Nanodiamond Research Articles

A dual-functional electrolyte additive displaying hydrogen bond fusion enables highly reversible aqueous zinc ion batteries

In recent years, aqueous zinc-ion batteries (AZIBs) have attracted significant attention in energy storage due to their notable advantages, including high safety, low cost, high capacity, and environmental friendliness. However, side reactions like hydrogen evolution and zinc (Zn) dendrites can significantly impact their Coulombic efficiency (CE) and lifespan. Effectively addressing these issues has become a focus of research in this field. In our study, dimethyl sulfoxide (DMSO) and nanodiamonds (NDs) were used to optimize the electrolyte of AZIBs. Benefiting from the hydrogen bond fusion of DMSO and NDs, which regulates the Zn deposition behavior, effectively inhibiting the growth of Zn dendrites, hydrogen evolution, and corrosion. The Zn | |Zn symmetric cells using NDs-DMSO-ZS demonstrate exceptional cycling stability for over 1500 h at 1 mA cm−2, while the Zn//Cu asymmetric cells achieve up to 99.8% CE at 2 mA cm−2. This study not only shows the application prospects of electrolyte optimization in enhancing AZIBs performance, but also provides a reference for the advancement of electrolyte technology in advanced AZIBs technology.

Correction to “General Strategy for High-Density Covalent Functionalization of Diamond Nanoparticles Using Fenton Chemistry”

Correction to “General Strategy for High-Density Covalent Functionalization of Diamond Nanoparticles Using Fenton Chemistry”

Designing A Selective Electrochemical Nanosensor Based on Molecularly Imprinted Polymer for Detection of Pirfenidone

In this study, an electrochemical determination of pirfenidone(PIR), an antifibrotic drug, was developed for the first time with a bare glassy carbon electrode(GCE) and a molecularly imprinted polymer(MIP)-based nanosensor. A molecularly imprinted polymer(MIP) incorporating o-phenylenediamine(o-PD), chitosan(CHIT), ionic liquid(IL), and diamond nanoparticles(DiaNPs) was utilized to modify a glassy carbon electrode(GCE), developing a stable and selective electrochemical nanosensor(MIP/CHIT@IL@DiaNPs/GCE) for PIR detection. The designed MIP/CHIT@IL@DiaNPs/GCE was characterized by electrochemical impedance spectroscopy(EIS), cyclic voltammetry(CV), scanning electron microscopy(SEM) and atomic force microscopy(AFM). The [Fe(CN)6]3−/4− redox couple was used as a probe to characterize the nanosensor by using voltammetric methods. Under optimum conditions, the bare GCE showed a linear response in the concentration range of 9.90 μM to 260.0 μM for the determination of PIR, and the detection limit was calculated to be 2.48 μM. While, the MIP/CHIT@IL@DiaNPs/GCE nanosensor exhibited good sensitivity with a linear range of 30.0 pM−1.0 nM and a detection limit of 9.29 pM. To demonstrate the applicability of the developed nanosensors to real samples, the determination was made from Pirfect® tablet and human serum.

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.

Effect of Ellipsoidal Particle Shape on Tribological Properties of Lubricants Containing Nanoparticles

Adding nanoparticles can significantly improve the tribological properties of lubricants. However, there is a lack of understanding regarding the influence of nanoparticle shape on lubrication performance. In this work, the influence of diamond nanoparticles (DNPs) on the tribological properties of lubricants is investigated through friction experiments. Additionally, the friction characteristics of lubricants regarding ellipsoidal particle shape are investigated using molecular dynamics (MD) simulations. The results show that DNPs can drastically lower the lubricant's friction coefficient μ from 0.21 to 0.117. The shearing process reveals that as the aspect ratio (α) of the nanoparticles approaches 1.0, the friction performance improves, and wear on the wall diminishes. At the same time, the shape of the nanoparticles tends to be spherical. When 0.85 ≤ α ≤ 1.0, rolling is ellipsoidal particles' main form of motion, and the friction force changes according to a periodic sinusoidal law. In the range of 0.80 ≤ α < 0.85, ellipsoidal particles primarily exhibit sliding as the dominant movement mode. As α decreases within this range, the friction force progressively increases. The friction coefficient μ calculated through MD simulation is 0.128, which is consistent with the experimental data.

Realized Record Capacity and Rate Performance of Dual-Carbon Batteries Constructed by Introducing Superhard Nanodiamonds.

Dual-ion batteries (DIBs) are becoming an important technology for energy storage. To overcome the disadvantages of traditional electrodes and electrolytes, here we assemble a dual-carbon DIB with nanodiamond (ND)-modified crimped graphene (DCG) and electrolyte. The DCG anode and cathode realize high capacities of 1121 mA h g-1 and 149 mA h g-1, respectively, at 0.1 A g-1. The corresponding DCG//DCG full cells present a high capacity of 143 mA h g-1 at 1 A g-1 after 3300 cycles, which is superior to most reported results. Achieving these record performances is strongly dependent on the formed DCG electrodes with expanded interlayer spacing and abundant active sites, and NDs dispersed in DCG and electrolytes are very helpful for enhancing the storage of both cations and anions, effectively suppressing the irreversible decomposition of electrolytes. This work breaks through the bottleneck of graphitic-based DIBs, paving the way for realizing high-performance DIBs applied in industry.

Experimental and theoretical investigation of nanodiamond insertion on the interlayer interaction in multilayer stacking graphene

Multilayer stacked graphene (Gr) exhibits a wider range of novel properties than monolayer Gr, and it can be further applied to larger scales. Moreover, by modulating the interlayer structure and interactions, we can move beyond the energetically favorable AB stacking and explore unprecedented phenomena. In this study, nanodiamonds (ND) were introduced as nanospacers to manipulate the microstructure of multilayer Gr stacking. The presence of nanospacers increases the interlayer spacing and reduces interlayer interaction, which retrieves the linear band structure. The Gr and ND (Gr–ND) stacking structure was fabricated experimentally using a layer-by-layer transfer method. Raman spectroscopy confirms a decrease in interlayer interaction within the stacking structure, and atomic force microscopy reveals an expansion of the interlayer distance, contributing to the weakening of interlayer interactions. Theoretical analysis was conducted by combining molecular dynamic simulation and a continuum model to understand the experimentally observed change in microstructure caused by ND insertion. The ND density and size determine the interlayer distance, indicating the preference for configuration with lower system energy. The guideline for forming Gr–ND stacking structures obtained in this study can contribute to the property modulation and application of multilayer stacked Gr.

A novel treatment approach using vitamin B12-conjugated sericin for mitigating nanodiamond-induced toxicity in darkling beetles.

The escalating use of nanodiamonds (NDs) has raised concerns about their ecotoxicological impact, prompting exploration of therapeutic interventions. This paper pioneers the examination of Vitamin B12-conjugated sericin (VB12-SER) as a potential therapeutic approach against ND-induced toxicity in darkling beetles (Blaps polychresta). The study analyzes mortality rates and organ-specific effects, covering the testis, ovary, and midgut, before and after treatments. Following exposure to 10 mg NDs/g body weight, within a subgroup of individuals termed ND2 with a mortality rate below 50%, two therapeutic treatments were administered, including pure sericin (SER) at 10 mg/mL and VB12-SER at 10.12 mg/mL. Consequently, five experimental groups (control, SER, ND2, ND2+SER, ND2+SER+VB12) were considered. Kaplan-Meier survival analysis was performed to assess the lifespan distribution of the insects in these groups over a 30-d period. Analyses revealed increased mortality and significant abnormalities induced by NDs within the examined organs, including cell death, DNA damage, enzyme dysregulation, antioxidant imbalances, protein depletion, lipid peroxidation, and morphological deformities. In contrast, the proposed treatments, especially (ND2+SER+VB12), demonstrated remarkable recovery, highlighting VB12-conjugated SER's potential in mitigating ND-triggered adverse effects. Molecular docking simulations affirmed binding stability and favorable interactions of the VB12-SER complex with target proteins. This research enhances understanding of NDs' effects on B. polychresta, proposing it as an effective bioindicator, and introduces VB12-conjugated SER as a promising therapeutic strategy in nanotoxicological studies.

The oxidation of carbon nanostructures imaged by electron microscopy: Comparison between in-situ TEM and TGA experiments

The development of a model of carbon oxidation has engaged researchers for decades. Yet many outstanding questions remain due to the inability to experimentally study the details of the oxidation. Today, novel techniques such as environmental transmission electron microscopy (ETEM), allowing for in-situ nanoscale observations of the oxidation process, can help illuminate some of these questions. In this study of few layer graphene (FLG), multi-walled carbon nanotubes (MWCNTs), buckminsterfullerene (C60), and nanodiamonds (NDs) oxidizing in temperatures up to 1100 °C and we analyze the importance of nanostructure for the thermal stability of nanocarbons. The study was complemented with thermogravimetric analysis (TGA) and the experiments were in good agreement with oxidation rates increasing sharply with temperature and the thermal stability of the materials MWCNTs, FLG, C60 and NDs in descending order. Based on the direct nanoscale visualization obtained in the ETEM the materials can be divided into two overall categories: materials with low strain sp2-bonds (FLG and MWCNT); and materials with high strain sp2-bonds (C60) or sp3-bonds (NDs). For materials in the first category, it is possible to identify several different phenomena as their oxidation rate increases as a function of temperatures whereas materials in the second category appear to be more influenced by extrinsic factors such as the electron beam and by structural transformation upon heating. This study clearly shows the value of adding ETEM results to traditional TGA investigations since it gives both a complementary and more detailed information about the dynamic oxidation process.

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.

Application of Cyrene solvent for the fabrication of polymethyl methacrylate, polyethyl methacrylate and composite films containing hydroxyapatite and diamonds

AbstractCyrene is a new biodegradable solvent, which represents a green alternative to many traditional toxic solvents for advanced polymers. Therefore, this investigation is motivated by interest in applications of Cyrene for polymer processing. The feasibility of solubilization of polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA) in Cyrene is demonstrated. The ability to form relatively concentrated solutions of the high molecular mass polymers is an important factor for the formation of PMMA and PEMA films by a dip coating method. It was found that the polymer coatings provide corrosion protection of stainless steel in 30 g L−1 NaCl solutions. Another important finding is that the use of Cyrene facilitates the fabrication of stable suspensions of hydroxyapatite (HAp), microdiamond, and nanodiamond particles. Therefore, the problems of the dispersant selection for dispersion of chemically inert diamond and development of biocompatible dispersants are avoided using Cyrene. For the fabrication of composite films, HAp nanorods with reduced particle size are obtained using rutin as a chelating capping agent. Composite films containing HAp, microdiamond and nanodiamond in the PMMA or PEMA matrix are obtained. The composite films are promising for biomedical applications. It was found that the film morphology, composition and microstructure are influenced by the solvent–particle–polymer interactions and processing conditions.

Tribological behavior of MoS2–Sb2O3-annealed nanodiamond coating on PEO-LST treated Ti6Al4V

MoS2–Sb2O3 coating is commonly used as solid lubricant for titanium alloys, but the wear-resistance performance is still limited. Core-shell annealed nanodiamond (AND) particle is used as reinforcement for MoS2–Sb2O3 coating on Ti6Al4V substrate treated by plasma electrolytic oxidation (PEO) and laser surface texturing (LST). The incorporation of AND particles into the MoS2–Sb2O3 coating results in a 39 % decrease in friction and significantly reduces wear on the composite coating. Structural transformation of AND particles to amorphous carbon and graphitic structure promotes the densification of top-layer coating, enhancing lubrication and wear-resistance. Change of contact stress by PEO-LST promotes the formation of dense tribofilm and re-orientation of MoS2. This study has implications for the development of solid lubrication coatings for aerospace applications through functional nanomaterials and targeted designed surfaces.

Creation, Control, and Modeling of NV Centers in Nanodiamonds

AbstractSensing based on Nitrogen‐Vacancy (NV) centers in nanodiamonds (NDs) represents a potentially groundbreaking technology with broad applications. Nevertheless, the optimization of their quantum‐optical properties is still a challenging issue. The present work aims at enhancing and controlling NV centers optical properties in NDs by combining their surface chemistry tuning and proton beam irradiation. Systematic thermal oxidations are carried out to study the evolution of surface chemical groups (IR spectroscopy), as well as their influence on optical properties (photoluminescence spectroscopy, PL decay measurements). Proton irradiation is performed by exploring a wide range of fluences (1014 – 1017 cm−2) in order to precisely control the amount of NV centers, thus defining the conditions that maximize their creation and emission intensity. In addition, NV centers charge state control is achieved by assessing NV−/NV0 ratio upon different surface termination tuning and NV centers amount. Finally, a novel predictive mathematical model is developed, allowing for the evaluation of the efficiencies of the formation of both NV− and NV0. Although the model is tested in the specific case study with proton irradiated NDs, it offers a broad applicability, thus representing a key landmark in the prediction of the outcome of ion‐beam‐based color centers generation in diamond.

Refractometric method to study the coating thickness of diamond nanoparticles

A method based on refractometric measurements of liquid nanodisperse systems has been developed to determine the quantitative composition of diamond-amorphous carbon colloidal particles. It was demonstrated that by measuring the changes in the refractive index and density of sols caused by changes in particle concentration it is possible to determine the thickness of the particle surface layer, assuming its composition is known. Within the framework of the Mie theory, the influence of the size of diamond particles with carbon coating on the refractive index of hydrosols was quantified. The limits of applicability of the developed method have been determined. For several polydisperse sols with coated diamond particles the thickness of carbon coating was determined.

Optimization of the properties of nematic matrix suspended with subtle quantities of the nanoparticles for improved alignment and operating voltage

ABSTRACT The current study examines and reflects the effect of minute quantity of Diamond nanoparticles (DNPs) in the Nematic liquid crystal (NLC) matrix. A well structured and strategized study is performed in order to get a deep understanding about the interactions that might have taken place between the guests and the hosts. Our study professed a significant alteration in the number of parameters of guest-host system in comparison to the pure liquid crystal (LC) matrix that could be found extremely promising for the display devices and low-power switching machines. 0.05, 0.07 and 0.1 wt/wt% concentrations of the NPs incorporated in the LC matrix and the composites are prepared with the high precision weight measurement using electrical balance. Dielectric spectrum is catalogued for both the homogeneous and vertical alignments of sample cells. Threshold voltage and operating voltage are found to be significantly decreased for 0.05 wt/wt% composite. Response time for the prepared composites is profoundly abated which is a crucial factor for the fast response devices. Careful examination of pretilt angles is executed and an improvement in the alignment is found as one more perk of this study.

Advanced electrochemical sensing of cyanuric acid: An integration of transition metal dichalcogenides, copper and diamond nanoparticles

In the present study, we demonstrate the synergistic effect of copper nanoparticles, tungsten disulfide, and diamond nanoparticles on the electrochemical detection of cyanuric acid, a compound conventionally employed for disinfection in aquatic recreational facilities such as swimming pools. First, copper nanoparticles were synthesized in-situ on a glassy carbon electrode through the electrochemical reduction of copper nitrate and their response towards cyanuric acid was assessed. In order to improve this response, we evaluated the inclusion of transition metal dichalcogenides nanosheets (MoS2, ReS2 or WS2), as well as diamond nanoparticles in the electrochemical sensor construction. These nanomaterials were incorporated onto the electrode via drop-casting from their respective suspensions. Specifically, the 2D transition metal dichalcogenide suspensions were obtained through a top-down exfoliation method, facilitated by ultrasonic assistance. After optimizing the arrangement of nanomaterials on the glassy carbon electrode to enhance cyanuric acid detection, we characterized the morphology of the resulting surfaces at each stage of electrode surface modification by atomic force microscopy and scanning electron microscopy. The optimized methodology revealed that the sensor response exhibited a linear relationship with cyanuric acid concentrations ranging from 0.077 to 0.70 mM with a detection limit of 23 µM. The sensor was applied to cyanuric acid determination in a swimming pool water sample, obtaining very good recoveries. The results are in good agreement with those obtained by HPLC-UV–vis measurements.

Production of Cu/Diamond Composite Coatings and Their Selected Properties.

This article presents Cu/diamond composite coatings produced by electrochemical reduction on steel substrates and a comparison of these coatings with a copper coating without diamond nanoparticles (<10 nm). Deposition was carried out using multicomponent electrolyte solutions at a current density of 3 A/dm2 and magnetic stirring speed of 100 rpm. Composite coatings were deposited from baths with different diamond concentrations (4, 6, 8, 10 g/dm3). This study presents the surface morphology and structure of the produced coatings. The surface roughness, coating thickness (XRF), mechanical properties (DSI), and adhesion of coatings to substrates (scratch tests) were also characterized. The coatings were also tested to assess their solderability, including their spreadability, wettability of the solder, durability of solder-coating bonds, and a microstructure study.

Probing the 13C nuclear spin relaxation of diamond nanoparticles with solid-state NMR

Probing the 13C nuclear spin relaxation of diamond nanoparticles with solid-state NMR

Multifunctional Nanodiamond Interfacial Layer for Ultra‐Stable Zinc‐Metal Anodes

AbstractAchieving reversible plating/stripping of zinc (Zn) anodes is crucial in aqueous Zn‐ion batteries (AZIBs). However, undesired dendrite growth and parasitic side reactions severely deteriorate battery lifespan. The construction of stable protective coating is an effective strategy to enhance anode stability. In this study, a multifunctional nanodiamond (ND) inorganic layer is designed and constructed on both Zn and Cu electrodes that can both effectively inhibit dendrite growth and suppress Zn anode corrosion. Experimental results and theoretical calculations demonstrate that this artificial protective layer, with ultra‐high surface energy, enables the controlled creation of abundant nucleation sites (in the order of 1012 cm−2) for the homogenization of ion flux and electric field on the anode. It is found that zinc ions preferentially adhere to the diamond surfaces with lower diffusion barriers, leading to uniform zinc deposition. A symmetric cell with the ND‐protected Zn (Zn‐ND) anode exhibits reversible plating/stripping behavior for an impressive duration of over 3600 h at 1 mA cm−2. Furthermore, the MnO2||Zn full battery retains 90% of its initial capacity after 3500 cycles at 2 A g−1, and assembled hybrid capacitor operates smoothly over 65 000 cycles at 10 A g−1. These results underscore the potential of this coating as a promising solution for achieving highly stable Zn anodes for aqueous batteries.

A New Electrochemical Sensor for the Detection of Azithromycin using Screen‐Printed Carbon Electrode Modified with Boron‐Doped Diamond Nanoparticles and Reduced‐Graphene Oxide

AbstractExcessive use of azithromycin (AZM) is associated with resistance and negative impacts on the environment. Therefore, this study aimed to develop an electrochemical sensor for AZM. The screen‐printed carbon electrode (SPCE) modified with boron‐doped diamond nanoparticle (BDDNP) and reduced‐graphene oxide (rGO) was successfully applied to measure the AZM concentration. The morphology of the modified electrode was characterized by scanning electron microscopy‐energy dispersive X‐ray (SEM‐EDX). Furthermore, the effect of electrochemical parameters, such as signal per background, scan rate, and selectivity was determined. The results showed that under optimum conditions, the plot of AZM demonstrated linearity in the range of 30–100 μM with a limit of detection (LOD) at 1.6 μM. The repeatability and recovery were also investigated, and the sensor was applied to real samples obtained from hospital wastewater. A remarkable 93.27 % recovery rate and excellent precision were recorded with an %RSD of 2.41 %. This study underscores the potential of SPCE modified with rGO/BDDNP for accurate and reliable measurement of AZM levels, showcasing great applicability in addressing the challenges associated with monitoring AZM in various environmental settings.