endow a protection layer, carbon is coated on the surface using the CVD method. The designed structure demonstrates enhanced integrity based on electrochemical performance. The MSG (methane decomposed SiO_x@G) electrode demonstrates a high ICE of 85.6% with 429.8 mA h g⁻¹ initial discharge capacity. In addition, the MSG anode has superior capacity retention (89.3%) after 100 cycles, with enhanced volumetric expansion (12.7%) after 50 cycles. We believe that the excellent electrochemical performance of MSG is attributed to increased integrity by using APS (3-aminopropyltrimethoxysilane) with a CVD carbon coating.

This study demonstrates the increased integrity of graphite–SiO_x–C hierarchical structure using 3-aminopropyltrimethoxysilane (APS). Furthermore, the carbon coating contributes to elec-trode stability.     

Microfluidics for core–shell drug carrier particles – a review

Core–shell drug-carrier particles are known for their unique features. Due to the combination of superior properties not exhibited by the individual components, core–shell particles have gained a lot of interest. The structures could integrate core and shell characteristics and properties. These particles were designed for controlled drug release in the desired location. Therefore, the side effects would be minimized. So, these particles'' advantages have led to the introduction of new methods and ideas for their fabrication. In the past few years, the generation of drug carrier core–shell particles in microfluidic chips has attracted much attention. This method makes it possible to produce particles at nanometer and micrometer levels of the same shape and size; it usually costs less than other methods. The other advantages of using microfluidic techniques compared to conventional bulk methods are integration capability, reproducibility, and higher efficiency. These advantages have created a positive outlook on this approach. This review gives an overview of the various fluidic concepts that are used to generate microparticles or nanoparticles. Also, an overview of traditional and more recent microfluidic devices and their design and structure for the generation of core–shell particles is given. The unique benefits of the microfluidic technique for core–shell drug carrier particle generation are demonstrated.

Microfluidics application for core–shell drug carrier particles synthesis and the advantages of using this technique compared to conventional bulk methods.     

Fabrication of a novel core–shell–shell temperature-sensitive magnetic composite with excellent performance for papain adsorption

Herein, a novel temperature-sensitive magnetic composite (Fe₃O₄@SiO₂@P(NIPAM-co-VI)/Cu²⁺) with a uniform core–shell–shell structure was successfully prepared via a layer-by-layer method. The resulting magnetic composite revealed good magnetic properties and remarkable affinity to papain with a maximum adsorption capacity of 199.17 mg g⁻¹. The adsorption equilibrium data fitted the pseudo-second-order kinetic and Freundlich models well, and the major thermodynamics parameters indicated that adsorption was an endothermic and spontaneous process. Fe₃O₄@SiO₂@P(NIPAM-co-VI)/Cu²⁺ could thermally protect papain, which is attributed to the reversible hydrophilic–hydrophobic transition of the composite at temperatures below and above the lower critical solution temperature. More importantly, the magnetic composite could be recycled at least six times without a remarkable loss in its adsorption capacity, and the process of adsorption and elution had no significant effect on the activity and structure of papain. This work could provide a novel separation method for papain without loss of its activity.

A novel core–shell–shell temperature-sensitive magnetic composite was designed. The composites showed excellent performance for papain adsorption and could thermally protect papain.     

A porous Co–Ru@C shell as a bifunctional catalyst for lithium–oxygen batteries

We use SiO₂ as a template and dopamine as a carbon source to synthesize a hollow C shell, and we load Co and Ru nanoparticles onto it to obtain a Co–Ru@C shell composite. The diameter and thickness of the C shell are 100 nm and 5–10 nm, respectively, and numerous holes of different sizes exist on the C shell. Meanwhile, numerous C shells stack together to form macropores, thereby forming a hierarchical porous structure in the material. Brunauer–Emmett–Teller surface area analysis reveals that the specific surface area and pore volume of the Co–Ru@C shell are 631.57 m² g⁻¹ and 2.20 cc g⁻¹, respectively, which can result in many three-phase interfaces and provide more space for the deposition of discharge products. Compared with Co@C shell and C shell electrodes, the obtained Co–Ru@C shell-based electrodes exhibit the highest discharge capacity, the lowest oxygen reduction reaction/oxygen evolution reaction overpotential and the best cycle stability, indicating the excellent catalytic ability of the Co–Ru@C shell.

We use SiO₂ as a template and dopamine as a carbon source to synthesize a hollow C shell, and we load Co and Ru nanoparticles onto it to obtain a Co–Ru@C shell composite.     

Preparation of Co–N carbon nanosheet oxygen electrode catalyst by controlled crystallization of cobalt salt precursors for all-solid-state Al–air battery

Production of bifunctional catalysts for catalyzing both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is highly advisable but challenging with respect to the applications of these catalysts in renewable energy conversion and storage technologies. Herein, we prepared highly reactive and stable cobalt-embedded nitrogen-rich carbon nanosheets (Co–N/CNs). Based on density functional theory (DFT) calculations and experiments, the as-prepared Co–N/CNs showed outstanding catalytic activities toward both OER and ORR. The optimized Co–N/CNs-800 catalyst revealed outstanding bifunctional catalytic activities for both ORR and OER with high catalytic efficiency and long-term durability, which were even comparable with those of the state-of-the-art Pt/C and RuO₂ catalysts. Furthermore, we observed that different cobalt salt precursors affected the size of Co nanoparticles, and both ORR and OER catalytic activities displayed completely consistent variations (sulfate < acetate < chloride < nitrate). An all-solid-state Al–air battery device comprising this hybrid catalyst showed superior performance when compared with the device containing the Pt/C catalyst.

Production of bifunctional catalysts for catalyzing both ORR and OER is highly advisable but challenging with respect to the applications of these catalysts in renewable energy conversion and storage technologies.     

Constructing high-performance electrode materials using core–shell ZnCo2O4@PPy nanowires for hybrid batteries and water splitting

Heterogeneity can be used as a promising method to improve the electrochemical performance of electrode materials; thus, ZnCo₂O₄@PPy samples were prepared using a facile hydrothermal route and an electrochemical deposition process. The as-prepared products possess a specific capacitance of 605 C g⁻¹ at a current density of 1 A g⁻¹. The asymmetric supercapacitor (ASC) possesses an energy density of 141.3 W h kg⁻¹ at a power density of 2700.5 W kg⁻¹ and capacity retention of 88.1% after 10 000 cycles, indicating its promising potential for energy devices. ZnCo₂O₄@PPy-50 exhibited an excellent OER performance and outstanding HER performance in alkaline media. As an advanced bifunctional electrocatalyst for overall water splitting, a voltage of 1.61 V at a current density of 50 mA cm⁻² outperforms the majority of noble-metal-free electrocatalysts.

Heterogeneity can be used as a promising method to improve the electrochemical performance of electrode materials; thus, ZnCo₂O₄@PPy samples were prepared using a facile hydrothermal route and an electrochemical deposition process.     

Core–shell Pd–P@Pt–Ni nanoparticles with enhanced activity and durability as anode electrocatalyst for methanol oxidation reaction

Pd–P@Pt–Ni core–shell nanoparticles, which consisted of a Pd–P alloy as a core and Pt–Ni thin layer as a shell, were explored as electrocatalysts for methanol oxidation reaction. The crystallographic information and the electronic properties were fully investigated by X-ray diffraction and X-ray photoelectron spectroscopy. In the methanol electrooxidation reaction, the particles showed high catalytic activity and strong resistance to the poisoning carbonaceous species in comparison with those of commercial Pt/C and the as-prepared Pt/C catalysts. The excellent durability was demonstrated by electrochemically active surface area loss and chronoamperometric measurements. These results would be due to the enhanced catalytic properties of Pt by the double synergistic effects from the core part and the nickel species in the shell part.

The Pd–P@Pt–Ni core–shell nanoparticles consist of an amorphous core and a low-crystalline shell. They exhibit the excellent catalytic properties in MOR owing to the double synergistic effects from the core and the nickel species in the shell.     

Co/N-Doped hierarchical porous carbon as an efficient oxygen electrocatalyst for rechargeable Zn–air battery

Developing efficient electrocatalysts for ORR/OER is the key issue for the large-scale application of rechargeable Zn–air batteries. The design of Co and N co-doped carbon matrices has become a promising strategy for the fabrication of bi-functional electrocatalysts. Herein, the surface-oxidized Co nanoparticles (NPs) encapsulated into N-doped hierarchically porous carbon materials (Co/NHPC) are designed as ORR/OER catalysts for rechargeable Zn–air batteries via dual-templating strategy and pyrolysis process containing Co²⁺. The fabricated electrocatalyst displays a core–shell structure with the surface-oxidized Co nanoparticles anchored on hierarchically porous carbon sheets. The carbon shells prevent Co NP cores from aggregating, ensuring excellent electrocatalytic properties for ORR with a half-wave potential of 0.82 V and a moderate OER performance. Notably, the obtained Co/NHPC as a cathode was further assembled in a zinc–air battery that delivered an open-circuit potential of 1.50 V, even superior to that of Pt/C (1.46 V vs. RHE), a low charge–discharge voltage gap, and long cycle life. All these results demonstrate that this study provides a simple, scalable, and efficient approach to fabricate cost-effective high-performance ORR/OER catalysts for rechargeable Zn–air batteries.

The surface-oxidized Co nanoparticles incorporated in N-doped hierarchically porous carbon materials are designed as ORR/OER catalyst for rechargeable Zn–air batteries via dual-templating strategy and pyrolysis process.     

Screening of metal–organic frameworks for water adsorption heat transformation using structure–property relationships

It is of great importance to correlate the water adsorption performance of MOFs to their physicochemical features in order to design and prepare MOFs for applications in adsorption heat transformation. In this work, both data analysis from existing studies and Grand Canonical Monte Carlo molecular simulation investigations were carried out. The results indicated that the highest water adsorption capacity was determined by the pore volume of MOF adsorbents, while there was a linear correlation interrelationship between isosteric heats of adsorption and the water adsorption performance at a low relative pressure. More detailed analysis showed that the charge distribution framework and pore size of MOFs contributed together to the hydrophilicity. Electrostatic interaction between water molecules and the framework atoms played a key role at low relative water pressure. A quantitative structure–property relationship model that can correlate the hydrophilicity of MOFs to their pore size and atomic partial charge was established. Along with some qualitative considerations, the screening methodology is proposed and is used to screen proper MOFs in the CoRE database. Seven MOFs were detected, and four of them were synthesized to validate the screening principle. The results indicated that these four MOFs possessed outstanding water adsorption performance and could be considered as promising candidates in applications for adsorption heating and cooling.

Quantitative structure–property relationship models that correlate the water adsorption performance of MOFs to their physicochemical features have been established.     

Hydrated negative air ions generated by air–water collision with TiO2 photocatalytic materials

Photocatalytic materials are often used in the field of electrolysis of water for its competitive performance and low cost. This study describes the use of TiO₂ for providing free electrons to prepare hydrated negative air ions together with the Lenard effect caused by air–water collision. The lifetime of HNAIs increased by 47.62% in comparison with the traditional corona discharge method; both the stability and the actual yield of the HNAIs increased significantly. The stability of HNAIs has a correlative relationship with the molecular weight and relative humidity. Lower mobility of the HNAIs with larger molecular weight results in low probability of collision with other air particles, making it relatively stable. Water molecules could form a water shell around the cluster ions in a high relative humidity environment, which can protect the ions, avoiding physical collision to extend the lifetime.

Illustration of a hydrated negative air ion generation system, water droplets and O₂ molecular capture electrons generated by TiO₂ to form water cluster ions.     

All solid state rechargeable aluminum–air battery with deep eutectic solvent based electrolyte and suppression of byproducts formation

In order to create a rechargeable aluminum (Al)–air battery, an aluminum–air battery with a deep eutectic solvent-based solid electrolyte was prepared. The prepared battery demonstrated a capacity smaller than the theoretical value although we observed stable electrochemical reactions. When TiN was used as an air cathode material, byproducts of the aluminum–air battery such as Al(OH)₃ and Al₂O₃ were not detected on either the Al anode nor the air cathode. Even though we did not detect byproducts, we observed NaCl and NH₄Cl phases on the air cathode, and they did not hinder the electrochemical reaction.

In order to create a rechargeable aluminum (Al)–air battery, an aluminum–air battery with a deep eutectic solvent-based solid electrolyte was prepared.     

Thermal responses to whole‐body cooling in air with special reference to arteriovenous anastomoses in fingers

The arteriovenous anastomoses (AVAs) in the distal parts of the extremities play a significant role in the heat exchange with the environment. The aim of the study was to examine the thermal responses to whole‐body cooling in air, and especially the behaviour of finger skin temperature (T_f, rich in AVAs). Eight young men sat in minimal clothing at 32°C air temperature (T_a), which was then lowered gradually to 13°C in 100 min. In the beginning of cooling, T_f was high and fluctuating, and then suddenly exhibited a rapid fall, while temperatures in other skin sites fell fairly linearly along decreasing T_a to the end of cooling. During the period from start to the rapid fall in T_f, rectal temperature decreased from 37·4°C (SD 0·2) to 37·2°C (0·2), mean skin temperature (T_sk) from 34·6°C (0·5) to 31·2°C (2·0) and whole‐body thermal sensation from ‘slightly warm/warm’ to ‘slightly cool/cold’. The start of the steep fall in T_f varied considerably between individuals in terms of time (2–75 min), T_a (16·7–32·0°C) and T_sk (28·8–34·7°C). On the other hand, the range of T_f at that point was narrower (32·1–35·8°C). The findings stress the importance of taking into account the distal skin temperatures in thermoregulatory studies in addition to the ordinarily used more proximal and central skin sites. Also, it might be advisable to start such experiments with relatively high and fluctuating T_f to guarantee that the thermal state of the subject is well defined.     

Continuous syntheses of carbon-supported Pd and Pd@Pt core–shell nanoparticles using a flow-type single-mode microwave reactor

Continuous syntheses of carbon-supported Pd@Pt core–shell nanoparticles were performed using microwave-assisted flow reaction in polyol to synthesize carbon-supported core Pd with subsequent direct coating of a Pt shell. By optimizing the amount of NaOH, almost all Pt precursors contributed to shell formation without specific chemicals.

Continuous syntheses of carbon-supported Pd@Pt core–shell nanoparticles were performed using flow processes including microwave-assisted Pd core–nanoparticle formation.

Continuous flow syntheses have attracted attention as a powerful method for organic, nanomaterial, and pharmaceutical syntheses because of various features that produce benefits in terms of efficiency, safety, and reduction of environmental burdens.^1–7 Advances of homogeneous heating and mixing techniques in continuous flow reactors have engendered further developments for precise reaction control, which is expected to create innovative materials through combination with multiple-step flow syntheses.Microwave (MW) dielectric heating has been recognized as a promising methodology for continuous flow syntheses because rapid or selective heating raises the reaction rate and product yield.^8–18 For the last two decades, most MW apparatus has been batch-type equipped with a stirring mechanism in a multi-mode cavity. Therefore, conventionally used MW-assisted flow reactors have been mainly of the modified batch-type. Results show that the electromagnetic field distribution can be spatially disordered, causing inhomogeneous heating of the reactor.^19–25 Improvements of reactors suitable for flow-type work have been studied actively in recent years to improve their energy efficiency and to make irradiation of MW more homogeneous.^26–37We originally designed a MW flow reactor system that forms a homogeneous heating zone through generation of a uniform electromagnetic field in a cylindrical single-mode MW cavity.^26,30 The temperatures of flowing liquids in the reactor were controlled precisely via the resonance frequency auto-tracking function. Continuous flow syntheses of metal nanoparticle, metal-oxide, and binary metal core–shell systems with uniform particle size have been achieved using our MW reactor system.^26,38,39 Furthermore, large-scale production necessary for industrial applications can be achieved through integration of multiple MW reactors.³⁰Carbon-supported metal catalysts are widely used in various chemical transformations and fine organic syntheses. Particularly, binary metal systems such as Pd@Pt core–shell nanoparticles have attracted considerable interest for electro-catalysis in polymer electrolyte membrane fuel cells (PEMFC) because of their enhanced oxygen reduction activity compared to a single-use Pt catalyst. Binary metal systems also contribute to minimization of the usage of valuable Pt.^40–51 Earlier studies of carbon-supported Pd@Pt syntheses involved multiple steps of batch procedures such as separation, washing and pre-treatment of core metal nanoparticles, coating procedures of metal shells, and dispersion onto carbon supports. Flow-through processes generally present advantages over batch processes in terms of simplicity and high efficiency in continuous material production.We present here a continuous synthesis of carbon-supported Pd and Pd@Pt core–shell nanoparticles as a synthesis example of a carbon-supported metal catalyst using our MW flow reactor. This system incorporates the direct transfer of a core metal dispersion into a shell formation reaction without isolation. Nanoparticle desorption is prevented by nanoparticle synthesis directly on a carbon support. The presence of protective agents that are commonly used in nanoparticle syntheses, such as poly(N-vinylpyrrolidone), can limit the chemical activity of the catalyst. Nevertheless, this system requires no protective agent. Moreover, this system is a simple polyol synthesis that uses no strong reducing agent. It therefore imposes little or no environmental burden. For this study, the particle size and distribution of metals in Pd and Pd@Pt core–shell nanoparticles were characterized using TEM, HAADF-STEM observations, and EDS elemental mapping. From electrochemical measurements, the catalytic performance of Pd@Pt core–shell nanoparticles was evaluated.A schematic view of the process for the continuous synthesis of carbon-supported Pd@Pt core–shell nanoparticles is presented in Fig. 1. Details of single-mode MW flow reactor are described in ESI.^† We attempted to conduct a series of reactions coherently in a flow reaction system, i.e., MW-assisted flow reaction for the synthesis of carbon supported core Pd nanoparticles with subsequent deposition of the Pt shell. Typically, a mixture containing Na₂[PdCl₄] (1–4 mM) in ethylene glycol (EG), carbon support (Vulcan XC72, 0.1 wt%), and an aqueous NaOH solution were prepared. This mixture was introduced continuously into the PTFE tube reactor placed in the center of the MW cavity. Here, EG works as the reaction solvent as well as the reducing agent that converts Pd(ii) into Pd(0) nanoparticles. The MW heating temperature was set to 100 °C with the flow rate of 80 ml h^−l, which corresponds to residence time of 4 s. The carbon-supported Pd nanoparticles were transferred directly to the Pt shell formation process without particle isolation. The dispersed solution was introduced into a T-type mixer and was mixed with a EG solution of H₂[PtCl₆]·6H₂O (10 mM). The molar ratio of Pd : Pt was fixed to 1 : 1. Subsequently, after additional aqueous NaOH solution was mixed at the second T-mixer, the reaction mixture was taken out of the mixer and was let to stand at room temperature (1–72 h) for Pt shell growth.Open in a separate windowFig. 1Schematic showing continuous synthesis of carbon-supported Pd and Pd@Pt core–shell nanoparticles. The Pd nanoparticles were dispersed on the carbon support by MW heating of the EG solution. The solution was then transferred directly to Pt shell formation.Rapid formation of Pd nanoparticles with average size of 3.0 nm took place at the carbon-support surface during MW heating in the tubular reactor (Fig. 2a). Most of the Pd(ii) precursor was converted instantaneously to Pd(0) nanoparticles and was well dispersed over the carbon surface. Fig. 2b shows the time profile of the outlet temperature and applied MW power during continuous synthesis of carbon-supported Pd nanoparticles. The solution temperature rose instantaneously, reaching the setting temperature in a few seconds. This temperature was maintained with high precision (±2 °C) by the continuous supply of ca. 18 W microwave power. No appreciable deposition of metal was observed inside of the PTFE tube. It is noteworthy that Pd of 98% or more was supported on carbon by heating for 4 s at 100 °C from ICP-OES measurement. Our earlier report described continuous polyol (EG) synthesis of Pd nanoparticles as nearly completed with 6 s at 200 °C.³⁹ The reaction temperature in polyol synthesis containing the carbon was considerably low, suggesting that selective reduction reaction occurs on the carbon surface, which is a high electron donating property.Open in a separate windowFig. 2(a) TEM image of carbon-supported Pd nanoparticles synthesized using the MW flow reactor. The average particle size was 3.0 nm. (b) The time profile of the temperature at the reactor outlet and applied microwave power during continuous synthesis of carbon-supported Pd nanoparticles. Na₂[PdCl₄] = 2 mM, NaOH = 10 mM.The concentrations of Na₂[PdCl₄] precursor and NaOH affect the Pd nanoparticle size. Results show that the Pd particle size increased as the initial concentration of Na₂[PdCl₄] increased (Fig. S1a and b^†). Change of NaOH concentration exerted a stronger influence on the particle size. Nanoparticles of 12.3 nm were observed without addition of NaOH, whereas 2.6 nm size particles were deposited at the concentration of 20 mM (Fig. S1c and d^†). The higher NaOH concentration led to instantaneous nucleation and rapid completion of reduction. The Pd nanoparticle surface is equilibrated with Pd–O⁻ and Pd–OH depending on the NaOH concentration. The surface is more negative at high concentrations of NaOH because of the increase of the number of Pd–O⁻, which inhibits the mutual aggregation and further particle growth. Furthermore, to control the Pd nanoparticle morphology, we conducted synthesis by adding NaBr, which has been reported as effective for cubic Pd nanoparticle synthesis.⁵² However, because reduction of the Pd precursor derives from electron donation from both the polyol and the carbon support, morphological control was not achieved (Fig. S2^†). That finding suggests that morphological control is difficult to achieve by adding surfactant agents to the polyol.For Pt shell formation, carbon supported Pd nanoparticles (3.0 nm average particle size) were mixed with H₂[PtCl₆]·6H₂O solution with the molar ratio of Pd : Pt = 1 : 1. Then additional NaOH solution was mixed. As described in earlier reports,³⁹ alkaline conditions under which base hydrolysis and reduction of [PtCl₆]²⁻ to [Pt(OH)₄]²⁻ takes place are necessary for effective Pt shell formation. It is noteworthy that the added Pt precursor was almost entirely supported on carbon within 24 h in cases where an appropriate amount of additional NaOH (5 mM) was mixed by the second T-mixer (Fig. 3a). However, for 10 mM, nucleation and growth of single Pt nanoparticles were enhanced in place of core–shell formation. Consequently, a mixture of Pd@Pt and single Pt nanoparticles was formed on the carbon support (Fig. 3b). Very fine Pt nanoparticles were observed in the supernatant solution.Open in a separate windowFig. 3(a) Time profiles of residual ratio of Pt in the mixed solutions. Horizontal axis was left standing time. Carbon-support in the mixed solution after added the Pt precursor was precipitated by centrifugation. The supernatant solution was measured by ICP-OES. Concentrations of additional NaOH were 0, 5, and 10 mM. (b) TEM image of carbon-supported Pd@Pt core–shell nanoparticles. The synthesis conditions of Pd nanoparticles were Na₂[PdCl₄] (2 mM) and NaOH (10 mM). The molar ratio of Na₂[PdCl₄] : H₂[PtCl₆]·6H₂O was 1 : 1, and additional NaOH concentration was 10 mM. After left standing for 72 h, the mixture of Pd@Pt and single Pt nanoparticles (1–2 nm) was formed on carbon-support. Fig. 4a portrays a TEM image of carbon supported Pd@Pt core–shell nanoparticles. The average particle size of Pd@Pt core–shell nanoparticles was 3.6 nm after being left to stand for 24 h: larger than the initial Pd nanoparticles (3.0 nm). Fig. 4b shows the HAADF-STEM image of Pd@Pt core–shell nanoparticles supported on carbon. The core–shell structure of the particles can be ascertained from the contrast of the image. The Z-contrast image shows the presence of brighter shells over darker cores. Actually, the contrast is strongly dependent on the atomic number (Z) of the element.⁵³ The Z values of Pt (Z = 78) and Pd (Z = 46) differ considerably. Therefore, the image shows the formation of Pd@Pt core–shell structure with the uniform elemental distribution. Elemental mapping images by STEM-EDS show that both Pd and Pt metals were present in all the observed nanoparticles (Fig. 4c). Based on the atomic ratio (Pd : Pt = 49 : 51), they show good agreement with the designed values. The Pt shell thickness was estimated as about 0.6 nm, which corresponds to 2–3 atomic layer thickness of Pt encapsulating the Pd core metal, indicating good agreement with Fig. 4b image. For an earlier study, uniform Pt shells were formed by dropwise injection of the Pt precursor solution because the Pt shell growth rate differs depending on the crystal plane of the Pd nanoparticle.⁴⁶ For more precise control of shell thickness in our system, the Pt precursor solution should be mixed in multiple steps.Open in a separate windowFig. 4(a) TEM image and (b) HAADF-STEM image of carbon-supported Pd@Pt core–shell nanoparticles and the line profile of contrast. (c) Elemental mapping image of carbon-supported Pd@Pt core–shell nanoparticles, where Pd and Pt elements are displayed respectively as red and green. The EDS atomic ratio of Pd : Pt was 49 : 51. The synthesis conditions of Pd nanoparticles were Na₂[PdCl₄] (2 mM) and NaOH (10 mM). The molar ratio of Na₂[PdCl₄] : H₂[PtCl₆]·6H₂O was 1 : 1. The concentration of additional NaOH were 5 mM. It was left standing for 24 h.A comparison of the catalytic performance of the carbon-supported Pd@Pt core–shell and Pt nanoparticles is shown in Fig. S3.^† For this experiment, carbon-supported Pt nanoparticles with Pt 2 mM were prepared as a reference catalyst using a similar synthetic method. The initial Pt mass activities of the carbon-supported Pd@Pt and Pt nanoparticles were, respectively, 0.39 and 0.24 A mg_Pt⁻¹, improving by the core–shell structure. In addition, durability tests for carbon-supported Pd@Pt nanoparticles show that the reduction rate of Pt mass activity after 5000 cycles was only 2%. The catalytic activities of carbon-supported Pd@Pt nanoparticles were superior in terms of durability, suggesting that the Pt shell was firmly formed.     

Counterion coupled (COCO) gemini surfactant capped Ag/Au alloy and Ag@Au core–shell nanoparticles for cancer therapy

Hybrid silver (Ag)–gold (Au) nanoparticles (NPs) with different sizes and compositions were synthesized. Ag/Au alloy and Ag@Au core–shell type NPs were prepared from Ag and Au with various ratios using the COCO gemini surfactant, 1,6-bis (N,N-hexadecyldimethylammonium) adipate (COCOGS), 16-6-16 as a stabilizer. The formation of the Ag/Au alloy and Ag@Au core–shell was confirmed by UV-visible absorption spectroscopy, high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDX) and selected area electron diffraction (SAED) patterns. Depending on the composition of the Ag/Au alloy NPs, the λ_max values varied from 408 nm to 525 nm. FTIR measurements were used to evaluate the adsorption of the COCO gemini surfactant (16-6-16) on the Ag/Au alloy and Ag@Au core–shell surface. In this present work, we study how to achieve the stability and activity of the COCO gemini surfactant (16-6-16) capped Ag/Au alloy and Ag@Au core–shell NPs for developing novel anti-cancer agents by evaluating their potentials in the Hep-2 cell line model. Thus the developed core–shell NPs were possibly involved in inducing cytotoxicity followed by inhibition of cell proliferation to the cancer cells with apoptosis induction. The developed core–shell NPs might serve as highly applicable agents in the development of next-generation cancer chemotherapeutic agents.

In this work hybrid silver (Ag)–gold (Au) nanoparticles (NPs) with different sizes and compositions were synthesized and applied for anticancer evaluations and which is effectively involved in cancer cell apoptosis through DNA damage.     

Layered metal–organic framework based on tetracyanonickelate as a cathode material for in situ Li-ion storage

Prussian blue analogs (PBAs) formed with hexacyanide linkers have been studied for decades. The framework crystal structure of PBAs mainly benefits from the six-fold coordinated cyano functional groups. In this study, in-plane tetracyanonickelate was utilized to engineer an organic linker and design a family of four-fold coordinated PBAs (FF-PBAs; Fe²⁺Ni(CN)₄, MnNi(CN)₄, Fe³⁺Ni(CN)₄, CuNi(CN)₄, CoNi(CN)₄, ZnNi(CN)₄, and NiNi(CN)₄), which showed an interesting two-dimensional (2D) crystal structure. It was found that these FF-PBAs could be utilized as cathode materials of Li-ion batteries, and the Ni/Fe²⁺ system exhibited superior electrochemical properties compared to the others with a capacity of 137.9 mA h g⁻¹ at a current density of 100 mA g⁻¹. Furthermore, after a 5000-cycle long-term repeated charge/discharge measurement, the Ni/Fe²⁺ system displayed a capacity of 60.3 mA h g⁻¹ with a coulombic efficiency of 98.8% at a current density of 1000 mA g⁻¹. In addition, the capacity of 86.1% was preserved at 1000 mA g⁻¹ as compared with that at 100 mA g⁻¹, implying a good rate capability. These potential capacities can be ascribed to an in situ reduction of Li⁺ in the interlayer of Ni/Fe²⁺ instead of the formation of other compounds with the host material according to ex situ XRD characterization. These specially designed FF-PBAs are expected to inspire new concepts in electrochemistry and other applications requiring 2D materials.

Prussian blue analogs (PBAs) with tetracyanide linkers have been studied as electrode materials for Li-ion storage.     

Synthesis and characterization of sulfonated mesoporous NiO–ICG core–shell solid sphere catalyst with superior capability for methyl ester production

In the present research, a mesoporous NiO core–shell solid sphere was hydrothermally synthesized, using polyethylene glycol (PEG; 4000) as a surfactant and incomplete carbonized glucose (ICG) as a template. Then, thermal decomposition of ammonium sulphate was employed to convert the as-synthesized material to sulfonated mesoporous NiO–ICG catalyst, in order to accelerate conversion of waste cooking palm oil (WCPO) into ester. The structural, textural, morphological, and thermal characteristics of the synthesized sulfonated mesoporous NiO–ICG catalyst were evaluated using X-ray diffraction (XRD), Raman spectroscopy, temperature programed desorption (TPD), Brunauer–Emmet–Teller (BET), thermogravimetric analysis (TGA), and transmission electron microscopy (TEM). Furthermore, the effect of different reaction parameters against reaction time were investigated. Under the optimal transesterification conditions; catalyst loading of 1 wt%, methanol to WCPO ratio of 9 : 1, operation temperature of 100 °C and mixing intensity of 450 rpm, an optimum ester yield of 95.6% was achieved. Additionally, a recyclability study proved that the spent catalyst was highly potential to be reused for nine successive transesterification reactions without further treatment. Finally, the physicochemical characteristics of the produced WCPO methyl ester were evaluated which were highly in accordance with both European (EN; 14214) and American Standards for Testing Materials (ASTM; D6751) specifications.

In the present research, a mesoporous NiO core–shell solid sphere was hydrothermally synthesized, using polyethylene glycol (PEG; 4000) as a surfactant and incomplete carbonized glucose (ICG) as a template.     

Regulation of polylactic acid using irradiation and preparation of PLA–SiO2–ZnO melt-blown nonwovens for antibacterial and air filtration

Since the COVID-19 pandemic, polypropylene melt-blown nonwovens (MBs) have been widely used in disposable medical surgical masks and medical protective clothing, seriously threatening the environment. As a bio-based biodegradable polymer, polylactic acid (PLA) has attracted great attention in fabricating MBs. However, there are still issues with the undesirable spinnability of PLA and the limited filtration and antibacterial performance of PLA MBs. Herein, a high-efficiency, low-resistance, and antibacterial PLA filter is fabricated by melt-blown spinning and electret postprocessing technology. The irradiation technique is used to tune PLA chain structure, improving its spinnability. Further, silica (SiO₂) nanoparticles are added to enhance the charge storage stability of PLA MBs. With a constant airflow rate of 32 L min⁻¹, the PLA-based MBs exhibit a high particulate filtration efficiency of 94.8 ± 1.5%, an ultralow pressure drop of 14.1 ± 1.8 Pa, and an adequate bacterial filtration efficiency of 98 ± 1.2%, meeting the medical protective equipment standard. In addition, the zinc oxide (ZnO) masterbatches are doped into the blend and the antibacterial rate of PLA-based MBs against Escherichia coli and Staphylococcus aureus is higher than 99%. This successful preparation and modification method paves the way for the large-scale production of PLA MBs as promising candidates for high-efficacy and antibacterial filters.

PLA MBs with high filtration efficiency and antibacterial activity were prepared by reducing viscosity by irradiation and blending ZnO and SiO₂.