Processing of Composite Electrodes of Carbon Nanotube Fabrics and Inorganic Matrices via Rapid Joule Heating.

Composites of nanocarbon network structures are interesting materials, combining mechanical properties and electrical conductivity superior to those of granular systems. Hence, they are envisaged to have applications as electrodes for energy storage and transfer. Here, we show a new processing route using Joule heating for a nanostructured network composite of carbon nanotube (CNT) fabrics and an inorganic phase (namely, MoS2), and then study the resulting structure and properties. To this end, first, a unidirectional fabric of conductive CNT bundles is electrochemically coated with MoS2. Afterward, the conformally coated inorganic phase is crystallized via heat generated by direct current passing through the CNT ensemble. The Joule heating process is rapid (maximum heating rate up to 31.7 °C/s), enables accurate temperature control, and takes only a few minutes. The resulting composite material combines a high electrical conductivity of up to 1.72 (±0.25) × 105 S/m, tensile modulus as high as 8.82 ± 5.5 GPa/SG, and an axial tensile strength up to 200 ± 58 MPa/SG. Both electrical and mechanical properties are orders of magnitude above those of wet-processed nanocomposites of similar composition. The extraordinary longitudinal properties stem from the network of interconnected and highly aligned CNT bundles. Conductivity and modulus follow approximately a rule of mixtures, similar to a continuous fiber composite, whereas strength scales almost quadratically with the mass fraction of the inorganic phase due to the inorganic constraining realignment of CNTs upon stretching. This processing route is applicable to a wide range of nanocarbon-based composites with inorganic phases, leading to composites with specific strength above steel and electrical conductivity beyond the threshold for electronic limitations in battery electrodes.

Transparent and flexible high-power supercapacitors based on carbon nanotube fibre aerogels.

In this work, we report the fabrication of continuous transparent and flexible supercapacitors by depositing a CNT network onto a polymer electrolyte membrane directly from an aerogel of ultra-long CNTs produced floating in the gas phase. The supercapacitors show a combination of a power density of 1370 kW kg-1 at high transmittance (ca. 70%), and high electrochemical stability during extended cycling (>94% capacitance retention over 20 000 cycles) and against repeated 180° flexural deformation. They represent a significant enhancement of 1-3 orders of magnitude compared to prior state-of-the-art transparent supercapacitors based on graphene, CNTs, and rGO. These features mainly arise from the exceptionally long length of CNTs, which makes the material behave as a bulk conductor instead of an aspect ratio-limited percolating network, even for electrodes with >90% transparency. The electrical and capacitive figures-of-merit for the transparent conductor are FoMe = 2.7, and FoMc = 0.46 F S-1 cm-2 respectively.

Origin of the electrocatalytic activity in carbon nanotube fiber counter-electrodes for solar-energy conversion.

Carbon nanotubes are a versatile platform to develop sustainable and stable electrodes for energy-related applications. However, their electrocatalytic activity is still poorly understood. This work deciphers the origin of the catalytic activity of counter-electrodes (CEs)/current collectors made of self-standing carbon nanotube fibers (CNTfs) using Co2+/Co3+ redox couple electrolytes. This is based on comprehensive electrochemical and spectroscopic characterization of fresh and used electrodes applied to symmetric electrochemical cells using platinum-based CEs as a reference. As the most relevant findings, two straight relationships were established: (i) the limiting current and stability increase rapidly with the surface concentration of oxygen-containing functional groups, and (ii) the catalytic potential is inversely related to the amount of residual metallic Fe catalyst nanoparticles interspersed in the CNTf network. Finally, the fine tuning of the metal nanoparticle content and the degree of functionalization enabled fabrication of efficient and stable dye-sensitized solar cells with cobalt electrolytes and CNTf-CEs outperforming those with reference Pt-CEs.

Self-immobilized Pd nanowires as an excellent platform for a continuous flow reactor: efficiency, stability and regeneration.

Despite extensive use of Pd nanocrystals as catalysts, the realization of a Pd-based continuous flow reactor remains a challenge. Difficulties arise due to ill-defined anchoring of the nanocrystals on a substrate and reactivity of the substrate under different reaction conditions. We demonstrate the first metal (Pd) nanowire-based catalytic flow reactor that can be used across different filtration platforms, wherein, reactants flow through a porous network of nanowires (10-1000 nm pore sizes) and the product can be collected as filtrate. Controlling the growth parameters and obtaining high aspect ratio of the nanowires (diameter = ∼13 nm and length > 8000 nm) is necessary for successful fabrication of this flow reactor. The reactor performance is similar to a conventional reactor, but without requiring energy-expensive mechanical stirring. Synchrotron-based EXAFS studies were used to examine the catalyst microstructure and Operando FT-IR spectroscopic studies were used to devise a regenerative strategy. We show that after prolonged use, the catalyst performance can be regenerated up to 99% by a simple wash-off process without disturbing the catalyst bed. Thus, collection, regeneration and redispersion processes of the catalyst in conventional industrial reactors can be avoided. Another important advantage is avoiding specific catalyst-anchoring substrates, which are not only expensive, but also non-universal in nature.

Emerging Materials in Heterogeneous Electrocatalysis Involving Oxygen for Energy Harvesting.

Water-based renewable energy cycle involved in water splitting, fuel cells, and metal-air batteries has been gaining increasing attention for sustainable generation and storage of energy. The major challenges in these technologies arise due to the poor kinetics of the oxygen reduction reaction (ORR) and the oxygen evolution reactions (OER), besides the high cost of the catalysts. Attempts to address these issues have led to the development of many novel and inexpensive catalysts as well as newer mechanistic insights, particularly so in the last three-four years when more catalysts have been investigated than ever before. With the growing emphasis on bifunctionality, that is, materials that can facilitate both reduction and evolution of oxygen, this review is intended to discuss all major families of ORR, OER, and bifunctional catalysts such as metals, alloys, oxides, other chalcogenides, pnictides, and metal-free materials developed during this period in a single platform, while also directing the readers to specific and detailed review articles dealing with each family. In addition, each section highlights the latest theoretical and experimental insights that may further improve ORR/OER performances. The bifunctional catalysts being sufficiently new, no consensus appears to have emerged about the efficiencies. Therefore, a statistical analysis of their performances by considering nearly all literature reports that have appeared in this period is presented. The current challenges in rational design of these catalysts as well as probable strategies to improve their performances are presented.

Wound Healing and Bone Regeneration in Postextraction Sockets with and without Platelet-rich Fibrin.

CONTEXT AND AIM: In today's world of advanced dentistry, there are various aspects of restorative, esthetic, and surgical processes. Healing of an extraction socket comprises of bone as well as soft-tissue remodeling with maximum dimensional changes occurring during the first 3 months. Platelet-rich fibrin (PRF) was first developed in France as a therapeutic alternative to platelet-rich plasma to overcome many of its limitations. The present study was planned to evaluate and compare wound healing and bone regeneration in extraction sockets with and without PRF. MATERIALS AND METHODS: The present study was carried out on 30 patients selected from the outpatient department over a period of 2½ years starting from May 2013 undergoing extraction of maxillary or mandibular teeth simultaneously to conduct a split-mouth study. The research protocol was approved by the Institutional Ethics Committee governing the use of human subjects in clinical experimentation. STATISTICAL ANALYSIS USED: Descriptive and analytical statistics were calculated using Statistical Package for Social Sciences version 19. Chi-square test was used to assess wound healing score in the two groups while paired t-test was used to compare the bone density in the socket and periapical regions at different time intervals, and unpaired t-test was used for the intergroup comparisons. P < 0.05 was considered to be significant while P < 0.001 was considered highly significant. RESULTS: Patients in PRF group had better healing index when compared to without PRF group. Use of PRF showed a comparable increase in bone density too. CONCLUSION: An appreciable wound healing and bone regeneration was seen in the experimental group when compared to the control sites where no PRF was used substantiating the use of PRF as an inexpensive autologous material for socket preservation and future rehabilitation. The present study, also, showed that minimal operator expertise was required to conduct the procedure of PRF preparation and grafting when compared to bone harvesting from distant sites. The shorter duration between extractions and further rehabilitation obviates the need for a second procedure.

Pd-Pt alloys nanowires as support-less electrocatalyst with high synergistic enhancement in efficiency for methanol oxidation in acidic medium.

In a facile approach, Pd73Pt27 alloy nanowires (NWs) with large aspect ratios were synthesized in high yield by using sacrificial templates. Unlike majority of processes, our synthesis was carried out in aqueous solution with no intermittent separating stages for the products, while maintaining the NW morphology up to ∼30% of Pt. Upon evaporation of their dispersion, the NWs transform into a stable porous membrane due to self-entanglement and can be directly lifted and employed for electrocatalytic applications without external catalyst supports. We show that the NW membranes exhibit efficient electrocatalytic performance for methanol oxidation reaction (MOR) with 10 times higher mass activity and 4.4 times higher specific activity in acidic media as compared to commercial Pt catalysts. The membrane electrocatalysts is robust and exhibited very good stability with retention of ∼70% mass-activity after 4000 potential cycles. Since Pd was found to be inert towards MOR in acidic medium, our investigation provides a direct estimate of synergistic enhancement of efficiency. Over 10 times increment of mass activity appears to be significantly higher than previous investigations in various other reaction media.

Mechanochemical Synthesis of Free-Standing Platinum Nanosheets and Their Electrocatalytic Properties.

Robust, 26 nm thick free-standing platinum nanosheets, an extremely rare morphology for metal nanostructures, are obtained by employing fluid induced shearing force of the order of 1.8 N and differential shear-stress of 0.5 kPa across the diameter of a Te template nanorod undergoing galvanic displacement by Pt4+ . Corrugation leads to their large surface area and much improved electrocatalytic properties when compared with conventional Pt catalysts.

High-yield synthesis of sub-10 nm Pt nanotetrahedra with bare ⟨111⟩ facets for efficient electrocatalytic applications.

Unlike other shapes, the design of tetrahedral Pt nanocrystals (Pt-NTd), which have the largest number of Pt(111) surface atoms and highest catalytic activities toward the electron transfer reactions, has widely been considered a synthetic challenge due to their thermodynamic instability. Here, we show that, by inducing their nucleation on functionalized carbon, Pt NTds can be obtained with tunable sizes and high yields. The carbon support anchors the nanocrystals early and prevents their oriented attachment leading to nanowire formation. Therein, an in situ generated amine is crucial for stabilization of Pt-NTds, which can later be removed to expose the Pt(111) facets for higher catalytic efficiency. The bare nanocrystals exhibit much improved stability and electrocatalytic activity characteristic of Pt(111) toward oxygen reduction reaction (ORR) and methanol and formic acid oxidation reactions. For example, ∼90% of their activity was retained after 5000 potential cycles, while the ORR onset potential was recorded to be very high, 1.01 V vs reversible hydrogen electrode (RHE).

N- and S-doped high surface area carbon derived from soya chunks as scalable and efficient electrocatalysts for oxygen reduction.

Highly stable, cost-effective electrocatalysts facilitating oxygen reduction are crucial for the commercialization of membrane-based fuel cell and battery technologies. Herein, we demonstrate that protein-rich soya chunks with a high content of N, S and P atoms are an excellent precursor for heteroatom-doped highly graphitized carbon materials. The materials are nanoporous, with a surface area exceeding 1000 m2 g-1, and they are tunable in doping quantities. These materials exhibit highly efficient catalytic performance toward oxygen reduction reaction (ORR) with an onset potential of -0.045 V and a half-wave potential of -0.211 V (versus a saturated calomel electrode) in a basic medium, which is comparable to commercial Pt catalysts and is better than other recently developed metal-free carbon-based catalysts. These exhibit complete methanol tolerance and a performance degradation of merely ∼5% as compared to ∼14% for a commercial Pt/C catalyst after continuous use for 3000 s at the highest reduction current. We found that the fraction of graphitic N increases at a higher graphitization temperature, leading to the near complete reduction of oxygen. It is believed that due to the easy availability of the precursor and the possibility of genetic engineering to homogeneously control the heteroatom distribution, the synthetic strategy is easily scalable, with further improvement in performance.

C60 -mediated molecular shape sorting: separation and purification of geometrical isomers.

A supramolecular crystallization-based approach has been developed for the shape-dependent separation of geometrical isomers under near-ambient conditions. Difficulties to separate such isomers arise because of their very similar physical properties. The present approach relies on the ability of C60 to preferentially form solvate crystals with molecules of a specific geometry. Subsequently, these molecules are released upon mild heating to regenerate pure C60 . By taking isomers of xylene and trimethylbenzene (TMB) as examples, we show that one of the isomers can be extracted from the rest with very high purity. To separate TMB isomers, a new C60 -1,3,5-TMB solvate was developed, which led to the isolation of isomer purities greater than 99.6 %. Versatility, a low operating temperature of approximately 100 °C, a separation efficiency of more than 10 weight % of C60 per cycle, and reagent recyclability makes this a promising molecular shape-sorting approach.