Showing papers by "Pulickel M. Ajayan published in 2016"

High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells

Abstract: Three-dimensional organic-inorganic perovskites have emerged as one of the most promising thin-film solar cell materials owing to their remarkable photophysical properties, which have led to power conversion efficiencies exceeding 20 per cent, with the prospect of further improvements towards the Shockley-Queisser limit for a single‐junction solar cell (33.5 per cent). Besides efficiency, another critical factor for photovoltaics and other optoelectronic applications is environmental stability and photostability under operating conditions. In contrast to their three-dimensional counterparts, Ruddlesden-Popper phases--layered two-dimensional perovskite films--have shown promising stability, but poor efficiency at only 4.73 per cent. This relatively poor efficiency is attributed to the inhibition of out-of-plane charge transport by the organic cations, which act like insulating spacing layers between the conducting inorganic slabs. Here we overcome this issue in layered perovskites by producing thin films of near-single-crystalline quality, in which the crystallographic planes of the inorganic perovskite component have a strongly preferential out-of-plane alignment with respect to the contacts in planar solar cells to facilitate efficient charge transport. We report a photovoltaic efficiency of 12.52 per cent with no hysteresis, and the devices exhibit greatly improved stability in comparison to their three-dimensional counterparts when subjected to light, humidity and heat stress tests. Unencapsulated two-dimensional perovskite devices retain over 60 per cent of their efficiency for over 2,250 hours under constant, standard (AM1.5G) illumination, and exhibit greater tolerance to 65 per cent relative humidity than do three-dimensional equivalents. When the devices are encapsulated, the layered devices do not show any degradation under constant AM1.5G illumination or humidity. We anticipate that these results will lead to the growth of single-crystalline, solution-processed, layered, hybrid, perovskite thin films, which are essential for high-performance opto-electronic devices with technologically relevant long-term stability.

Defects Engineered Monolayer MoS2 for Improved Hydrogen Evolution Reaction.

Abstract: MoS2 is a promising and low-cost material for electrochemical hydrogen production due to its high activity and stability during the reaction. However, the efficiency of hydrogen production is limited by the amount of active sites, for example, edges, in MoS2. Here, we demonstrate that oxygen plasma exposure and hydrogen treatment on pristine monolayer MoS2 could introduce more active sites via the formation of defects within the monolayer, leading to a high density of exposed edges and a significant improvement of the hydrogen evolution activity. These as-fabricated defects are characterized at the scale from macroscopic continuum to discrete atoms. Our work represents a facile method to increase the hydrogen production in electrochemical reaction of MoS2 via defect engineering, and helps to understand the catalytic properties of MoS2.

Room-temperature ferroelectricity in CuInP2S6 ultrathin flakes.

Abstract: Two-dimensional (2D) materials have emerged as promising candidates for various optoelectronic applications based on their diverse electronic properties, ranging from insulating to superconducting. However, cooperative phenomena such as ferroelectricity in the 2D limit have not been well explored. Here, we report room-temperature ferroelectricity in 2D CuInP2S6 (CIPS) with a transition temperature of ∼320 K. Switchable polarization is observed in thin CIPS of ∼4 nm. To demonstrate the potential of this 2D ferroelectric material, we prepare a van der Waals (vdW) ferroelectric diode formed by CIPS/Si heterostructure, which shows good memory behaviour with on/off ratio of ∼100. The addition of ferroelectricity to the 2D family opens up possibilities for numerous novel applications, including sensors, actuators, non-volatile memory devices, and various vdW heterostructures based on 2D ferroelectricity. Two dimensional materials are promising for electronic applications, which await the exploration of cooperative phenomena. Here, Liu et al. report switchable ferroelectric polarization in thin CuInP2S6film at room temperature, demonstrating good memory behaviour with on/off ratio of ∼100 based on two-dimensional ferroelectricity.

A metal-free electrocatalyst for carbon dioxide reduction to multi-carbon hydrocarbons and oxygenates

Abstract: Electroreduction of carbon dioxide into higher-energy liquid fuels and chemicals is a promising but challenging renewable energy conversion technology. Among the electrocatalysts screened so far for carbon dioxide reduction, which includes metals, alloys, organometallics, layered materials and carbon nanostructures, only copper exhibits selectivity towards formation of hydrocarbons and multi-carbon oxygenates at fairly high efficiencies, whereas most others favour production of carbon monoxide or formate. Here we report that nanometre-size N-doped graphene quantum dots (NGQDs) catalyse the electrochemical reduction of carbon dioxide into multi-carbon hydrocarbons and oxygenates at high Faradaic efficiencies, high current densities and low overpotentials. The NGQDs show a high total Faradaic efficiency of carbon dioxide reduction of up to 90%, with selectivity for ethylene and ethanol conversions reaching 45%. The C2 and C3 product distribution and production rate for NGQD-catalysed carbon dioxide reduction is comparable to those obtained with copper nanoparticle-based electrocatalysts.

Incorporation of Nitrogen Defects for Efficient Reduction of CO2 via Two-Electron Pathway on Three-Dimensional Graphene Foam

Abstract: The practical recycling of carbon dioxide (CO2) by the electrochemical reduction route requires an active, stable, and affordable catalyst system. Although noble metals such as gold and silver have been demonstrated to reduce CO2 into carbon monoxide (CO) efficiently, they suffer from poor durability and scarcity. Here we report three-dimensional (3D) graphene foam incorporated with nitrogen defects as a metal-free catalyst for CO2 reduction. The nitrogen-doped 3D graphene foam requires negligible onset overpotential (−0.19 V) for CO formation, and it exhibits superior activity over Au and Ag, achieving similar maximum Faradaic efficiency for CO production (∼85%) at a lower overpotential (−0.47 V) and better stability for at least 5 h. The dependence of catalytic activity on N-defect structures is unraveled by systematic experimental investigations. Indeed, the density functional theory calculations confirm pyridinic N as the most active site for CO2 reduction, consistent with experimental results.

Two-dimensional van der Waals materials

Abstract: Graphene is not the only atomically thin material of technological importance. Diverse families of newly harnessed monolayers have far-reaching implications for basic physics, materials science, and engineering.

Pyridinic-Nitrogen-Dominated Graphene Aerogels with Fe–N–C Coordination for Highly Efficient Oxygen Reduction Reaction

Abstract: Here, pyridinic nitrogen dominated graphene aerogels with/without iron incorporation (Fe-NG and NG) are prepared via a facile and effective process including freeze-drying of chemically reduced graphene oxide with/without iron precursor and thermal treatment in NH3. A high doping level of nitrogen has been achieved (up to 12.2 at% for NG and 11.3 at% for Fe-NG) with striking enrichment of pyridinic nitrogen (up to 90.4% of the total nitrogen content for NG, and 82.4% for Fe-NG). It is found that the Fe-NG catalysts display a more positive onset potential, higher current density, and better four-electron selectivity for ORR than their counterpart without iron incorporation. The most active Fe-NG exhibits outstanding ORR catalytic activity, high durability, and methanol tolerance ability that are comparable to or even superior to those of the commercial Pt/C catalyst at the same catalyst loading in alkaline environment. The excellent ORR performance can be ascribed to the synergistic effect of pyridinic N and Fe-N x sites (where iron probably coordinates with pyridinic N) that serve as active centers for ORR. Our Fe-NG can be developed into cost-effective and durable catalysts as viable replacements of the expensive Pt-based catalysts in practical fuel cell applications.

Highly Sensitive Detection of Polarized Light Using Anisotropic 2D ReS2

Abstract: Due to the novel optical and optoelectronic properties, 2D materials have received increasing interests for optoelectronics applications. Discovering new properties and functionalities of 2D materials is challenging yet promising. Here broadband polarization sensitive photodetectors based on few layer ReS2 are demonstrated. The transistor based on few layer ReS2 shows an n-type behavior with the mobility of about 40 cm2 V−1 s−1 and on/off ratio of 105. The polarization dependence of photoresponse is ascribed to the unique anisotropic in-plane crystal structure, consistent with the optical absorption anisotropy. The linear dichroic photodetection with a high photoresponsivity reported here demonstrates a route to exploit the intrinsic anisotropy of 2D materials and the possibility to open up new ways for the applications of 2D materials for light polarization detection.

Ultrafast formation of interlayer hot excitons in atomically thin MoS2/WS2 heterostructures.

Abstract: Van der Waals heterostructures composed of two-dimensional transition-metal dichalcogenides layers have recently emerged as a new family of materials, with great potential for atomically thin opto-electronic and photovoltaic applications. It is puzzling, however, that the photocurrent is yielded so efficiently in these structures, despite the apparent momentum mismatch between the intralayer/interlayer excitons during the charge transfer, as well as the tightly bound nature of the excitons in 2D geometry. Using the energy-state-resolved ultrafast visible/infrared microspectroscopy, we herein obtain unambiguous experimental evidence of the charge transfer intermediate state with excess energy, during the transition from an intralayer exciton to an interlayer exciton at the interface of a WS2/MoS2 heterostructure, and free carriers moving across the interface much faster than recombining into the intralayer excitons. The observations therefore explain how the remarkable charge transfer rate and photocurrent generation are achieved even with the aforementioned momentum mismatch and excitonic localization in 2D heterostructures and devices.

Wafer-scale monodomain films of spontaneously aligned single-walled carbon nanotubes

Abstract: The one-dimensional character of electrons, phonons and excitons in individual single-walled carbon nanotubes leads to extremely anisotropic electronic, thermal and optical properties. However, despite significant efforts to develop ways to produce large-scale architectures of aligned nanotubes, macroscopic manifestations of such properties remain limited. Here, we show that large (>cm(2)) monodomain films of aligned single-walled carbon nanotubes can be prepared using slow vacuum filtration. The produced films are globally aligned within ±1.5° (a nematic order parameter of ∼1) and are highly packed, containing 1 × 10(6) nanotubes in a cross-sectional area of 1 μm(2). The method works for nanotubes synthesized by various methods, and film thickness is controllable from a few nanometres to ∼100 nm. We use the approach to create ideal polarizers in the terahertz frequency range and, by combining the method with recently developed sorting techniques, highly aligned and chirality-enriched nanotube thin-film devices. Semiconductor-enriched devices exhibit polarized light emission and polarization-dependent photocurrent, as well as anisotropic conductivities and transistor action with high on/off ratios.

Self-optimizing layered hydrogen evolution catalyst with high basal-plane activity

Abstract: Hydrogen is a promising energy carrier and key agent for many industrial chemical processes1. One method for generating hydrogen sustainably is via the hydrogen evolution reaction (HER), in which electrochemical reduction of protons is mediated by an appropriate catalyst-traditionally, an expensive platinum-group metal. Scalable production requires catalyst alternatives that can lower materials or processing costs while retaining the highest possible activity. Strategies have included dilute alloying of Pt2 or employing less expensive transition metal alloys, compounds or heterostructures (e.g., NiMo, metal phosphides, pyrite sulfides, encapsulated metal nanoparticles)3-5. Recently, low-cost, layered transition-metal dichalcogenides (MX2)6 based on molybdenum and tungsten have attracted substantial interest as alternative HER catalysts7-11. These materials have high intrinsic per-site HER activity; however, a significant challenge is the limited density of active sites, which are concentrated at the layer edges.8,10,11. Here we use theory to unravel electronic factors underlying catalytic activity on MX2 surfaces, and leverage the understanding to report group-5 MX2 (H-TaS2 and H-NbS2) electrocatalysts whose performance instead derives from highly active basal-plane sites. Beyond excellent catalytic activity, they are found to exhibit an unusual ability to optimize their morphology for enhanced charge transfer and accessibility of active sites as the HER proceeds. This leads to long cycle life and practical advantages for scalable processing. The resulting performance is comparable to Pt and exceeds all reported MX2 candidates.

High temperature electrical energy storage: advances, challenges, and frontiers

Abstract: With the ongoing global effort to reduce greenhouse gas emission and dependence on oil, electrical energy storage (EES) devices such as Li-ion batteries and supercapacitors have become ubiquitous. Today, EES devices are entering the broader energy use arena and playing key roles in energy storage, transfer, and delivery within, for example, electric vehicles, large-scale grid storage, and sensors located in harsh environmental conditions, where performance at temperatures greater than 25 °C are required. The safety and high temperature durability are as critical or more so than other essential characteristics (e.g., capacity, energy and power density) for safe power output and long lifespan. Consequently, significant efforts are underway to design, fabricate, and evaluate EES devices along with characterization of device performance limitations such as thermal runaway and aging. Energy storage under extreme conditions is limited by the material properties of electrolytes, electrodes, and their synergetic interactions, and thus significant opportunities exist for chemical advancements and technological improvements. In this review, we present a comprehensive analysis of different applications associated with high temperature use (40–200 °C), recent advances in the development of reformulated or novel materials (including ionic liquids, solid polymer electrolytes, ceramics, and Si, LiFePO4, and LiMn2O4 electrodes) with high thermal stability, and their demonstrative use in EES devices. Finally, we present a critical overview of the limitations of current high temperature systems and evaluate the future outlook of high temperature batteries with well-controlled safety, high energy/power density, and operation over a wide temperature range.

Surface functionalization of two-dimensional metal chalcogenides by Lewis acid–base chemistry

Abstract: Precise control of the electronic surface states of two-dimensional (2D) materials could improve their versatility and widen their applicability in electronics and sensing. To this end, chemical surface functionalization has been used to adjust the electronic properties of 2D materials. So far, however, chemical functionalization has relied on lattice defects and physisorption methods that inevitably modify the topological characteristics of the atomic layers. Here we make use of the lone pair electrons found in most of 2D metal chalcogenides and report a functionalization method via a Lewis acid-base reaction that does not alter the host structure. Atomic layers of n-type InSe react with Ti(4+) to form planar p-type [Ti(4+)n(InSe)] coordination complexes. Using this strategy, we fabricate planar p-n junctions on 2D InSe with improved rectification and photovoltaic properties, without requiring heterostructure growth procedures or device fabrication processes. We also show that this functionalization approach works with other Lewis acids (such as B(3+), Al(3+) and Sn(4+)) and can be applied to other 2D materials (for example MoS2, MoSe2). Finally, we show that it is possible to use Lewis acid-base chemistry as a bridge to connect molecules to 2D atomic layers and fabricate a proof-of-principle dye-sensitized photosensing device.

Mass and Charge Transfer Coenhanced Oxygen Evolution Behaviors in CoFe‐Layered Double Hydroxide Assembled on Graphene

Abstract: The earth-abundant electrocatalysts with high activity are highly desired and required for high-efficient oxygen evolution reaction (OER). Herein, we report that 2D nanosheet-shaped cobalt–iron-layered double hydroxide (CoFe-LDH) is a highly active and stable oxygen evolution catalyst. The Fe3+ is capable of tailoring the component ranging from hydroxides to LDH and broadening the interlayer space of as-made 2D materials. Benefiting from the synergistic effects between Co and Fe species and the LDH-layered structure, the shortened ion transport distance in the nanoscale dimension, and the broader interlayer space, an enhanced mass transfer behavior for OER is demonstrated. The as-made CoFe-LDH shows high electrocatalytic activity, which is superior to those of corresponding Co(OH)2 and the mixed phase samples of Co(OH)2 and FeOOH, as well as RuO2 and commercial Pt/C catalysts. Assembling CoFe-LDH on reduced graphene oxide (rGO) to configure the 2D sheet-on-sheet binary architectures (CoFe-LDH/rGO) can further create well-interconnected conductive networks within the electrode matrix, leading to the lowest overpotential of 325 mV at 10 mA cm−2. Collectively, such integrated characteristics with alternated components will endow the as-made 2D-structured catalysts with a potential and superb superiority as low-cost earth-abundance catalysts for water oxidation.

Power from nature: designing green battery materials from electroactive quinone derivatives and organic polymers

Abstract: Current lithium ion battery technologies suffer from challenges derived from the eco-toxicity, costliness, and energetic inefficiency of contemporary inorganic materials used in these devices. Small organic molecules containing polycyclic aromatic moieties and polar functional groups have recently been presented as attractive electron donors that bind lithium and other small metal ions. This has endowed them with the potential to replace traditional inorganic electrodes consisting of metal composites. A family of naturally occurring carbonyl compounds, or quinones, have been of particular interest to the scientific community. However, they themselves have been plagued by issues of low voltages, poor conductivity, and capacity fading due to solubility in common polar electrolytes. Herein, we review a number of theoretical and experimental solutions to this problem, which include the use of heterocyclic derivatives, polymers, and conductive supramolecular carbon frameworks as electrochemical property enhancers, or stabilizers, of potential organic electrodes. This review focuses on the benign synthesis, current status, and future direction of organic battery materials with the aim of developing sustainable energy storage systems to meet the demands of a greener future.

Synthesis of Millimeter-Scale Transition Metal Dichalcogenides Single Crystals

Abstract: The emergence of semiconducting transition metal dichalcogenide (TMD) atomic layers has opened up unprecedented opportunities in atomically thin electronics. Yet the scalable growth of TMD layers with large grain sizes and uniformity has remained very challenging. Here is reported a simple, scalable chemical vapor deposition approach for the growth of MoSe2 layers is reported, in which the nucleation density can be reduced from 105 to 25 nuclei cm-2, leading to millimeter-scale MoSe2 single crystals as well as continuous macrocrystalline films with millimeter size grains. The selective growth of monolayers and multilayered MoSe2 films with well-defined stacking orientation can also be controlled via tuning the growth temperature. In addition, periodic defects, such as nanoscale triangular holes, can be engineered into these layers by controlling the growth conditions. The low density of grain boundaries in the films results in high average mobilities, around ≈42 cm2 V-1 s-1, for back-gated MoSe2 transistors. This generic synthesis approach is also demonstrated for other TMD layers such as millimeter-scale WSe2 single crystals.

CoNi2S4‐Graphene‐2D‐MoSe2 as an Advanced Electrode Material for Supercapacitors

Abstract: 3D CoNi2S4-graphene-2D-MoSe2 (CoNi2S4-G-MoSe2) nanocomposite is designed and prepared using a facile ultrasonication and hydrothermal method for supercapacitor (SC) applications. Because of the novel nanocomposite structures and resultant maximized synergistic effect among ultrathin MoSe2 nanosheets, highly conductive graphene and CoNi2S4 nanoparticles, the electrode exhibits rapid electron and ion transport rate and large electroactive surface area, resulting in its amazing electrochemical properties. The CoNi2S4-G-MoSe2 electrode demonstrates a maximum specific capacitance of 1141 F g−1, with capacitance retention of ≈108% after 2000 cycles at a high charge–discharge current density of 20 A g−1. As to its symmetric device, 109 F g−1 at a scan rate of 5 mV s−1 is exhibited. This pioneering work should be helpful in enhancing the capacitive performance of SC materials by designing nanostructures with efficient synergetic effects.

Controllable Codoping of Nitrogen and Sulfur in Graphene for Highly Efficient Li-Oxygen Batteries and Direct Methanol Fuel Cells

Abstract: Lithium–oxygen batteries (LOBs) and direct methanol fuel cells (DMFCs) are both attractive technologies for the development of future energy storage and conversion devices, while the lack of highly active electrocatalysts has largely hampered their large-scale commercial applications. In the present work, we have demonstrated the controllable synthesis of nitrogen and sulfur codoped graphene (NS-G) nanosheets via a simple and cost-effective approach. Owing to their distinctive structural advantages, such as large surface areas, good flexibility, coexistence of N and S atoms with tunable doping contents and positions, and high electrical conductivity, the obtained NS-G sheets exhibit low discharge–recharge voltage gaps and high round-trip efficiencies as well as exceptional rate capability when used as cathode materials for LOBs. Furthermore, the NS-G layers are also identified to be an ideal substrate for the decoration of ultrafine Pt nanoparticles. Benefiting from the synergetic effects, exceptional ele...

Exfoliated 2D Transition Metal Disulfides for Enhanced Electrocatalysis of Oxygen Evolution Reaction in Acidic Medium

Abstract: The scarcity of inexpensive and efficient electrocatalyst for acid water oxidation to molecular oxygen presents the development of nonprecious catalysts for water oxidation a scientific priority. For water splitting, transition-metal dichalcogenides have attracted great interest as advanced catalysts for hydrogen evolution reaction, but there has been no sincere attention to generate significant anodic current density of oxygen evolution reaction (OER) with these materials. Addressing this unmet need, here, the outstanding catalytic performance of MoS2 and TaS2 in OER is demonstrated. Chemically exfoliated 2D thin sheets of MoS2 and TaS2, in both of their 1T and 2H polymorph, have been employed for OER catalysis in acid medium. The best performance for oxygen evolution, which is also comparable to benchmark IrO2, comes out from 1T-MoS2 followed by 1T-TaS2, 2H-MoS2, and 2H-TaS2. Theoretical study reveals that the dominant catalytic activity is on edge sites instead of surface and corroborates the experimental results of polymorphic dependence of electrocatalytic activity. The materials have also shown moderate durability in the harsh acidic medium. The study brings up new set of electrocatalyst for oxygen evolution in acid regime that hitherto has remained largely unrevealed.

Surface Tension Components Based Selection of Cosolvents for Efficient Liquid Phase Exfoliation of 2D Materials.

Abstract: A proper design of direct liquid phase exfoliation (LPE) for 2D materials as graphene, MoS2 , WS2 , h-BN, Bi2 Se3 , MoSe2 , SnS2 , and TaS2 with common cosolvents is carried out based on considering the polar and dispersive components of surface tensions of various cosolvents and 2D materials. It has been found that the exfoliation efficiency is enhanced by matching the ratio of surface tension components of cosolvents to that of the targeted 2D materials, based on which common cosolvents composed of IPA/water, THF/water, and acetone/water can be designed for sufficient LPE process. In this context, the library of low-toxic and low-cost solvents with low boiling points for LPE is infinitely enlarged when extending to common cosolvents. Polymer-based composites reinforced with a series of different 2D materials are compared with each other. It is demonstrated that the incorporation of cosolvents-exfoliated 2D materials can substantially improve the mechanical and thermal properties of polymer matrices. Typically, with the addition of 0.5 wt% of such 2D material as MoS2 nanosheets, the tensile strength and Young's modulus increased up to 74.85% and 136.97%, respectively. The different enhancement effect of 2D materials is corresponded to the intrinsic properties and LPE capacity of 2D materials.

Bridging of Ultrathin NiCo2O4 Nanosheets and Graphene with Polyaniline: A Theoretical and Experimental Study

Abstract: Ultrathin inorganic nanosheets that enable fast electrochemical reaction kinetics are highly required in many energy-related applications. Herein, we report a simple strategy for in situ assembly of ultrathin NiCo2O4 nanosheets with enriched surface active sites on graphene surface in a vertical orientation way by employing polyaniline (PANI) as the structure coupling bridge between the two components (denoted by NiCo2O4–P-G). The as-made ultrathin NiCo2O4 nanosheets are rich in metal ions in high valence state and oxygen defective sites, and feature 3D open frameworks with hierarchical pore structure. It has been found that the nitrogen species derived from PANI building blocks as bridging sites tend to bond with metal ions, which effectively tune the electronic structural states and result in strong coupling effects with the NiCo2O4 nanosheets. Benefiting from these structural characteristics, the as-made NiCo2O4–P-G hybrids, when used as pseudocapacitive electrode materials, can deliver a high specific...

Strain-Induced Electronic Structure Changes in Stacked van der Waals Heterostructures.

Abstract: Vertically stacked van der Waals heterostructures composed of compositionally different two-dimensional atomic layers give rise to interesting properties due to substantial interactions between the layers. However, these interactions can be easily obscured by the twisting of atomic layers or cross-contamination introduced by transfer processes, rendering their experimental demonstration challenging. Here, we explore the electronic structure and its strain dependence of stacked MoSe2/WSe2 heterostructures directly synthesized by chemical vapor deposition, which unambiguously reveal strong electronic coupling between the atomic layers. The direct and indirect band gaps (1.48 and 1.28 eV) of the heterostructures are measured to be lower than the band gaps of individual MoSe2 (1.50 eV) and WSe2 (1.60 eV) layers. Photoluminescence measurements further show that both the direct and indirect band gaps undergo redshifts with applied tensile strain to the heterostructures, with the change of the indirect gap being...

Hexagonal Boron Nitride‐Based Electrolyte Composite for Li‐Ion Battery Operation from Room Temperature to 150 °C

Abstract: Batteries for high temperature applications capable of withstanding over 60 °C are still dominated by primary cells. Conventional rechargeable energy storage technologies which have exceptional performance at ambient temperatures employ volatile electrolytes and soft separators, resulting in catastrophic failure under heat. A composite electrolyte/separator is reported that holds the key to extend the capability of Li-ion batteries to high temperatures. A stoichiometric mixture of hexagonal boron nitride, piperidinium-based ionic liquid, and a lithium salt is formulated, with ionic conductivity reaching 3 mS cm−1, electrochemical stability up to 5 V and extended thermal stability. The composite is used in combination with conventional electrodes and demonstrates to be stable for over 600 cycles at 120 °C, with a total capacity fade of less than 3%. The ease of formulation along with superior thermal and electrochemical stability of this system extends the use of Li-ion chemistries to applications beyond consumer electronics and electric vehicles.

Tuning the Electrochemical Reactivity of Boron- and Nitrogen-Substituted Graphene

Abstract: The structural modification of nanomaterials at the atomic level has the potential to generate tailor-made components with enhanced performance for a variety of tasks. The chemical versatility of graphene has been constantly employed to fabricate multi-functional doped 2D materials with applications encompassing energy storage and electrocatalysis. Despite the many reports on boron- and nitrogen-doped graphenes, the possible synergy that arises from combining these electronically complementary elements has yet to be fully understood and explored. The techniques used for the fabrication of these nanomaterials are reviewed, along with the most recent reports on the benefits of B, N singly doping and co-doping in the electrocatalysis for oxygen reduction reactions and for energy storage in supercapacitors and lithium secondary batteries. The investigation of bulk co-doped materials has intrinsic limitations in fully understanding the real role of heteroatoms in the above applications. Ultimately, the design and creation of substituted monolayers with controlled compositions might hold the key for carbon-based energy-related applications.

Alloyed 2D Metal-Semiconductor Atomic Layer Junctions.

Abstract: Heterostructures of compositionally and electronically variant two-dimensional (2D) atomic layers are viable building blocks for ultrathin optoelectronic devices. We show that the composition of interfacial transition region between semiconducting WSe2 atomic layer channels and metallic NbSe2 contact layers can be engineered through interfacial doping with Nb atoms. WxNb1–xSe2 interfacial regions considerably lower the potential barrier height of the junction, significantly improving the performance of the corresponding WSe2-based field-effect transistor devices. The creation of such alloyed 2D junctions between dissimilar atomic layer domains could be the most important factor in controlling the electronic properties of 2D junctions and the design and fabrication of 2D atomic layer devices.

Electromechanically Responsive Liquid Crystal Elastomer Nanocomposites for Active Cell Culture

Abstract: Liquid crystal elastomers (LCEs) are unique among shape-responsive materials in that they exhibit large and reversible shape changes and can respond to a variety of stimuli. However, only a handful of studies have explored LCEs for biomedical applications. Here, we demonstrate that LCE nanocomposites (LCE-NCs) exhibit a fast and reversible electromechanical response and can be employed as dynamic substrates for cell culture. A two-step method for preparing conductive LCE-NCs is described, which produces materials that exhibit rapid (response times as fast at 0.6 s), large-amplitude (contraction by up to 30%), and fully reversible shape changes (stable to over 5000 cycles) under externally applied voltages (5–40 V). The electromechanical response of the LCE-NCs is tunable through variation of the electrical potential and LCE-NC composition. We utilize conductive LCE-NCs as responsive substrates to culture neonatal rat ventricular myocytes (NRVM) and find that NRVM remain viable on both stimulated and stati...