Toward the Production of Hydroxyapatite/Poly(Ether-Ether-Ketone) (PEEK) Biocomposites: Exploring the Physicochemical, Mechanical, Cytotoxic and Antimicrobial Properties.

The development of hydroxyapatite (HAp) and polyether ether ketone (PEEK) biocomposites has been extensively studied for bone repair applications due to the synergistic properties of the involved materials. In this study, we aimed to develop HAp/PEEK biocomposites using high-energy ball milling, with HAp concentrations (20%, 40%, and 60% w/v) in PEEK, to evaluate their physicochemical, mechanical, cytotoxicity, and antimicrobial properties for potential applications in Tissue Engineering (TE). The biocomposites were characterized by structure, morphology, apparent porosity, diametral compression strength, cytotoxicity, and antimicrobial activity. The study results demonstrated that the HAp/PEEK biocomposites were successfully synthesized. The C2 biocomposite, containing 40% HAp, stood out due to the optimal distribution of HAp particles in the PEEK matrix, resulting in higher compression strength (246 MPa) and a homogeneous microstructure. It exhibited antimicrobial activity against Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli, with no cytotoxicity observed. These properties make the C2 biocomposite promising for regenerative medicine applications, combining mechanical strength, bioactivity, and biocompatibility.

Technologies for Mechanical Recycling of Carbon Fiber-Reinforced Polymers (CFRP) Composites: End Mill, High-Energy Ball Milling, and Ultrasonication.

Carbon fiber reinforced polymer (CFRP) composites have very high specific properties, which is why they are used in the aerospace, wind power, and sports sectors. However, the high consumption of CFRP compounds leads to a high volume of waste, and it is necessary to formulate mechanical recycling strategies for these materials at the end of their useful life. The recycling differences between cutting-end mills and high-energy ball milling (HEBM) were evaluated. HEBM recycling allowed us to obtain small recycled particles, but separating their components, carbon fiber, epoxy resin, and CFRP particles, was impossible. In the case of mill recycling, these were obtained directly from cutting a CFRP composite laminate. The recycled materials resulted in a combination of long fibers and micrometric particles-a sieving step allowed for more homogeneous residues. Although long, individual carbon fibers can pass through the sieve. Ultrasonication did not significantly affect HEBM recyclates because of the high energy they are subjected to during the grinding process, but it was influential on end mill recyclates. The ultrasonication amplitude notably impacted the separation of the epoxy resin from the carbon fiber. The end mill and HEBM waste production process promote the presence of trapped air and electrostatics, which allows recyclates to float in water and be hydrophobic.

Nanoscale Stolephorus sp. powder fabrication using high-energy milling for bioactive materials in dentistry.

BACKGROUND: The application of natural products in dentistry has been widely explored. Anchovy (Stolephorus in Latin) has been examined for its bioactive content (calcium, phosphorus and fluoride) as an agent for bone stimulation and tooth development, topical fluoridation and pulp capping. Ball milling has been used to prepare calcium oxide nanoparticles from snakehead fish bone. OBJECTIVES: The aim of the study was to reduce the particle size of Stolephorus sp. powder to the nanoscale using high-energy ball milling for 8, 12 and 24 h, and to analyze the optimal milling time by comparing the powder characteristics. MATERIAL AND METHODS: The Stolephorus sp. were oven-dried at 50°C for 6 h, after which the entire fish were crushed into powder. The fish powder was produced by blending the material for 5 min and passing it through a 200-mesh sieve. The remaining dried fish was blended again for 5 min until it passed through the sieve. The top-down approach to the particle size reduction was performed using high-energy milling at 3 distinct time points (8, 12 and 24 h). The characteristics of the powder were evaluated using a particle size analyzer, a Fourier-transform infrared spectrometer (FTIR) and scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS). RESULTS: The Stolephorus sp. powder contained 64.50% protein, 7,420 mg/kg sodium, 28,912 mg/kg calcium, and 1,924 mg/kg magnesium. The high-energy milling process resulted in a reduction of the particle size from the microscale to the nanoscale. The analysis of the average particle size and polydispersity index indicated that 24 h of milling showed the most optimal results. Furthermore, the functional groups exhibited no significant alteration at 3 milling times (p ≥ 0.05, FTIR analysis). CONCLUSIONS: The high-energy milling method has the potential to reduce the particle size of Stolephorus sp. powder to the nanoscale at the 8- and 24-h milling periods. The powder resulting from the 24-h milling process had a size of 789.3 ±170.7 nm, smooth size distribution, good size uniformity, a polydispersity index of 0.763, no significant change in organic and inorganic compound content, and a calcium/phosphorus ratio that was the closest to that of hydroxyapatite (HAp).

The Influence of High-Energy Milling on the Phase Formation, Structural, and Photoluminescent Properties of CaWO4 Nanoparticles.

CaWO4 nanoparticles were obtained by facile mechanochemical synthesis at room temperature, applying two different milling speeds. Additionally, a solid-state reaction was employed to assess the phase composition, structural, and optical characteristics of CaWO4. The samples were analyzed by X-ray diffraction (XRD), transition electron microscopy (TEM), and Raman, infrared (IR), ultraviolet-visible (UV-Vis) reflectance, and photoluminescence (PL) spectroscopies. The phase formation of CaWO4 was achieved after 1 and 5 h of applied milling speeds of 850 and 500 rpm, respectively. CaWO4 was also obtained after heat treatment at 900 °C for 12 h. TEM and X-ray analyses were used to calculate the average crystallite and grain size. The Raman and infrared spectroscopies revealed the main vibrations of the WO4 groups and indicated that more distorted structural units were formed when the compound was synthesized by the solid-state method. The calculated value of the optical band gap of CaWO4 significantly increased from 2.67 eV to 4.53 eV at lower and higher milling speeds, respectively. The determined optical band gap of CaWO4, prepared by a solid-state reaction, was 5.36 eV. Blue emission at 425 (422) nm was observed for all samples under an excitation wavelength of 230 nm. CaWO4 synthesized by the solid-state method had the highest emission intensity. It was established that the intensity of the PL peak depended on two factors: the morphology of the particles and the crystallite sizes. The calculated color coordinates of the CaWO4 samples were located in the blue region of the CIE diagram. This work demonstrates that materials with optical properties can be obtained simply and affordably using the mechanochemical method.

Bosentan monohydrate and sildenafil base as two companions in enabling formulations.

HYPOTHESIS: Sildenafil base and bosentan monohydrate are co-administered in a chronic therapy of pulmonary arterial hypertension (PAH). Both drugs are poorly soluble in water, and their bioavailability is limited to ca. 50 %. Since bosentan is a weak acid, whereas sildenafil is a weak base, we assumed that their co-amorphization could: (i) improve their solubility in the gastrointestinal fluids, (ii) enable to reach supersaturation and (iii) ensure stabilization of supersaturated solutions. If successful, this could accelerate the development of new fixed-dose combination drugs. EXPERIMENTS: The co-amorphous formulations were prepared using high energy ball milling. Their solid state properties were assessed using XRD, DSC, FT-MIR, and dielectric spectroscopy. Particle size distribution and surface wetting were also analyzed. Polarizing optical microscopy and scanning electron microscopy were applied to assess the microstructure of these powders. A new HPLC-DAD method was developed for a simultaneous quantification of both drugs. FINDINGS: It was shown that binary formulations in which bosentan was molecularly dispersed in sildenafil base (Tg = 64-78 °C) could be manufactured in the high energy ball milling process. When the sildenafil load was below 50 wt. %, the formulations showed the greatest thermal stability and formed long-lasting bosentan supersaturation in PBS.

Enhanced microstructure and mechanical properties of ZrN-reinforced AlSi10Mg aluminum matrix composite.

Aluminum matrix composites (AMCs), incorporating Zirconium Nitride (ZrN) as reinforcing additives, demonstrate immense promise for applications in aerospace, automotive, and power generation due to their unique combination of low density, superior mechanical properties, and excellent thermal/electrical conductivity. This study explores the influence of ZrN reinforcement on the microstructure and mechanical properties of AlSi10Mg metal-matrix composites. Utilizing high-energy ball milling (HEBM) and spark-plasma sintering (SPS), ZrN/AlSi10Mg composites were synthesized, achieving nearly full density with uniform ZrN distribution, while phase and chemical transformations were not observed in the bulk composites. The addition of ZrN resulted in a notable increase in hardness of 237% (182 ± 8 HV2), elastic modulus of 56% (114 ± 3 GPa), compressive and tensile strength of 183% (565 ± 15 GPa), and 125% (387 ± 9 GPa), respectively, for composites containing 30% ZrN, compared to the non-reinforced alloy. Experimentally determined coefficients of thermal expansion (CTEs) for composites with 10%, 20%, and 30% ZrN content were 19.8 × 10-6 °C-1, 19.1 × 10-6 °C-1, and 18 × 10-6 °C-1, respectively, which well relates to Schapery's model. These findings contribute to understanding the synthesis, mechanical behavior, and thermal properties of ZrN/AlSi10Mg composites, demonstrating their potential for diverse engineering applications.

Effect of Milling Time and Reinforcement Volume Fraction on Microstructure and Mechanical Properties of SiCp-Reinforced AA2017 Composite Powder Produced by High-Energy Ball Milling.

The influence of milling time and volume fraction of reinforcement on the morphology, microstructure, and mechanical behaviors of SiCp-reinforced AA2017 composite powder produced by high-energy ball milling (HEBM) was investigated. AA2017 + SiCp composite powder with different amounts of SiC particles (5, 10, and 15 vol%) was successfully prepared from gas-atomized AA2017 aluminum alloy powder with a particle size of <100 µm and silicon carbide (SiC) powder particles with an average particle size of <1 µm. An optical microscope (OM), X-ray diffraction (XRD), and scanning electron microscope (SEM) were utilized to characterize the microstructure of the milled composite powder at different milling periods. The results indicated that the SiC particles were homogeneously distributed in the AA2017 matrix after 5 h of HEBM time. The morphology of the particles transformed from a laminar to a nearly spherical shape, and the size of the milled powder particles reduced with increasing the content of SiC particles. The XRD analysis was carried out to characterize the phase constituents, crystallite size, and lattice strain of the composite powders at different milling periods. It was found that with increasing milling time and SiC volume fraction, the crystallite size of the aluminum alloy matrix decreased while the lattice strain increased. The average crystallite sizes were reduced from >300 nm to 68 nm, 64 nm, and 64 nm after 5 h of milling, corresponding to SiC contents of 5, 10, and 15 vol%, respectively. As a result, the lattice strain increased from 0.15% to 0.5%, which is due to significant plastic deformation during the ball milling process. XRD results showed a rapid decrease in crystallite size during the early milling phase, and the minimum grain size was achieved at a higher volume fraction of SiC particles. Microhardness tests revealed that the milling time has a greater influence on the hardness than the amount of SiC reinforcements. Therefore, the composite powder milled for 5 h showed an average microhardness three times higher than that of the unmilled powder particles.

Structural analysis of potato starch transformation during high-energy ball-milling: Oxygen and humidity content effects.

High Energy Ball-Milling (HEBM) modifies starchs' granule morphology, physicochemical properties, and chemical structure. However, understanding how the HEBM changes the starch chemical structure is necessary to control these modifications. Therefore, this study aimed to investigate the changes in potato starch's long- and short-range molecular order during HEBM at different environmental conditions such as oxygen (Air) and humidity content. Due to the correlation between the starch modification and the energy supplied (Esupp) by the HEBM, Burgio's equation was used to calculate this energy. The starch transformation was followed by X-ray diffraction, Fourier Transform-Infrared Spectroscopy, and Raman spectroscopy. A Principal Component Analysis (PCA) was conducted to reduce the HEBM variables. PAC analysis demonstrated that the different oxygen-humidity conditions do not affect the HEBM of potato starch. Based on the starch chemical structure transformation correlated with Esupp during HEBM, four stages were observed: orientation, modification, mechanolysis, and over-destruction. It was identified for the first time that at low milling energy (<1.5 kJ/g, orientation stage), the glycosidic rings change their orientation, and starch-water interaction increases while the starch's organization reduces. Ergo, the potato starch could be more susceptible to chemical modifications during the first two stages.

Silver-Assisted Hydrogen Evolution from Aluminum Oxidation in Saline Media.

A swarf of aluminum alloy with high corrosion resistance and ductility was successfully converted into fine hydro reactive powders via ball milling with silver powder and either lithium chloride or gallium. The latter substances significantly intensified particle size reduction, while silver formed 'cathodic' sites (Ag, Ag2Al), promoting Al corrosion in aqueous saline solutions with hydrogen generation. The diffraction patterns, microphotographs, and elemental analysis results demonstrated partial aluminum oxidation in the samples and their contamination with tungsten carbide from milling balls. Those factors were responsible for obtaining lower hydrogen yields than expected. For AlCl3 solution at 60 °C, Al-LiCl-Ag, Al-LiCl, Al-Ga-Ag, and Al-Ga composites delivered (84.6 ± 0.2), (86.8 ± 1.4), (80.2 ± 0.5), and (76.7 ± 0.7)% of the expected hydrogen, respectively. Modification with Ag promoted Al oxidation, thus providing higher hydrogen evolution rates. The samples with Ag were tested in a CaCl2 solution as well, for which the reaction proceeded much more slowly. At a higher temperature (80 °C) after 3 h of experiment, the corresponding hydrogen yields for Al-LiCl-Ag and Al-Ga-Ag powders were (46.7 ± 2.1) and (31.8 ± 1.9)%. The tested Ag-modified composite powders were considered promising for hydrogen generation and had the potential for further improvement to deliver higher hydrogen yields.

Magnetic and Electrical Properties of CuCr2Se4 Nanoparticles.

CuCr2Se4 nanoparticles were obtained by the high-energy ball milling of CuCr2Se4 single crystals, which had a size of approximately 32 nm after 5 h of milling. Structural, magnetic, and electrical studies have shown that a reduction in CuCr2Se4 single crystals to the nanosize leads to (1) a weakening of ferromagnetic interactions, both long and short range, (2) a lack of saturation of magnetization at 5 K and 70 kOe, (3) a change in the nature of electrical conductivity from metallic to semiconductor, and (4) a reduction in the thermoelectric power factor S2σ by an order of magnitude of 400 K. The above results were considered in terms of the parameters of the band model, derived from the high-temperature expansion of magnetic susceptibility and from the diffusive component of thermoelectric power. Theoretical calculations showed a significant weakening of both the superexchange and double exchange mechanisms, a reduction in the [Cr3+,Cr4+] band width from 0.76 to 0.19 eV, and comparable values of the Fermi energy and the activation energy (0.46 eV) in the intrinsic region of electrical conductivity. The main advantage of high-energy ball milling is the ability to modify the physicochemical properties of already existing compounds for desired applications.

Te-rP-C Anodes Prepared Using a Scalable Milling Process for High-Performance Lithium-Ion Batteries.

Red phosphorus (rP) is one of the most promising anode materials for lithium-ion batteries, owing to its high theoretical capacity. However, its low electronic conductivity and large volume expansion during cycling limit its practical applications, as it exhibits low electrochemical activity and unstable cyclability. To address these problems, tellurium (Te)-rP-C composites, which have active materials (Te, rP) that are uniformly distributed within the carbon matrix, were fabricated through a simple high-energy ball milling method. Among the three electrodes, the Te-rP (1:2)-C electrode with a 5% FEC additive delivers a high initial CE of 80% and a high reversible capacity of 734 mAh g-1 after 300 cycles at a current density of 100 mA g-1. Additionally, it exhibits a high-rate capacity of 580 mAh g-1 at a high current density of 10,000 mA g-1. Moreover, a comparison of the electrolytes with and without the 5% FEC additive demonstrated improved cycling stability when the FEC additive was used. Ex situ XRD analysis demonstrated the lithiation/delithiation mechanism of Te-rP (1:2)-C after cycling based on the cyclic voltammetry results. Based on the electrochemical impedance spectroscopy analysis results, a Te-rP-C composite with its notable electrochemical performance as an anode can sufficiently contribute to the battery anode industry.

Preparation, Characterization, and Properties of UV-Curable Coating Doped with Nano-SiO2.

In this study, a hydrophobic, wear-resistant ultraviolet (UV)-curable coating was investigated as an alternative to traditional coatings with low hardness and high susceptibility to scratching. The SiO2 nanoparticles were ground and modified using high-energy ball milling, during which the surface energy of nano-SiO2 particles rapidly increased as their particle size decreased. Different proportions of modified nano-SiO2 particles were added to the coating and cured into a film. The structure of the composite coating was analyzed via infrared spectroscopy, scanning electron microscopy, and X-ray diffraction, which confirmed the successful preparation of the composite coating. The mechanical and optical property tests of the coating were investigated. With a 5% nano-SiO2 content, the hardness of the coating reached 5H, whereas the adhesion was poor (2B), and the flexibility was 1. The overall comprehensive performance of the coating was best when the addition amount was 3%. The coating exhibited good hardness, flexibility, and adhesion. The hardness of the coating reached 4H, the adhesion was 4B, the flexibility was 5, the coating haze was 12.38 HZ, and the contact angle was 118°.

Synthesis and Luminescent Properties of Barium Molybdate Nanoparticles.

BaMoO4 was obtained via facile mechanochemical synthesis at room temperature and a solid-state reaction. An evaluation of the phase composition and structural and optical properties of BaMoO4 was conducted. The influence of different milling speeds on the preparation of BaMoO4 was explored. A shorter reaction time for the phase formation of BaMoO4 was achieved using a milling speed of 850 rpm. A milling speed of 500 rpm led to partial amorphization of the initial reagents and to prolongation of the synthesis time of up to 3 h of milling time. Solid-state synthesis was performed via heat treatment at 900 °C for 15 h. X-ray diffraction analysis (XRD), infrared (IR) and UV diffuse reflectance (UV-Vis) and photoluminescence (PL) spectroscopy were carried out to characterize the samples. Independently of the method of preparation, the obtained samples had tetragonal symmetry. The average crystallite sizes of all samples, calculated using Scherrer's formula, were in the range of 240 to 1540 Å. IR spectroscopy showed that more distorted structural MoO4 units were formed when the compound was synthesized via a solid-state reaction. The optical band gap energy of the obtained materials was found to decrease from 4.50 to 4.30 eV with increasing crystallite sizes. Green- and blue-light emissions were observed for BaMoO4 phases under excitation wavelengths of 330 and 488 nm. It was established that the intensity of the PL peaks depends on two factors: the symmetry of MoO4 units and the crystallite sizes.

Effect of Doping with Different Nb Contents on the Properties of CoCrFeNi High-Entropy Alloys.

A series of five-element CoCrFeNi-Nbx (x = 0, 1, 3, 5, 7, and 9 wt%) high-entropy alloys were prepared using high-energy ball milling and discharge plasma sintering methods. Then, the effects of doping with Nb elements on the organization and properties of the CoCrFeNi HEAs were systematically investigated by tensile testing, hardness testing, and examining their micro-morphologies. The results show that with the addition of the Nb element, the lattice distortion of the alloy due to the large size of the Nb atoms causes the microstructure of CoCrFeNi HEAs to change from a single-phase FCC structure to a dual-phase structure of FCC and Laves. With the increase in the Nb content, the increase in the volume fraction of the hard and brittle Laves phase leads to the enhancement of the HEA's tensile strength, yield strength, and hardness, and a decrease in plasticity. The Nb5 alloy showed the most excellent comprehensive performance, with a tensile strength, yield strength, and plasticity of 879.1 MPa, 491.8 MPa, and 39.8%, respectively, and all the properties were improved compared with those of the HEAs obtained by the arc melting method. The increase in the hardness of the HEAs was nearly proportional to the increase in the volume fraction of the Laves phase, which was the direct cause of the increase in the hardness of the HEA. Therefore, since the Laves phase is the direct cause of the increase in HEA hardness, the doping of CoCrFeNi HEAs with Nb can significantly improve the properties of HEAs.

Preparation of Dispersed Copper(II) Oxide Nanosuspensions as Precursor for Femtosecond Reductive Laser Sintering by High-Energy Ball Milling.

This contribution demonstrates and discusses the preparation of finely dispersed copper(II) oxide nanosuspensions as precursors for reductive laser sintering (RLS). Since the presence of agglomerates interferes with the various RLS sub-processes, fine dispersion is required, and oversized particles must be identified by a measurement methodology. Aside from the established method of scanning electron microscopy for imaging individual dried particles, this work applies the holistic and statistically more significant laser diffraction in combination with dynamic image analysis in wet dispersion. In addition to direct ultrasonic homogenization, high-energy ball milling is introduced for RLS, to produce stable nanosuspensions with a high fine fraction, and, above all, the absence of oversize particles. Whereas ultrasonic dispersion stagnates at particle sizes between 500 nm and 20 µm, even after 8 h, milled suspension contains a high proportion of finest particles with diameters below 100 nm, no agglomerates larger than 1 µm and a trimodal particle size distribution with the median at 50 nm already, after 100 min of milling. The precursor layers produced by doctor blade coating are examined for their quality by laser scanning microscopy. The surface roughness of such a dry film can be reduced from 1.26 µm to 88 nm by milling. Finally, the novel precursor is used for femtosecond RLS, to produce homogeneous, high-quality copper layers with a sheet resistance of 0.28Ω/sq and a copper mass concentration of 94.2%.

High-Energy Ball Milling Promoted Sulfur Immobilization for Constructing High-Performance Na-Storage Carbon Anodes.

Sulfur (S) doping is an effective method for constructing high-performance carbon anodes for sodium-ion batteries. However, traditional designs of S-doped carbon often exhibit low initial Coulombic efficiency (ICE), poor rate capability, and impoverished cycle performance, limiting their practical applications. This study proposes an innovative design strategy to fabricate S-doped carbon using sulfonated sugar molecules as precursors via high-energy ball milling. The results show that the high-energy ball milling can immobilize S for sulfonated sugar molecules by modulating the chemical state of S atoms, thereby creating a S-rich carbon framework with a doping level of 15.5 wt %. In addition, the S atoms are present mainly in the form of C-S bonds, facilitating a stable electrochemical reaction; meanwhile, S atoms expand the spacing between carbon layers and contribute sufficient capacitance-type Na-storage sites. Consequently, the S-doped carbon exhibits a large capacity (>600 mAh g-1), a high ICE (>90%), superior cycling stability (490 mAh g-1 after 1100 cycles at 5 A g-1), and outstanding rate performance (420 mAh g-1 at a high current density of 50 A g-1). Such excellent Na-storage properties of S-doped carbon have rarely been reported in the literatures before.

Amorphous MXene Opens New Perspectives.

Recently, novel amorphous nanomaterials formed by introducing atomic irregular arrangement factors have been successfully fabricated, showing superior performance in catalysis, energy storage, and mechanics. Among them, 2D amorphous nanomaterials are the stars, as they combine the benefits of both 2D structure and amorphous. Up to now, many research studies have been published on the study of 2D amorphous materials. However, as one of the most important parts of 2D materials, the research on MXenes mainly focuses on the crystalline counterpart, while the study of highly disordered forms is much less. This work will provide insight into the possibility of MXenes amorphization, and discusses the application prospect of amorphous MXenes materials.

Rapid and simple isolation and detection of exosomes using CaTiO3:Eu3+@Fe3O4 multifunctional nanocomposites.

Exosomes are potential biomarkers for disease diagnosis and treatment, as well as drug carriers. However, as their isolation and detection remain critical issues, convenient, rapid, low-cost, and effective methods are necessary. In this study, we present a rapid and simple method for directly capturing and analyzing exosomes from complex cell culture media using CaTiO3:Eu3+@Fe3O4 multifunctional nanocomposites. The CaTiO3:Eu3+@Fe3O4 nanocomposites were prepared by high-energy ball-milling and used to isolate exosomes by binding CaTiO3:Eu3+@Fe3O4 nanocomposites and the hydrophilic phosphate head of the exosome phospholipids. Notably, the developed CaTiO3:Eu3+@Fe3O4 multifunctional nanocomposites achieved results comparable with those of commercially available TiO2 and were separated using a magnet within 10 min. Moreover, we report a surface-enhanced Raman scattering (SERS)-based immunoassay for detecting the exosome biomarker CD81. Gold nanorods (Au NRs) were modified with detection antibodies, and antibody-conjugated Au NRs were labeled with 3, 3, diethylthiatricarbocyanine iodide (DTTC) as the SERS tags. A method combining magnetic separation and SERS was developed to detect exosomal biomarker CD81. The results of this study demonstrate the feasibility of this new technique as a useful tool for exosome isolation and detection.

Precisely manipulated π-π stacking of catalytic exfoliated iron polyphthalocyanine/reduced graphene oxide hybrid via pyrolysis-free path.

Metal macrocycles with well-defined molecular structures are ideal platforms for the in-depth study of electrochemical oxygen reduction reaction (ORR). Structural integrity of metal macrocycles is vital but remain challenging since the commonly used high-temperature pyrolysis would cause severe structure damage and unidentifiable active sites. Herein, we propose a pyrolysis-free strategy to precisely manipulate the exfoliated 2D iron polyphthalocyanine (FePPc) anchored on reduced graphene oxide (rGO) via π-π stacking using facile high-energy ball milling. A delocalized electron shift caused by π-π interaction is firstly found to be the mechanism of facilitating the remarkable ORR activity of this hybrid catalyst. The optimal FePPc@rGO-HE achieves superior half-wave potential (0.90 V) than 20 % Pt/C. This study offers a new insight in designing stable and high-performance metal macrocycle catalysts with well-defined active sites.

Review on Generation and Characterization of Copper Particles and Copper Composites Prepared by Mechanical Milling on a Lab-Scale.

This review aims to expose mechanical milling as an alternative method for generating copper-based particles (copper particles (CuP) and copper composites (CuC)); more specifically, via a top-down or bottom-up approach, on a lab-scale. This work will also highlight the different parameters that can affect the size distribution, the type, and the morphology of the obtained CuP or CuC, such as the type of mechanical mill, ball-to-powder ratios (BPR), the milling speed, milling time, and the milling environment, among others. This review analyzes various papers based on the Cu-based particle generation route, which begins with a pretreatment step, then mechanical milling, its approach (top-down or bottom-up), and the post-treatment. Finally, the characterization methods of the resulting CuP and CuC through mechanical milling are also discussed.