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).

Ceria-Catalyzed Hydrolytic Cleavage of Sulfonamides.

Nanoceria is a promising nanomaterial for the catalytic hydrolysis of a wide variety of substances. In this study, it was experimentally demonstrated for the first time that CeO2 nanostructures show extraordinary reactivity toward sulfonamide drugs (sulfadimethoxine, sulfamerazine, and sulfapyridine) in aqueous solution without any illumination, activation, or pH adjustment. Hydrolytic cleavage of various bonds, including S-N, C-N, and C-S, was proposed as the main reaction mechanism and was indicated by the formation of various reaction products, namely, sulfanilic acid, sulfanilamide, and aniline, which were identified by HPLC-DAD, LC-MS/MS, and NMR spectroscopy. The kinetics and efficiency of the ceria-catalyzed hydrolytic cleavage were dependent on the structure of the sulfonamide molecule and physicochemical properties of Nanoceria prepared by three different precipitation methods. However, in general, all three ceria samples were able to cleave SA drugs tested, proving the robust and unique surface reactivity toward these compounds inherent to cerium dioxide. The demonstrated reactivity of CeO2 to molecules containing sulfonamide or even sulfonyl (and similar) functional groups may be significant for both heterogeneous catalysis and environmentally important degradation reactions.

Correlative atomic force microscopy and scanning electron microscopy of bacteria-diamond-metal nanocomposites.

Research investigating the interface between biological organisms and nanomaterials nowadays requires multi-faceted microscopic methods to elucidate the interaction mechanisms and effects. Here we describe a novel approach and methodology correlating data from an atomic force microscope inside a scanning electron microscope (AFM-in-SEM). This approach is demonstrated on bacteria-diamond-metal nanocomposite samples relevant in current life science research. We describe a procedure for preparing such multi-component test samples containing E. coli bacteria and chitosan-coated hydrogenated nanodiamonds decorated with silver nanoparticles on a carbon-coated gold grid. Microscopic topography information (AFM) is combined with chemical, material, and morphological information (SEM using SE and BSE at varied acceleration voltages) from the same region of interest and processed to create 3D correlative probe-electron microscopy (CPEM) images. We also establish a novel 3D RGB color image algorithm for merging multiple SE/BSE data from SEM with the AFM surface topography data which provides additional information about microscopic interaction of the diamond-metal nanocomposite with bacteria, not achievable by individual analyses. The methodology of CPEM data interpretation is independently corroborated by further in-situ (EDS) and ex-situ (micro-Raman) chemical characterization as well as by force volume AFM analysis. We also discuss the broader applicability and benefits of the methodology for life science research.

Absolute energy levels in nanodiamonds of different origins and surface chemistries.

Nanodiamonds (NDs) are versatile, broadly available nanomaterials with a set of features highly attractive for applications from biology over energy harvesting to quantum technologies. Via synthesis and surface chemistry, NDs can be tuned from the sub-micron to the single-digit size, from conductive to insulating, from hydrophobic to hydrophilic, and from positively to negatively charged surface by simple annealing processes. Such ND diversity makes it difficult to understand and take advantage of their electronic properties. Here we present a systematic correlated study of structural and electronic properties of NDs with different origins and surface terminations. The absolute energy level diagrams are obtained by the combination of optical (UV-vis) and photoelectron (UPS) spectroscopies, Kelvin probe measurements, and energy-resolved electrochemical impedance spectroscopy (ER-EIS). The energy levels and density of states in the bandgap of NDs are correlated with the surface chemistry and structure characterized by FTIR and Raman spectroscopy. We show profound differences in energy band shifts (by up to 3 eV), Fermi level position (from p-type to n-type), electron affinity (from +0.5 eV to -2.2 eV), optical band gap (5.2 eV to 5.5 eV), band gap states (tail or mid-gap), and electrical conductivity depending on the high-pressure, high-temperature and detonation origin of NDs as well as on the effects of NDs' oxidation, hydrogenation, sp2/sp3 carbon phases and surface adsorbates. These data are fundamental for understanding and designing NDs' optoelectrochemical functional mechanisms in diverse application areas.

Cerium-Bismuth Oxides/Oxynitrates with Low Toxicity for the Removal and Degradation of Organophosphates and Bisphenols.

Nanoscale cerium-bismuth oxides/oxynitrates were prepared by a scalable low-temperature method at ambient pressure using water as the sole solvent. Solid solutions were formed up to a 1:1 Ce/Bi molar ratio, while at higher doping levels, bismuth oxynitrate photocatalysts with a pronounced layered structure were formed. Bismuth caused significant changes in the structure and surface properties of nanoceria, such as the formation of defects, oxygen-containing surface groups, and Lewis and Brønsted acid sites. The prepared bifunctional adsorbents/photocatalysts were efficient in the removal of toxic organophosphate (methyl paraoxon) from water by reactive adsorption followed by photocatalytic decomposition of the parent compound and its degradation product (p-nitrophenol). Bi-doped ceria also effectively adsorbed and photodegraded the endocrine disruptors bisphenols A and S and outperformed pure ceria and the P25 photocatalyst in terms of efficiency, durability, and long-term stability. The very low toxicity of Bi-nanoceria to mammalian cells, aquatic organisms, and bacteria has been demonstrated by comprehensive in vivo/in vitro testing, which, in addition to its simple "green" synthesis, high activity, and durability, makes Bi-doped ceria promising for safe use in abatement of toxic chemicals.

Size-Dependent Thermal Stability and Optical Properties of Ultra-Small Nanodiamonds Synthesized under High Pressure.

Diamond properties down to the quantum-size region are still poorly understood. High-pressure high-temperature (HPHT) synthesis from chloroadamantane molecules allows precise control of nanodiamond size. Thermal stability and optical properties of nanodiamonds with sizes spanning range from <1 to 8 nm are investigated. It is shown that the existing hypothesis about enhanced thermal stability of nanodiamonds smaller than 2 nm is incorrect. The most striking feature in IR absorption of these samples is the appearance of an enhanced transmission band near the diamond Raman mode (1332 cm-1). Following the previously proposed explanation, we attribute this phenomenon to the Fano effect caused by resonance of the diamond Raman mode with continuum of conductive surface states. We assume that these surface states may be formed by reconstruction of broken bonds on the nanodiamond surfaces. This effect is also responsible for the observed asymmetry of Raman scattering peak. The mechanism of nanodiamond formation in HPHT synthesis is proposed, explaining peculiarities of their structure and properties.

Laser-Induced Modification of Hydrogenated Detonation Nanodiamonds in Ethanol.

Apart from the frequently used high-temperature annealing of detonation nanodiamonds (DNDs) in an inert environment, laser irradiation of DNDs in a liquid can be effectively used for onion-like carbon (OLC) formation. Here, we used fully de-aggregated hydrogenated DNDs (H-DNDs) dispersed in ethanol, which were irradiated for up to 60 min using a 532 nm NdYAG laser with an energy of 150 mJ in a pulse (5 J/cm2) at a pulse duration of 10 ns and a repetition rate of 10 Hz. We investigated the DND surface chemistry, zeta potential, and structure as a function of laser irradiation time. Infrared spectroscopy revealed a monotonical decrease in the C-Hx band intensities and an increase of the C-O and C=O features. Transmission electron microscopy (TEM) revealed the formation of OLC, as well as a gradual loss of nanoparticle character, with increasing irradiation time. Surprisingly, for samples irradiated up to 40 min, the typical and unchanged DND Raman spectrum was recovered after their annealing in air at 450 °C for 300 min. This finding indicates the inhomogeneous sp3 to sp2 carbon transformation during laser irradiation, as well as the insensitivity of DND Raman spectra to surface chemistry, size, and transient structural changes.

Nanodiamond surface chemistry controls assembly of polypyrrole and generation of photovoltage.

Nanoscale composite of detonation nanodiamond (DND) and polypyrrole (PPy) as a representative of organic light-harvesting polymers is explored for energy generation, using nanodiamond as an inorganic electron acceptor. We present a technology for the composite layer-by-layer synthesis that is suitable for solar cell fabrication. The formation, pronounced material interaction, and photovoltaic properties of DND-PPy composites are characterized down to nanoscale by atomic force microscopy, infrared spectroscopy, Kelvin probe, and electronic transport measurements. The data show that DNDs with different surface terminations (hydrogenated, oxidized, poly-functional) assemble PPy oligomers in different ways. This leads to composites with different optoelectronic properties. Tight material interaction results in significantly enhanced photovoltage and broadband (1-3.5 eV) optical absorption in DND/PPy composites compared to pristine materials. Combination of both oxygen and hydrogen functional groups on the nanodiamond surface appears to be the most favorable for the optoelectronic effects. Theoretical DFT calculations corroborate the experimental data. Test solar cells demonstrate the functionality of the concept.

Silicon-Vacancy Centers in Ultra-Thin Nanocrystalline Diamond Films.

Color centers in diamond have shown excellent potential for applications in quantum information processing, photonics, and biology. Here we report the optoelectronic investigation of shallow silicon vacancy (SiV) color centers in ultra-thin (7⁻40 nm) nanocrystalline diamond (NCD) films with variable surface chemistry. We show that hydrogenated ultra-thin NCD films exhibit no or lowered SiV photoluminescence (PL) and relatively high negative surface photovoltage (SPV) which is ascribed to non-radiative electron transitions from SiV to surface-related traps. Higher SiV PL and low positive SPV of oxidized ultra-thin NCD films indicate an efficient excitation-emission PL process without significant electron escape, yet with some hole trapping in diamond surface states. Decreasing SPV magnitude and increasing SiV PL intensity with thickness, in both cases, is attributed to resonant energy transfer between shallow and bulk SiV. We also demonstrate that thermal treatments (annealing in air or in hydrogen gas), commonly applied to modify the surface chemistry of nanodiamonds, are also applicable to ultra-thin NCD films in terms of tuning their SiV PL and surface chemistry.

Hydroxylation and self-assembly of colloidal hydrogenated nanodiamonds by aqueous oxygen radicals from atmospheric pressure plasma jet.

Plasma chemical surface modification of nanoparticles in gas-liquid type reactors enables a controllable, specific, low-cost, and environmentally friendly alternative to wet chemistry methods or thermal and dry plasma treatments. Here the atmospheric pressure radio-frequency microplasma jet (µ-APPJ) operating with 0.6% O2 in He is used to deliver aqueous oxygen radicals (AOR) to the surface of ∼3 nm hydrogenated detonation nanodiamonds (H-DNDs) suspended in water. The AOR-treated H-DND samples are characterized by FTIR and XPS spectroscopies and by AFM and SEM imaging. The main chemical reaction mechanism is identified as the abstraction of surface hydrogen atoms by O or OH radicals and a consequent attachment of the OH group, thereby increasing concentration of alcohols, carboxyls, and aldehydes on the DND's surface. FTIR spectra reveal also a structural re-arrangement of the surface water on the AOR-treated H-DNDs. Yet zeta-potential of AOR-treated H-DNDs still remains positive (decreases from +45 mV to +30 mV). The chemical modification gives rise to formation of nanoscale chain-like aggregates when AOR-treated H-DNDs are deposited on Si substrate.

Ultrathin Nanocrystalline Diamond Films with Silicon Vacancy Color Centers via Seeding by 2 nm Detonation Nanodiamonds.

Color centers in diamonds have shown excellent potential for applications in quantum information processing, photonics, and biology. Here we report chemical vapor deposition (CVD) growth of nanocrystalline diamond (NCD) films as thin as 5-6 nm with photoluminescence (PL) from silicon-vacancy (SiV) centers at 739 nm. Instead of conventional 4-6 nm detonation nanodiamonds (DNDs), we prepared and employed hydrogenated 2 nm DNDs (zeta potential = +36 mV) to form extremely dense (∼1.3 × 1013 cm-2), thin (2 ± 1 nm), and smooth (RMS roughness < 0.8 nm) nucleation layers on an Si/SiOx substrate, which enabled the CVD growth of such ultrathin NCD films in two different and complementary microwave (MW) CVD systems: (i) focused MW plasma with an ellipsoidal cavity resonator and (ii) pulsed MW plasma with a linear antenna arrangement. Analytical ultracentrifuge, infrared and Raman spectroscopies, atomic force microscopy, and scanning electron microscopy are used for detailed characterization of the 2 nm H-DNDs and the nucleation layer as well as the ultrathin NCD films. We also demonstrate on/off switching of the SiV center PL in the NCD films thinner than 10 nm, which is achieved by changing their surface chemistry.

High-yield fabrication and properties of 1.4 nm nanodiamonds with narrow size distribution.

Detonation nanodiamonds (DNDs) with a typical size of 5 nm have attracted broad interest in science and technology. Further size reduction of DNDs would bring these nanoparticles to the molecular-size level and open new prospects for research and applications in various fields, ranging from quantum physics to biomedicine. Here we show a controllable size reduction of the DND mean size down to 1.4 nm without significant particle loss and with additional disintegration of DND core agglutinates by air annealing, leading to a significantly narrowed size distribution (±0.7 nm). This process is scalable to large quantities. Such molecular-sized DNDs keep their diamond structure and characteristic DND features as shown by Raman spectroscopy, infrared spectroscopy, STEM and EELS. The size of 1 nm is identified as a limit, below which the DNDs become amorphous.

Size and Purity Control of HPHT Nanodiamonds down to 1 nm.

High-pressure high-temperature (HPHT) nanodiamonds originate from grinding of diamond microcrystals obtained by HPHT synthesis. Here we report on a simple two-step approach to obtain as small as 1.1 nm HPHT nanodiamonds of excellent purity and crystallinity, which are among the smallest artificially prepared nanodiamonds ever shown and characterized. Moreover we provide experimental evidence of diamond stability down to 1 nm. Controlled annealing at 450 °C in air leads to efficient purification from the nondiamond carbon (shells and dots), as evidenced by X-ray photoelectron spectroscopy, Raman spectroscopy, photoluminescence spectroscopy, and scanning transmission electron microscopy. Annealing at 500 °C promotes, besides of purification, also size reduction of nanodiamonds down to ∼1 nm. Comparably short (1 h) centrifugation of the nanodiamonds aqueous colloidal solution ensures separation of the sub-10 nm fraction. Calculations show that an asymmetry of Raman diamond peak of sub-10 nm HPHT nanodiamonds can be well explained by modified phonon confinement model when the actual particle size distribution is taken into account. In contrast, larger Raman peak asymmetry commonly observed in Raman spectra of detonation nanodiamonds is mainly attributed to defects rather than to the phonon confinement. Thus, the obtained characteristics reflect high material quality including nanoscale effects in sub-10 nm HPHT nanodiamonds prepared by the presented method.

Nanoparticles assume electrical potential according to substrate, size, and surface termination.

Electrical potential of nanoparticles under relevant environment is substantial for their applications in electronics as well as sensors and biology. Here, we use Kelvin force microscopy to characterize electrical properties of semiconducting diamond nanoparticles (DNPs) of 5-10 nm nominal size and metallic gold nanoparticles (20 and 40 nm) on Si and Au substrates under ambient conditions. The DNPs are deposited on Si and Au substrates from dispersions with well-defined zeta-potential. We show that the nanoparticle potential depends on its size and that the only reliable potential characteristic is a linear fit of this dependence within a 5-50 nm range. Systematically different potentials of hydrogenated, oxidized, and graphitized DNPs are resolved using this methodology. The differences are within 50 mV, that is much lower than on monocrystalline diamond. Furthermore, all of the nanoparticles assume their potential within -60 mV according to the Au and Si substrate, thus gaining up to 0.4 V difference. This effect is attributed to DNP charging by charge transfer and/or polarization. This is confirmed by secondary electron emission. Such effects are general with broad implications for nanoparticles applications.

Sensitivity of diamond-capped impedance transducer to Tröger's base derivative.

Sensitivity of an intrinsic nanocrystalline diamond (NCD) layer to naphthalene Tröger's base derivative decorated with pyrrole groups (TBPyr) was characterized by impedance spectroscopy. The transducer was made of Au interdigitated electrodes (IDE) with 50 µm spacing on alumina substrate which were capped with the NCD layer. The NCD-capped transducer with H-termination was able to electrically distinguish TBPyr molecules (the change of surface resistance within 30-60 kΩ) adsorbed from methanol in concentrations of 0.04 mg/mL to 40 mg/mL. An exponential decay of the surface resistance with time was observed and attributed to the readsorption of air moisture after methanol evaporation. After surface oxidation the NCD cap layer did not show any leakage due to NCD grain boundaries. We analyzed electronic transport in the transducer and propose a model for the sensing mechanism based on surface ion replacement.