Nanodiamond Surface Research Articles

High‐Resolution Thermal Sensing Using Temperature‐Sensitive Cathodoluminescence Spectroscopy in Nitrogen‐Doped Nanodiamonds

The evolution of the cathodoluminescence spectra from commercially available nanodiamonds with high density of nitrogen‐vacancy defects has been studied in a large wavelength range, from 200 to 800 nm, and temperatures from 5 to 300 K, in order to achieve a temperature probe with high spatial resolution. The full width at half maximum of the peak associated to the neutral charge state of the NV center has been found to evolve with temperature in a predictable way, although its value may vary from sample to sample. We have attributed this shift to the differences in the nanodiamonds surface chemistry.

The influence of the sizes of nanodiamond aggregates in their suspensions on the efficiency of sorption of <sup>90</sup>Y and <sup>177</sup>Lu isotopes for their subsequent use in nuclear medicine

Nanodiamonds (NDs) are promising carriers of radionuclides in radiopharmaceuticals for use in nuclear medicine. In this work, we investigated the influence of the properties of ND suspensions, including the sizes of their aggregates, in aqueous solutions with different pH on their binding of medical isotopes 90Y and 177Lu and found the conditions for obtaining promising conjugates for further in vivo studies. It was shown that sorption is influenced by the composition of the solution, which determines the properties of the ND surface, while the forms of cations of the studied nuclides in the solution do not affect the degree of sorption.

Purification and tailored functionalities in detonation nanodiamond

Abstract Nanodiamonds (NDs) offer immense potential in various fields, but graphitic or metal-based impurities hinder their widespread adoption. Conventional purification methods often employ harsh chemicals or high temperatures, raising concerns about ND integrity and surface properties. Herein, we compared various strategies to purify and tailor the surface functional groups in the detonation-derived NDs. A facile 2-step purification strategy combining salt-assisted air oxidation (SAAO) and Fenton chemistry is particularly interesting for efficient and selective removal of graphitic impurities while preserving the diamond lattice structure. SAAO selectively burns off graphitic impurities at 450 °C under controlled oxygen flow, minimizing damage to the diamond core. Subsequently, Fenton's reagent (H2O2/Fe2+) introduces hydrophilic functional groups onto the ND surface, further enhancing diamond purity and promoting subsequent functionalization. This synergistic approach enables (i) highly efficient removal of graphitic impurities while preserving ND morphology and crystal structure, (ii) controlled introduction of surface functionalities, and (iii) improved colloidal stability of purified NDs. This green and efficient purification protocol is beneficial for tailoring ND properties and unlocking their full potential in diverse applications ranging from biomedicine and electronics to catalysis and quantum technologies.

Ultrathin Boron Growth onto Nanodiamond Surfaces via Electrophilic Boron Precursors.

Diamond as a templating substrate is largely unexplored, and the unique properties of diamond, including its large bandgap, thermal conductance, and lack of cytotoxicity, makes it versatile in emergent technologies in medicine and quantum sensing. Surface termination of an inert diamond substrate and its chemical reactivity are key in generating new bonds for nucleation and growth of an overlayer material. Oxidized high-pressure high temperature (HPHT) nanodiamonds (NDs) are largely terminated by alcohols that act as nucleophiles to initiate covalent bond formation when an electrophilic reactant is available. In this work, we demonstrate a templated synthesis of ultrathin boron on ND surfaces using trigonal boron compounds. Boron trichloride (BCl3), boron tribromide (BBr3), and borane (BH3) were found to react with ND substrates at room temperature in inert conditions. BBr3 and BCl3 were highly reactive with the diamond surface, and sheet-like structures were produced and verified with electron microscopy. Surface-sensitive spectroscopies were used to probe the molecular and atomic structure of the ND constructs' surface, and quantification showed the boron shell was less than 1 nm thick after 1-24 h reactions. Observation of the reaction supports a self-terminating mechanism, similar to atomic layer deposition growth, and is likely due to the quenching of alcohols on the diamond surface. X-ray absorption spectroscopy revealed that boron-termination generated midgap electronic states that were originally predicted by density functional theory (DFT) several years ago. DFT also predicted a negative electron surface, which has yet to be confirmed experimentally here. The boron-diamond nanostructures were found to aggregate in dichloromethane and were dispersed in various solvents and characterized with dynamic light scattering for future cell imaging or cancer therapy applications using boron neutron capture therapy (BNCT). The unique templating mechanism based on nucleophilic alcohols and electrophilic trigonal precursors allows for covalent bond formation and will be of interest to researchers using diamond for quantum sensing, additive manufacturing, BNCT, and potentially as an electron emitter.

Improving Microcystis aeruginosa removal efficiency through enhanced sonosensitivity of nitrogen-doped nanodiamonds

Traditional methods for algae removal in drinking water treatment, such as coagulation and sedimentation, face challenges due to the negative charge on algae cells’ surfaces, resulting in ineffective removal. Ultrasonic cavitation has shown promise in enhancing coagulation performance by disrupting extracellular polymer structures and improving cyanobacteria removal through various mechanisms like shear force and free radical reactions. However, the short lifespan and limited mass transfer distance of free radicals in conventional ultrasonic treatment lead to high energy consumption, limiting widespread application. To overcome these limitations and enhance energy efficiency, advanced carbon-based materials were developed and tested. Nitrogen-doped functional groups on nanodiamond surfaces were found to boost sonosensitivity by increasing the production of reactive oxygen species at the sonosensitizer-water interface. Utilizing low-power ultrasound (0.12 W/mL) in combination with N-ND treatment for 5 min, removal rates of Microcystis aeruginosa cells in water exceeded 90 %, with enhanced removal of algal organic matters and microcystins in water. Visualization through confocal microscopy highlighted the role of positively charged nitrogen-doped nanodiamonds in aggregating algae cells. The synergy between cell capturing and catalysis of N-ND indicates that efficient mass transfer of free radicals from the sonosensitizer’s surface to the microalgae’s surface is critical for promoting cyanobacteria floc formation. This study underscores the potential of employing a low-intensity ultrasound and N-ND system in effectively improving algae removal in water treatment processes.

Effect of nanodiamonds surface deposition on hydrophilicity, bulk degradation and in-vitro cell adhesion of 3D-printed polycaprolactone scaffolds for bone tissue engineering

This study was designed to deposit nanodiamonds (NDs) on 3D-printed poly-ϵ-caprolactone (PCL) scaffolds and evaluate their effect on the surface topography, hydrophilicity, degradation, andin-vitrocell adhesion compared to untreated PCL scaffolds. The PCL scaffold specimens were 3D-printed by fused deposition modeling (FDM) technique with specific porosity parameters. The 3D-printed specimens' surfaces were modified by NDs deposition followed by oxygen plasma post-treatment using a plasma focus device and a non-thermal atmospheric plasma jet, respectively. Specimens were evaluated through morphological characterization by field emission scanning electron microscope (FESEM), microstructure characterization by Raman spectroscopy, chemical characterization by Fourier transform infrared (FTIR) spectroscopy, hydrophilicity degree by contact angle and water uptake measurements, andin-vitrodegradation measurements (n= 6). In addition,in-vitrobone marrow mesenchymal stem cells adhesion was evaluated quantitatively by confocal microscopy and qualitatively by FESEM at different time intervals after cell seeding (n= 6). The statistical significance level was set atp⩽ 0.05. The FESEM micrographs, the Raman, and FTIR spectra confirmed the successful surface deposition of NDs on scaffold specimens. The NDs treated specimens showed nano-scale features distributed homogeneously across the surface compared to the untreated ones. Also, the NDs treated specimens revealed a statistically significant smaller contact angle (17.45 ± 1.34 degrees), higher water uptake percentage after 24 h immersion in phosphate buffer saline (PBS) (21.56% ± 1.73), and higher degradation rate after six months of immersion in PBS (43.92 ± 0.77%). Moreover, enhanced cell adhesion at all different time intervals was observed in NDs treated specimens with higher nuclei area fraction percentage (69.87 ± 3.97%) compared to the untreated specimens (11.46 ± 1.34%). Surface deposition of NDs with oxygen-containing functional groups on 3D-printed PCL scaffolds increased their hydrophilicity and degradation rate with significant enhancement of thein-vitrocell adhesion compared to untreated PCL scaffolds.

Tritium-Labeled Nanodiamonds as an Instrument to Analyze Bioprosthetic Valve Coatings: A Case of Using a Nanodiamond Containing Coating on a Pork Aorta.

Coatings with xenogenic materials, made of detonation nanodiamonds, provide additional strength and increase elasticity. A functionally developed surface of nanodiamonds makes it possible to apply antibiotics. Previous experiments show the stability of such coatings; however, studies on stability in the bloodstream and calcification of the material in natural conditions have yet to be conducted. Tritium-labeled nanodiamonds (negative and positive) were obtained by the tritium activation method and used to develop coatings for a pork aorta to analyze their stability in a pig's bloodstream using a radiotracer technique. A chitosan layer was applied from a solution of carbonic acid under high-pressure conditions to prevent calcification. The obtained materials were used to prepare a porcine conduit, which was surgically stitched inside the pig's aorta for four months. The aorta samples, including nanodiamond-coated and control samples, were analyzed for nanodiamond content and calcium, using the radiotracer and ICP-AES methods. A histological analysis of the materials was also performed. The obtained coatings illustrate a high in vivo stability and low levels of calcification for all types of nanodiamonds. Even though we did not use additional antibiotics in this case, the development of infection was not observed for negatively charged nanodiamonds, opening up prospects for their use in developing coatings.

Quantitative measurement of graphitic sp[formula omitted] on single nanodiamonds with sub-monolayer sensitivity using differential interference contrast and photo-thermal microscopy

The surface of nanodiamonds is prone to be decorated with a graphitic layer due to the thermodynamic instability of diamond versus graphite. Notably, this surface layer affects the zeta-potential of nanodiamonds controlling their colloidal stability, modulates the charging of embedded nitrogen vacancy centres used for sensing and quantum technology, and introduces an optical absorption which leads to heating and destruction of nanodiamonds under intense laser irradiation. Physical and chemical treatments to reduce the graphitic carbon are available, but a sensitive method to measure this graphitic layer on single nanodiamonds is lacking. Here, we demonstrate a non-destructive method to quantitatively determine the graphitic carbon correlatively with the nanodiamond size, on individual nanodiamonds. The method allows determining the fraction of graphitic sp2 to diamond sp3 bonded atoms, and estimating the sp2 surface layer thickness. We investigated milled nanodiamonds, both untreated and chemically treated to remove sp2. We found that untreated nanodiamonds were covered by the equivalent of a single sp2 monolayer, which was reduced to 10% of a monolayer for treated nanodiamonds. In both cases, significant variations between individual nanodiamonds were observed. The minimum number of sp2 bonded atoms detectable under the measurement conditions reported here was found to be 2×104.

Utilizing Constant Energy Difference between sp-Peak and C 1s Core Level in Photoelectron Spectra for Unambiguous Identification and Quantification of Diamond Phase in Nanodiamonds.

The modification of nanodiamond (ND) surfaces has significant applications in sensing devices, drug delivery, bioimaging, and tissue engineering. Precise control of the diamond phase composition and bond configurations during ND processing and surface finalization is crucial. In this study, we conducted a comparative analysis of the graphitization process in various types of hydrogenated NDs, considering differences in ND size and quality. We prepared three types of hydrogenated NDs: high-pressure high-temperature NDs (HPHT ND-H; 0-30 nm), conventional detonation nanodiamonds (DND-H; ~5 nm), and size- and nitrogen-reduced hydrogenated nanodiamonds (snr-DND-H; 2-3 nm). The samples underwent annealing in an ultra-high vacuum and sputtering by Ar cluster ion beam (ArCIB). Samples were investigated by in situ X-ray photoelectron spectroscopy (XPS), in situ ultraviolet photoelectron spectroscopy (UPS), and Raman spectroscopy (RS). Our investigation revealed that the graphitization temperature of NDs ranges from 600 °C to 700 °C and depends on the size and crystallinity of the NDs. Smaller DND particles with a high density of defects exhibit a lower graphitization temperature. We revealed a constant energy difference of 271.3 eV between the sp-peak in the valence band spectra (at around 13.7 eV) and the sp3 component in the C 1s core level spectra (at 285.0 eV). The identification of this energy difference helps in calibrating charge shifts and serves the unambiguous identification of the sp3 bond contribution in the C 1s spectra obtained from ND samples. Results were validated through reference measurements on hydrogenated single crystal C(111)-H and highly-ordered pyrolytic graphite (HOPG).

Nanodiamonds: A Cutting-Edge Approach to Enhancing Biomedical Therapies and Diagnostics in Biosensing.

Nanodiamonds (NDs) have garnered attention in the field of nanomedicine due to their unique properties. This review offers a comprehensive overview of NDs synthesis methods, properties, and their uses in biomedical applications. Various synthesis techniques, such as detonation, high-pressure, high-temperature, and chemical vapor deposition, offer distinct advantages in tailoring NDs' size, shape, and surface properties. Surface modification methods further enhance NDs' biocompatibility and enable the attachment of bioactive molecules, expanding their applicability in biological systems. NDs serve as promising nanocarriers for drug delivery, showcasing biocompatibility and the ability to encapsulate therapeutic agents for targeted delivery. Additionally, NDs demonstrate potential in cancer treatment through hyperthermic therapy and vaccine enhancement for improved immune responses. Functionalization of NDs facilitates their utilization in biosensors for sensitive biomolecule detection, aiding in precise diagnostics and rapid detection of infectious diseases. This review underscores the multifaceted role of NDs in advancing biomedical applications. By synthesizing NDs through various methods and modifying their surfaces, researchers can tailor their properties for specific biomedical needs. The ability of NDs to serve as efficient drug delivery vehicles holds promise for targeted therapy, while their applications in hyperthermic therapy and vaccine enhancement offer innovative approaches to cancer treatment and immunization. Furthermore, the integration of NDs into biosensors enhances diagnostic capabilities, enabling rapid and sensitive detection of biomolecules and infectious diseases. Overall, the diverse functionalities of NDs underscore their potential as valuable tools in nanomedicine, paving the way for advancements in healthcare and biotechnology.

Unraveling Eumelanin Radical Formation by Nanodiamond Optical Relaxometry in a Living Cell.

Defect centers in a nanodiamond (ND) allow the detection of tiny magnetic fields in their direct surroundings, rendering them as an emerging tool for nanoscale sensing applications. Eumelanin, an abundant pigment, plays an important role in biology and material science. Here, for the first time, we evaluate the comproportionation reaction in eumelanin by detecting and quantifying semiquinone radicals through the nitrogen-vacancy color center. A thin layer of eumelanin is polymerized on the surface of nanodiamonds (NDs), and depending on the environmental conditions, such as the local pH value, near-infrared, and ultraviolet light irradiation, the radicals form and react in situ. By combining experiments and theoretical simulations, we quantify the local number and kinetics of free radicals in the eumelanin layer. Next, the ND sensor enters the cells via endosomal vesicles. We quantify the number of radicals formed within the eumelanin layer in these acidic compartments by applying optical relaxometry measurements. In the future, we believe that the ND quantum sensor could provide valuable insights into the chemistry of eumelanin, which could contribute to the understanding and treatment of eumelanin- and melanin-related diseases.

Powders of Diamond Nanoparticles as a Promising Material for Reflectors of Very Cold and Cold Neutrons.

More than 15 years ago, the study of nanodiamond (ND) powders as a material for designing reflectors of very cold neutrons (VCNs) and cold neutrons (CNs) began. Such reflectors can significantly increase the efficiency of using such neutrons and expand the scope of their application for solving applied and fundamental problems. This review considers the principle of operation of VCN and CN reflectors based on ND powders and their advantages. Information is presented on the performed experimental and theoretical studies of the effect of the size, structure, and composition of NDs on the efficiency of reflectors. Methods of chemical and mechanical treatments of powders in order to modify their chemical composition and structure are discussed. The aim is to avoid, or at least to decrease, the neutron inelastic scatterers and absorbers (mainly hydrogen atoms but also metallic impurities and nitrogen) as well as to enhance coherent elastic scattering (to destroy ND clusters and sp2 carbon shells on the ND surface that result from the preparation of NDs). Issues requiring further study are identified. They include deeper purification of NDs from impurities that can be activated in high radiation fluxes, the stability of NDs in high radiation fluxes, and upscaling methods for producing larger quantities of ND powders. Possible ways of solving these problems are proposed.

Investigating the Structure and Properties of Epoxy Nanocomposites Containing Nanodiamonds Modified with Aminoacetic Acid.

This paper presents a study on the prospects of functionalizing nanodiamonds (NDs) with aminoacetic acid to obtain high-strength composites based on an epoxy matrix. The impact of the functionalization of the ND surface with aminoacetic acid in various concentrations on the properties of the epoxy composite was assessed. The success of grafting amine onto the ND surface was confirmed by X-ray phase analysis and IR spectroscopy. The results show a significant decrease in the average size of ND particles, from 400 nm for the pristine ones to 35 nm, and the contact angle, from 27° to 22°, with an increase in the specific surface area after treatment with a 5% solution of aminoacetic acid. Reducing the average size of NDs allows them to be better distributed throughout the epoxy matrix, which, as a result of the formation of chemical interaction at the matrix-nanofiller phase interface, can significantly increase the strength of the obtained composite. The addition of NDs treated with aminoacetic acid ensures an increase in the deformation-strength properties of epoxy composites by 19-23% relative to an epoxy composite containing the pristine NDs. Moreover, the presence of functionalized NDs significantly influences the structure and thermal stability of the epoxy nanocomposite.

Enzyme Mimics Based on Guanidinocalix[4]arene/ Nanodiamond Hybrid Systems with Phosphodiesterase Activity

AbstractDiamond nanoparticles are an extremely promising class of carbon‐based nanomaterials. Because of their versatility, they have an interest in a large variety of applications, however, their use in the fabrication of enzyme mimics was not previously investigated. In this study, we realized hybrid systems based on guanidinium derivatives and diamond nanoparticles by simple adsorption of the organic material on their surface. The guanidinium derivatives chosen for this study are calix[4]arenes, blocked in the cone conformation via functionalization at the lower rim with alkyl chains, and decorated with guanidinium or arginine units at the upper rim. The corresponding monofunctional counterparts were also investigated as model compounds. These materials were characterized with different experimental techniques, i. e. thermogravimetric analysis, dynamic light scattering, ζ‐potential measurements and IR/Raman spectroscopy. Their catalytic properties in the cleavage of phosphodiesters were investigated by an in‐depth kinetic analysis. The whole experimental picture points to conclude that these compounds are stably adsorbed onto the nanodiamonds surface and are active in the transesterification reaction of the RNA model compound 2‐hydroxypropyl p‐nitrophenyl phosphate in water, with a notable advantage over their catalytic performances at the same concentration in solution.

Electrochemistry and Electronic Structure of the Deuterium-Grown Boron-Doped Diamond Interfaces

Integration of the first principles quantum mechanical simulations with electrochemistry represents a difficult research area due to the complexity and large size of real systems and computational limitations. On the one hand it is highly desirable to be able to predict electrochemical properties of materials and systems from simulations to limit the money expenditure for experimental work and accelerate applications [1]. On the other hand, utilization of ab-initio simulations to understand the experimentally observed phenomena is also required to embed them into a solid theoretical framework.To fulfill this task, several multiscale approaches are used with the density functional theory (DFT) being fundamental tool for investigation of electronic structure. DFT results can be further extended to build forcefields used in molecular dynamics (MD) [2] for larger scale simulations and non-equillibrium Green's functions for investigations of electronics and spintronics of nanodevices [3]. Semiconductor electrochemistry is one of the most important areas to explore this experiment-theory interface because of the necessity to develop new materials for photovoltaics, photoelectrochemistry, energy storage and conversion. The purpose of the following talk is to show the power of this paradigm by elucidation of the deuterium-grown boron doped diamond (BDD-D) material [4].A brief introduction to the material synthesis, chemical and physical properties is provided exploiting the synchrotron data of X-Ray absorption spectroscopy and X-Ray photoelectron spectroscopy. Then, a strong emphasis is put into merging the (photo)electrochemical data with the first principle results for better understanding of charge transfer phenomena in the nanoscale. Specifically, DFT calculations of projected local density of states clearly show the presence of highly occupied surface states on the (111) plane of BDD-D in contrast to its standard hydrogen-grown counterpart (BDD-H). The resulting surface states are capable of photocurrent generation in the visible light, which is strongly magnified in BDD-D. Moreover, photoelectrochemical measurements evidenced that photocurrents can be positive or negative depending on the bias - despite BDD being a p-type semiconductor. These confirm a profound role of surface states in the semiconductor electrochemistry and capability of photoinduced charge transfer in the modified materials. The proposed picture shines some new light on the commonly established paradigm of band bending as the key factor driving surface properties of the nanodiamond surfaces [5]. Figure. SEM images of a) BDD@D and b) BDD@H; c) grain size distribution among two samples; d) XRD patterns of the diamond films deposited in the D2/CH4 and H2/CH4 gas mixtures. Reflections at 2θ around 44°, 75°, and 91° correspond to the (111), (220), and (311) diamond lattice planes, respectively. Doubling of the reflections is related to the presence of Kα1 and Kα2 wavelengths in the X-ray radiation [4]. Acknowledgements: M.S., M.B., and M.F. thank Helmholtz-Zentrum Berlin (HZB) for the allocation of synchrotron radiation beamtime at HZB (Germany). M.S. gratefully acknowledges the financial support of these studies fromthe Gdansk University of Technology through the DEC-02/2021/IDUB/ II.1/AMERICIUM grant under the Americium – “Excellence Initiative – Research University” program. R.B. acknowledges the funding from the National Science Centre, Poland under the OPUS call in the Weave programme (Project number: 2021/43/I/ST7/03205).

In Situ Transmission Electron Microscopy Investigation on Oriented Attachment of Nanodiamonds.

Oriented attachment (OA) plays an important role in the assembly of nanoparticles and the regulation of their size and morphology, which is expected to be an effective means to modulate the properties of nanodiamonds (NDs). However, there remains a dearth of comprehensive investigation into the OA mechanism of NDs. Using in situ transmission electron microscopy, we conducted atomic-resolution investigation on the OA events of ND pairs under electron beam irradiation. The occurrence of an OA event is contingent upon the alignment between two ND surfaces, and the coalesced particles undergo recrystallization to form spherical shapes. Both experimental observations and molecular dynamics (MD) simulations reveal that ND pairs exhibit a preference for coalescing along the {111} surfaces. Additionally, MD simulations indicate that kinetic factors, such as contact surface area and contact angle, also influence the coalescence process.

Surface modification of nanodiamond with pH/thermo dual responsive polymer and hyper-branched dendrimer as a near-infrared photothermal-triggered drug delivery for cancer therapy

In this study, a pH/temperature-responsive drug delivery system based on nanodiamonds is successfully developed by grafting nanodiamonds with thermosensitive polymer and then coating with a hyper-branched dendrimer for docetaxel delivery. For this purpose, alyl alchol and poly (N-isopropylacrylamide) was grafted on the surface of nanodiamonds as functional monomer and thermo-sensitive polymer, respectively. Then, three generations of dendrimers were anchored to the grafted polymer chains by using 1, 3-phenylenediamine and methyl acrylate. Chemical bonding, phase analysis, morphology, and thermal behavior were studied by Fourier transform infrared, x-ray diffraction, field emission scanning electron microscopy, and thermogravimetric techniques, respectively. Equilibrium isotherm and kinetic data were fitted well with Langmuir and pseudo-second-order models by giving a maximum capacity of adsorption. The findings of in-vitro release studies shown that the prepared nanocarrier could be employed for docetaxel delivery due to the pH and temperature-dependent sustained release (99.78% after 6 h, at pH = 5.6, T = 45 °C). Using the near-infrared laser irradiation, the docetaxel release reached 90.97% in 20 min, which was about 4.5 folds faster than without laser irradiation. The drug release from nanocarrier was modeled and the Higuchi model was introduced as the best model predicting the release behavior.

2D WS2 and MoS2 functionalized nickel oxide/nanodiamond supported carbon electrocatalysts for oxygen reduction reaction

The design of a new electro-catalyst with rich active sites, sufficient surface areas, low cost, and excellent stability for promoting the oxygen reduction reaction (ORR) efficiency is a crucial research topic in the fuel cell's application. Herein, the successful preparation of 2D WS2 and MoS2 functionalized NiO nanoparticles onto the surface of nanodiamond and carbon support is reported. The effect of WS2 and MoS2 doping on nickel oxide/nanodiamond activity supported carbon composites (NiO/ND/C) as electro-catalysts for oxygen reduction reaction in an alkaline medium was evaluated. The combination of activated carbon with sp2 hybridization and nanodiamond with sp2 and sp3 hybridization allows for better materials support conductivity. All prepared electro-catalysts exhibit good electrochemical activity towards ORR. It's noticed that the most efficient electro-catalyst for ORR among all the prepared composites is WS2/NiO/ND/C, which exhibits the highest current density of −7.47 mA·cm−2 at a rotating speed of 2500 rpm and a retention stability of 94.3 % after 100-repetitive cycles. Moreover, the WS2/NiO/ND/C composite forces the ORR reaction through the direct four-electron pathway. This work spotlights the effect between the electronegative oxygen atoms, the electropositive Mo and W atoms, and the synergistic effect between WS2 and carbon support. All this information confirms that the as-reported WS2/NiO/ND/C nanocomposite may be considered a hopeful cathodic electrode for ORR catalysis as an alternative catalyst for platinum-based ones.

Analysis of transformation of a thin graphite-like carbon layer on the detonation nanodiamond surface into diamond

The article considers the process of obtaining nanostructured diamond materials due to phase transformation of thin films based on carbon non-diamond forms on the nanodiamond surface into diamond. For the synthesis of nanostructured diamond polycrystalline superhard material, various variants of the initial mixture based on nanodiamond with non-diamond carbon on the surface are proposed (surface-graphitized nanodiamond, surface-graphitized nanodiamond with addition of purified nanodiamond, detonation diamond-containing charge with a surface layer of “amorphous” carbon, including purified nanodiamond additives). The influence of the structure of a thin non-diamond layer on the parameters of graphite to diamond transition is revealed. For a carbon film with a disordered structure (the so-called “amorphous” carbon), the transition pressure to diamond will be about 10–15 GPa, which is significantly higher than the phase transformation pressure for thin graphite films in this temperature range. It is shown that the increase in the pressure of transformation of a thin layer of “amorphous” carbon is caused by its lower surface energy compared to the surface energy of graphite. It has been established that the region of transformation of a thin graphite-like film with a thickness of about 1 nm, formed on the 2–10 nm nanodiamond surface into diamond will be below the graphite-diamond equilibrium line in the temperature range of 1000– 2500 °C. Additional introduction of purified nanodiamond particles leads to a decrease in the pressure of transformation of thin layers of non-diamond carbon into a diamond structure from 10–15 to 2–7 GPa, which is due to the effect of the surface of catalytically active diamond nanoparticles on the thermodynamic stimulus of phase transformation.

ТЕРМОДИНАМИЧЕСКИЙ АНАЛИЗ ПРОЦЕССА ФОРМИРОВАНИЯ НАНОСТРУКТУРНОГО ПОЛИКРИСТАЛЛИЧЕСКОГО МАТЕРИАЛА НА ОСНОВЕ НАНОАЛМАЗОВ, МОДИФИЦИРОВАННЫХ НЕАЛМАЗНЫМ УГЛЕРОДОМ (ЧАСТЬ 1)

The influence of the size of carbon particles on the parameters of the graphite–diamond phase transformation is considered. It is shown that the surface energy of carbon nanoparticles of various shapes (spherical, columnar) makes a significant contribution to their total thermodynamic potential, which leads to a shift in the diamond–graphite equilibrium curve to the low pressure region and an expansion of the diamond phase stability region. At the same time, the change in the chemical potential (Gibbs free energy) during the direct (not catalytic) transition of thin-film graphite-like nanostructures into diamond will be higher than for “massive” graphite, which leads to an increase in the pressure of phase transformation into diamond. To reduce the parameters of diamond formation and obtain nanostructured diamond polycrystals, it is proposed to use nanodiamond particles with a nanometer surface layer of non-diamond (graphitelike) carbon as the starting material. In this case, the nanodiamond surface will influence the transition of a nanometer layer of graphite (graphite-like carbon) into diamond under more favorable thermodynamic parameters.