Transient chemical and structural changes in graphene oxide during ripening.

Graphene oxide (GO)-the oxidized form of graphene-is actively studied in various fields, such as energy, electronic devices, separation of water, materials engineering, and medical technologies, owing to its fascinating physicochemical properties. One major drawback of GO is its instability, which leads to the difficulties in product management. A physicochemical understanding of the ever-changing nature of GO can remove the barrier for its growing applications.

Direct Evidence of Reversible SnO-Li Reactions in Carbon Nanospaces.

We present herein that carbon nanospaces are the key reaction space to improve the reversibility of the reaction of SnO with Li-ions for lithium-ion batteries, demonstrated by both ex situ and in situ observations using high-resolution scanning transmission electron microscopy with electron energy loss spectroscopy. Conversion-type electrode materials, such as SnO, undergo large volume changes and phase separation during the charge-discharge process, which lead to degradation in the battery performance. By confining the SnO-Li reaction within carbon nanopores, the battery performance is improved.

Air-permeable redox mediated transcutaneous CO sensor.

Standard clinical care of neonates and the ventilation status of human patients affected with coronavirus disease involves continuous CO monitoring. However, existing noninvasive methods are inadequate owing to the rigidity of hard-wired devices, insubstantial gas permeability and high operating temperature. Here, we report a cost-effective transcutaneous CO sensing device comprising elastomeric sponges impregnated with oxidized single-walled carbon nanotubes (oxSWCNTs)-based composites.

Mitigation of Edge and Surface States Effects in Two-Dimensional WS for Photocatalytic H Generation.

Large scale development of the 2D transition metal di-chalcogenides (TMDC) relies on landmark improvement in performance, which could emerge from nanostructuration. Using p-WS nanoflakes with different degrees of exfoliation and fracturing, perspectives were provided to develop high-surface-area 2D p-WS films for the photocatalytic hydrogen generation. The critical role of inter-nanoflakes contacts within high-surface-area 2D films was demonstrated, highlighting the benefit of plane/plane versus edge/plane contacts.

Adsorption enhancement of nitrogen gas by atomically heterogeneous nanospace of boron nitride.

In this study, porous boron nitride (p-BN) with hexagonal phase boron nitride (h-BN) pore walls was synthesized using high-temperature calcination. Negligible variation in pore-wall structure can be observed in powder X-ray diffraction (XRD) profiles and infrared (IR) spectra. However, a highly stable p-BN with a stable pore structure even at 973 K under the oxidative conditions is obtained when synthesized at higher than 1573 K under nitrogen gas flow.

SnO-Embedded Nanoporous Carbon Electrode with a Reaction-Buffer Space for Stable All-Solid-State Li Ion Batteries.

The conventional approach for fabricating all-solid-state batteries has required a highly dense layer of electrode and electrolyte. Their close contact interface is not suitable for alloy- or conversion-based active materials because their large volume change in lithiation/delithiation reactions causes a collapse of the contact interface or reaction limitations under mechanical constriction. In this study, we propose that a SnO-embedded porous carbon electrode shows high cyclability and high capacity even at high constraint pressure owing to the nanopores, which work as a buffer space for the large volume change accompanied with SnO-Sn conversion reaction and Sn-Li alloying-dealloying reaction.

New insights into the heat of adsorption of water, acetonitrile, and n-hexane in porous carbon with oxygen functional groups.

Isosteric heat of adsorption is exquisitely sensitive to structural changes in carbon surfaces based on the energetic behavior of the interactions between adsorbates and carbon materials. We discuss the relationships between porous structures, oxygen functional groups, and heat of adsorption based on the behavior of the heat of adsorption of polar and non-polar fluids on porous carbon materials with oxygen functional groups. The porosity and functional groups of porous carbon materials were estimated from N adsorption isotherms at 77 K and temperature-programmed desorption.

High capacity and stable all-solid-state Li ion battery using SnO-embedded nanoporous carbon.

Extensive research efforts are devoted to development of high performance all-solid-state lithium ion batteries owing to their potential in not only improving safety but also achieving high stability and high capacity. However, conventional approaches based on a fabrication of highly dense electrode and solid electrolyte layers and their close contact interface is not always applicable to high capacity alloy- and/or conversion-based active materials such as SnO accompanied with large volume change in charging-discharging. The present work demonstrates that SnO-embedded nanoporous carbons without solid electrolyte inside the nanopores are a promising candidate for high capacity and stable anode material of all-solid-state battery, in which the volume change reactions are restricted in the nanopores to keep the constant electrode volume.

Nanoporosity Change on Elastic Relaxation of Partially Folded Graphene Monoliths.

Fabrication of nanographene shows a promising route for production of designed porous carbons, which is indispensable for highly efficient molecular separation and energy storage applications. This process requires a better understanding of the mechanical properties of nanographene in their aggregated structure. We studied the structural and mechanical properties of nanographene monoliths compressed at 43 MPa over different times from 3 to 25 h.

Water Adsorption Property of Hierarchically Nanoporous Detonation Nanodiamonds.

The detonation nanodiamonds form the aggregate having interparticle voids, giving a marked hygroscopic property. As the relationship between pore structure and water adsorption of aggregated nanodiamonds is not well understood yet, adsorption isotherms of N at 77 K and of water vapor at 298 K of the well-characterized aggregated nanodiamonds were measured. HR-TEM and X-ray diffraction showed that the nanodiamonds were highly crystalline and their average crystallite size was 4.

Experimental Information on the Adsorbed Phase of Water Formed in the Inner Pore of Single-Walled Carbon Nanotube Itself.

Thus far, nobody has successfully obtained the accurate information on the properties of the adsorbed phases of gases or vapors formed inside a cylindrical micropore of single-walled carbon nanotube (SWCNT) itself based on the experimental procedure. In this work, we succeeded in analyzing experimentally the properties of adsorbed nitrogen and water confined in the inner pore of SWCNT itself by opening the pore composed of close-ended SWCNT without any changes in the surface state and also by applying the unique method for characterization; both the amounts, as well as properties, of surface functional groups and the bundle structure are the same even after the treatments for introducing an open-ended structure to a close-ended one. As a result, the average pore sizes, as well as characteristic adsorption behavior, on the two types of sample were available from the analysis of respective difference adsorption isotherms of nitrogen measured at 77 K between the adsorbed amounts on the open-ended SWCNT and that on the close-ended one.

Enhanced charge-discharge properties of SnO2 nanocrystallites in confined carbon nanospace.

Almost perfect embedding of SnO2 nanocrystallites in carbon nanopores was achieved by in situ synthesis using vaporized SnCl2 and silica opal-derived nanoporous carbons. The reversibility of SnO2-Sn conversion and Sn-Li alloying/de-alloying reactions was greatly enhanced by the confinement in regulated carbon nanospace.

Enhanced electric double-layer capacitance by desolvation of lithium ions in confined nanospaces of microporous carbon.

Carbon electrodes with specific microporous structures are strongly desired to improve the performance of electric double-layer capacitors (EDLCs). We report solvated states of Li ions in confined carbon micropores affecting specific capacitance. The average Li(+) solvation number of 1 M LiClO4/propylene carbonate (PC) electrolyte introduced into porous carbon electrodes was determined using Raman spectroscopy and (7)Li NMR.

Nanospace-enhanced photoreduction for the synthesis of copper(I) oxide nanoparticles under visible-light irradiation.

Nanoparticles of copper(I) oxide (cuprous oxide; Cu2O) were able to be synthesized from nano-restricted copper acetate (Cu(OAc)2) in micropores of single-wall carbon nanotubes (SWNTs) by visible-light photoreduction. The specific structure of confined Cu(OAc)2 in the micropore is indispensable for the reduction process to Cu2O by the irradiation, because, in general, aqueous solution of Cu(OAc)2 can be reduced under UV-light irradiated conditions. The present results strongly suggest that the micropore of SWNTs whose pore width is in the micropore-size range can play as nanoreactor space for the synthesis of Cu2O through the nano-restricted precursor whose reactivity is different from that in the bulk phase.

Conducting linear chains of sulphur inside carbon nanotubes.

Despite extensive research for more than 200 years, the experimental isolation of monatomic sulphur chains, which are believed to exhibit a conducting character, has eluded scientists. Here we report the synthesis of a previously unobserved composite material of elemental sulphur, consisting of monatomic chains stabilized in the constraining volume of a carbon nanotube. This one-dimensional phase is confirmed by high-resolution transmission electron microscopy and synchrotron X-ray diffraction.

Direct synthesis of novel homogeneous nanocomposites of Li2MnSiO4 and carbon as a potential Li-ion battery cathode material.

Homogeneous nanocomposites of nanocrystalline Li2MnSiO4 and carbon as well as a carbon nanotubes-embedded nanocomposite are synthesized directly by a novel method using organic-inorganic hybrid polymers which consist of covalently bonded phenolic oligomer and siloxane parts. The nanocomposites show superior charge-discharge performance at room temperature in spite of low carbon contents.

Highly compressed nanosolution restricted in cylindrical carbon nanospaces.

We shed light on the specific hydration structure around a zinc ion of nanosolution restricted in a cylindrical micropore of single-wall carbon nanotube (SWNT) by comparison with the structure restricted in a cylindrical mesopore of multi-wall carbon nanotube (MWNT) and that of bulk aqueous solution. The average micropore width of open-pore SWNT was 0.87 nm which is equivalent to the size of a hydrated zinc ion having 6-hydrated water molecules.

Diffusion-barrier-free porous carbon monoliths as a new form of activated carbon.

For the practical use of activated carbon (AC) as an adsorbent of CH(4) , tightly packed monoliths with high microporosity are supposed to be one of the best morphologies in terms of storage capacity per apparent volume of the adsorbent material. However, monolith-type ACs may cause diffusion obstacles in adsorption processes owing to their necked pore structures among the densely packed particles, which result in a lower adsorption performance than that of the corresponding powder ACs. To clarify the relationship between the pore structure and CH₄ adsorptivity, microscopic observations, structural studies on the nanoscale, and conductivity measurements (thermal and electrical) were performed on recently developed binder-free, self-sinterable ACs in both powder and monolithic forms.

Selective probe of the morphology and local vibrations at carbon nanoasperities.

We introduce a way to selectively probe local vibration modes at nanostructured asperities such as tips of carbon nanohorns. Our observations benefit from signal amplification in surface-enhanced Raman scattering (SERS) at sites near a silver surface. We observe nanohorn tip vibration modes in the range 200-500 cm(-1), which are obscured in regular Raman spectra.

Selective D2 adsorption enhanced by the quantum sieving effect on entangled single-wall carbon nanotubes.

The quantum sieving effect of D(2) over H(2) is examined at 40 and 77 K by means of experiments and GCMC simulations, for two types of single-wall carbon nanotubes that are distinguishable by their unique entangled structures; (1) a well-bundled SWCNT and (2) loosely-assembled SWCNT produced by the super growth method (SG-SWCNT). Oxidized SWCNT samples of which the so-called internal sites are accessible for H(2) and D(2), are also studied. Experimental H(2) and D(2) adsorption properties on the well-bundled SWCNTs are compared with the simulated ones, revealing that pore-blocking and restricted diffusion of the molecules suppress the high selectivity of D(2) over H(2).

Anomaly of CH4 molecular assembly confined in single-wall carbon nanohorn spaces.

Vibrational-rotational properties of CH(4) adsorbed on the nanopores of single-wall carbon nanohorns (SWCNHs) at 105-140 K were investigated using IR spectroscopy. The difference vibrational-rotational bands of the ν(3) and ν(4) modes below 130 K show suppression of the P and R branches, while the Q branches remain. The widths of the Q branches are much narrower than in the bulk gas phase due to suppression of the Doppler effect.

Evidence of dynamic pentagon-heptagon pairs in single-wall carbon nanotubes using surface-enhanced Raman scattering.

Surface-enhanced Raman scattering (SERS) was applied to detecting pentagon-heptagon pairs, the so-called Stone-Wales defect, in single-wall carbon nanotubes (SWCNTs). When a probing laser light was scanned over a SWCNT-dispersed silver surface, two distinct SERS spectra were obtained: (1) temporally stable spectra similar to that of resonance Raman spectra of bulk SWCNTs and (2) temporally fluctuating spectra with additional peaks which were not observed in the non-SERS spectra. The fluctuations in the SERS spectra are discussed in association with dynamic reconstruction of defective structures of SWCNTs (nonhexagonal arrangements of carbon atoms) in the vicinity of SERS-active sites under irradiation of the laser light.

Effect of a quaternary ammonium salt on propylene carbonate structure in slit-shape carbon nanopores.

The effect of addition of tetraethylammonium tetrafluoroborate (Et(4)NBF(4)) on the structure of propylene carbonate (PC) confined in slit-shaped carbon nanopores of activated carbon fiber (pore width = 1.0 nm) was studied by synchrotron X-ray diffraction and reverse Monte Carlo simulation. PC molecules are randomly packed in the slit carbon nanopores of 1 nm in the absence of Et(4)NBF(4).