Carbon is one of the most fascinating elements due to its structurally diverse allotropic forms stemming from its bonding varieties (sp, sp2, and sp3). Exploring new forms of carbon has always been the eternal theme of scientific research. Herein, we report the amorphous (AM) carbon materials with high fraction of sp3 bonding recovered from compression of fullerene C60 under high pressure and high temperature previously unexplored. Analysis of photoluminescence and absorption spectra demonstrates that they are semiconducting with a bandgap range of 1.5–2.2 eV, comparable to that of widely used amorphous silicon. Comprehensive mechanical tests demonstrate that the synthesized AM-III carbon is the hardest and strongest amorphous material known so far, which can scratch diamond crystal and approach its strength. The produced AM carbon materials combine outstanding mechanical and electronic properties, and may potentially be used in photovoltaic applications that require ultrahigh strength and wear resistance.

Diamond anvil cell techniques have been improved to allow access to the multimegabar ultrahigh-pressure region for exploring novel phenomena in condensed matter. However, the only way to determine crystal structures of materials above 100 GPa, namely, X-ray diffraction (XRD), especially for low Z materials, remains nontrivial in the ultrahigh-pressure region, even with the availability of brilliant synchrotron X-ray sources. In this work, we perform a systematic study, choosing hydrogen (the lowest X-ray scatterer) as the subject, to understand how to better perform XRD measurements of low Z materials at multimegabar pressures. The techniques that we have developed have been proved to be effective in measuring the crystal structure of solid hydrogen up to 254 GPa at room temperature [C. Ji et al., Nature 573, 558–562 (2019)]. We present our discoveries and experiences with regard to several aspects of this work, namely, diamond anvil selection, sample configuration for ultrahigh-pressure XRD studies, XRD diagnostics for low Z materials, and related issues in data interpretation and pressure calibration. We believe that these methods can be readily extended to other low Z materials and can pave the way for studying the crystal structure of hydrogen at higher pressures, eventually testing structural models of metallic hydrogen.

The effect of high-pressure synthesis temperature on the structure and indentation characteristics of the superelastic hard carbon formed from amorphous fullerites and on the tribological properties of the Co-based composite materials (CM) reinforced by the particles of such carbon has been studied by Raman spectroscopy, high-resolution transmission electron microscopy (HRTEM), indentation measurements, and tribological tests. It is shown that ball milling (for 48 h) of C₆₀ fullerite crystals results in the amorphization of the product of fullerite transformation upon their high-pressure treatment at temperatures above the stability limit of fullerene molecule (~800°C). An increase in synthesis temperature at 8 GPa from 800°C to 1200°C leads to a gradual graphitization of the structure of amorphous fullerite derived carbon. This decreases its hardness and indentation modulus from 32 to 18 GPa and from 256 to 95 GPa, respectively, and increases the elastic recovery (from 80% to 86%). The best tribological characteristics of the CM are attained at the maximum particle hardness, which is realized in the CM synthesized at 800°C. When the synthesis temperature is elevated to 1200°C, the friction coefficient and wear rate of the CM increase, but they remain substantially lower than those of the matrix cobalt.

The synthesis of metal-matrix composite materials reinforced with superelastic hard carbon particles formed from C60 fullerites includes heating of the metal-fullerite powder mixture to temperatures above 800C under pressure. The structure evolution of the carbon particles upon heating from 700 to 800 C at a pressure of 5 GPa has been studied in detail by Raman spectroscopy and indentation hardness measurements. It is shown that the structure of the carbon particle passes the stage of a nanoscale mixture of one- and two-dimensional polymers with the resulting atomic superelastic solid phase. The determining properties of the carbon particles such as superplasticity and high hardness are attained before the complete disappearance of polymerized fullerites, the remnants of which are responsible for the disintegration of the material upon scratching.

Herein, a reduced graphene oxide–zinc oxide (rGO–ZnO) hybrid nanocomposite (1 wt% rGO) is synthesized and heat treated at different temperatures, aimed at modulating the intrinsic bulk/surface defects naturally present in nano‐ZnO. The correlation of both the dispersion of rGO within the metal oxide scaffold and the defects present on the semiconductor crystalline lattice with the photocatalytic performance toward the degradation of a molecular dye in water is investigated and discussed. It is shown that several processes compete to determine the catalytic skill of the nanocomposite, which can be enhanced by a simple thermal treatment at moderate temperatures.

Single-walled carbon nanotubes (SWCNTs) were functionalized by ferrocene through ethyleneglycol chains of different lengths (FcETGn) and the functionalized SWCNTs (f-SWCNTs) were characterized by different complementary analytical techniques. In particular, high-resolution scanning electron transmission microscopy (HRSTEM) and electron energy loss spectroscopy (EELS) analyses support that the outer tubes of the carbon-nanotube bundles were covalently grafted with FcETGn groups. This result confirms that the electrocatalytic effect observed during the oxidation of the reduced form of nicotinamide adenine dinucleotide (NADH) co-factor by the f-SWCNTs is due to the presence of grafted ferrocene derivatives playing the role of a mediator. This work clearly proves that residual impurities present in our SWCNT sample (below 5 wt. %) play no role in the electrocatalytic oxidation of NADH. Moreover, molecular dynamic simulations confirm the essential role of the PEG linker in the efficiency of the bioelectrochemical device in water, due to the favorable interaction between the ETG units and water molecules that prevents π-stacking of the ferrocene unit on the surface of the CNTs. This system can be applied to biosensing, as exemplified for glucose detection. The well-controlled and well-characterized functionalization of essentially clean SWCNTs enabled us to establish the maximum level of impurity content, below which the f-SWCNT intrinsic electrochemical activity is not jeopardized.

TEMPO (2,2,6,6-tetramethylpiperidine-1-oxylradical)-mediated oxidation nanofibers (TOCNF), as a biocompatible and bioactive material, have opened up a new application of nanocellulose for the removal of water contaminants. This development demands extremely sensitive and accurate methods to understand the surface interactions between water pollutants and TOCNF. In this report, we investigated the adsorption of metal ions on TOCNF surfaces using experimental techniques atthe nano and molecular scales with Cu(II) as the target pollutant in both aqueous and dry forms. Imaging with in situ atomic force microscopy (AFM), together with a study of the physiochemical properties of TOCNF caused by adsorption with Cu(II) in liquid, were conducted using the PeakForce Quantitative NanoMechanics (PF-QNM) mode at the nano scale. The average adhesion force between the tip and the target single TOCNF almost tripled after adsorption with Cu(II) from 50 pN to 140 pN. The stiffness of the TOCNF was also enhanced because the Cu(II) bound to the carboxylate groups and hardened the fiber. AFM topography, scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS) mapping and X-ray photoelectron spectroscopy (XPS) indicated that the TOCNF were covered by copper nanolayers and/or nanoparticles after adsorption. The changes in the molecular structure caused by the adsorption were demonstrated by Raman and attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). This methodology will be of great assistance to gain qualitative and quantitative information on the adsorption process and interaction between charged entities in aqueous medium.

Single-walled carbon nanotubes (SWCNTs) have been dynamically (shock) compressed to 0.5 Mbar, above the limit of their structural integrity. Two distinct types of material are identified by high-resolution transmission electron microscopy (HRTEM) and multi-wavelength Raman spectroscopy in the sample recovered after shock: multi-layer graphene (MLG) and a two-phase material composed of nano-clustered graphene and amorphous carbon whereas no diamond-like carbon or carbon nano-onions are found. Peak decomposition of the Raman spectra was used to estimate the coherent scatterers (clusters) size in MLG at 36 nm from the D- to G-band intensity ratio dependence on the photon excitation energy. Botella et al. (article no. 1700315) propose the peak fitting model for decomposition of the Raman spectra of highly disordered carbon material containing graphene nano-clusters and stress the importance of accounting for heptagonal- and pentagonal-ring defects in graphene layers for the analysis of such spectra. The cover image shows HRTEM images and the correspondent Raman spectra of the two types of material along with peak decomposition of the two-phase material with the peaks assigned to heptagons (a) and pentagons (b). Particulars of the SWCNTs transformation to other structural forms of carbon at high pressure/temperature are discussed

Single-walled carbon nanotubes (SWCNTs) have been dynamically (shock) compressed to 0.5 Mbar, above the limit of their structural integrity. Two distinct types of material are identified by high-resolution transmission electron microscopy (HRTEM) and multi-wavelength Raman spectroscopy in the sample recovered after shock: multi-layer graphene (MLG) and a two-phase material composed of nano-clustered graphene and amorphous carbon whereas no diamond-like carbon or carbon nano-onions are found. Peak decomposition of the Raman spectra was used to estimate the coherent scatterers (clusters) size in MLG at 36 nm from the D- to G-band intensity ratio dependence on the photon excitation energy. Botella et al. (article no. 1700315) propose the peak fitting model for decomposition of the Raman spectra of highly disordered carbon material containing graphene nano-clusters and stress the importance of accounting for heptagonal- and pentagonal-ring defects in graphene layers for the analysis of such spectra. The cover image shows HRTEM images and the correspondent Raman spectra of the two types of material along with peak decomposition of the two-phase material with the peaks assigned to heptagons (a) and pentagons (b). Particulars of the SWCNTs transformation to other structural forms of carbon at high pressure/temperature are discussed

While changes in resonant Raman scattering measurements are commonly used to measure the effect of chemical functionalization on single-walled carbon nanotubes, the precise effects of functionalization on these spectra have yet to be clearly identified. In this density functional theory study, we explore the effects of functionalization on both the nanotube resonance energy and frequency shifts in radial breathing mode. Charge transfer effects cause a shift in the first Van Hove singularity spacings, and hence resonance excitation energy, and lead to a decrease in the radial breathing mode frequency, notably when the Fermi level decreases. By varying stochastically the effective mass of carbon atoms in the tube, we simulate the mass effect of functionalization on breathing mode frequency. Finally, full density functional calculations are performed for different nanotubes with varying functional group distribution and concentration using fluorination and hydrogenation, allowing us to determine overall effect on radial breathing mode and charge transfer. The results concur well with experiment, and we discuss the importance when using Raman spectroscopy to interpret experimental functionalization treatments