Oxidation promoted osmotic energy conversion in black phosphorus membranes.

Two-dimensional (2D) nanofluidic ion transporting membranes show great promise in harvesting the "blue" osmotic energy between river water and sea water. Black phosphorus (BP), an emerging layered material, has recently been explored for a wide range of ambient applications. However, little attention has been paid to the extraction of the worldwide osmotic energy, despite its large potential as an energy conversion membrane. Here, we report an experimental investigation of BP membrane in osmotic energy conversion and reveal how the oxidation of BP influences power generation. Through controllable oxidation in water, power output of the BP membrane can be largely enhanced, which can be attributed to the generated charged phosphorus compounds. Depending on the valence of oxidized BP that is associated with oxygen concentration, the power density can be precisely controlled and substantially promoted by ∼220% to 1.6 W/m2 (compared with the pristine BP membrane). Moreover, through constructing a heterostructure with graphene oxide, ion selectivity of the BP membrane increases by ∼80%, contributing to enhanced charge separation efficiency and thus improved performance of ∼4.7 W/m2 that outperforms most of the state-of-the-art 2D nanofluidic membranes.

Ambient-Stable Two-Dimensional Titanium Carbide (MXene) Enabled by Iodine Etching.

MXene (e.g., Ti3 C2 ) represents an important class of two-dimensional (2D) materials owing to its unique metallic conductivity and tunable surface chemistry. However, the mainstream synthetic methods rely on the chemical etching of MAX powders (e.g., Ti3 AlC2 ) using hazardous HF or alike, leading to MXene sheets with fluorine termination and poor ambient stability in colloidal dispersions. Here, we demonstrate a fluoride-free, iodine (I2 ) assisted etching route for preparing 2D MXene (Ti3 C2 Tx , T=O, OH) with oxygen-rich terminal groups and intact lattice structure. More than 71 % of sheets are thinner than 5 nm with an average size of 1.8 µm. They present excellent thin-film conductivity of 1250 S cm-1 and great ambient stability in water for at least 2 weeks. 2D MXene sheets with abundant oxygen surface groups are excellent electrode materials for supercapacitors, delivering a high gravimetric capacitance of 293 F g-1 at a scan rate of 1 mV s-1 , superior to those made from fluoride-based etchants (<290 F g-1 at 1 mV s-1 ). Our strategy provides a promising pathway for the facile and sustainable production of highly stable MXene materials.

Electrochemically Exfoliated High-Quality 2H-MoS2 for Multiflake Thin Film Flexible Biosensors.

2D molybdenum disulfide (MoS2 ) gives a new inspiration for the field of nanoelectronics, photovoltaics, and sensorics. However, the most common processing technology, e.g., liquid-phase based scalable exfoliation used for device fabrication, leads to the number of shortcomings that impede their large area production and integration. Major challenges are associated with the small size and low concentration of MoS2 flakes, as well as insufficient control over their physical properties, e.g., internal heterogeneity of the metallic and semiconducting phases. Here it is demonstrated that large semiconducting MoS2 sheets (with dimensions up to 50 µm) can be obtained by a facile cathodic exfoliation approach in nonaqueous electrolyte. The synthetic process avoids surface oxidation thus preserving the MoS2 sheets with intact crystalline structure. It is further demonstrated at the proof-of-concept level, a solution-processed large area (60 × 60 µm) flexible Ebola biosensor, based on a MoS2 thin film (6 µm thickness) fabricated via restacking of the multiple flakes on the polyimide substrate. The experimental results reveal a low detection limit (in femtomolar-picomolar range) of the fabricated sensor devices. The presented exfoliation method opens up new opportunities for fabrication of large arrays of multifunctional biomedical devices based on novel 2D materials.

Fluoride-Free Synthesis of Two-Dimensional Titanium Carbide (MXene) Using A Binary Aqueous System.

Two-dimensional (2D) titanium carbide (Ti3 C2 ) is emerging as an important member of the MXene family. However, fluoride-based synthetic procedures remain an impediment to the practical applications of this promising class of materials. Here we demonstrate an efficient fluoride-free etching method based on the anodic corrosion of titanium aluminium carbide (Ti3 AlC2 ) in a binary aqueous electrolyte. The dissolution of aluminium followed by in situ intercalation of ammonium hydroxide results in the extraction of carbide flakes (Ti3 C2 Tx , T=O, OH) with sizes up to 18.6 µm and high yield (over 90 %) of mono- and bilayers. All-solid-state supercapacitor based on exfoliated sheets exhibits high areal and volumetric capacitances of 220 mF cm-2 and 439 F cm-3 , respectively, at a scan rate of 10 mV s-1 , superior to those of LiF/HCl-etched MXenes. Our strategy paves a safe way to the scalable synthesis and application of MXene materials.

A Delamination Strategy for Thinly Layered Defect-Free High-Mobility Black Phosphorus Flakes.

Extraordinary electronic and photonic features render black phosphorus (BP) an important material for the development of novel electronics and optoelectronics. Despite recent progress in the preparation of thinly layered BP flakes, scalable synthesis of large-size, pristine BP flakes remains a major challenge. An electrochemical delamination strategy is demonstrated that involves intercalation of diverse cations in non-aqueous electrolytes, thereby peeling off bulk BP crystals into defect-free flakes comprising only a few layers. The interplay between tetra-n-butylammonium cations and bisulfate anions promotes a high exfoliation yield up to 78 % and large BP flakes up to 20.6 µm. Bottom-gate and bottom-contact field-effect transistors, comprising single BP flakes only a few layers thick, exhibit a high hole mobility of 252±18 cm2 V-1 s-1 and a remarkable on/off ratio of (1.2±0.15)×105 at 143 K under vacuum. This efficient and scalable delamination method holds great promise for development of BP-based composites and optoelectronic devices.

Ultrafast Delamination of Graphite into High-Quality Graphene Using Alternating Currents.

To bridge the gap between laboratory-scale studies and commercial applications, mass production of high quality graphene is essential. A scalable exfoliation strategy towards the production of graphene sheets is presented that has excellent yield (ca. 75 %, 1-3 layers), low defect density (a C/O ratio of 21.2), great solution-processability, and outstanding electronic properties (a hole mobility of 430 cm2 V-1 s-1 ). By applying alternating currents, dual exfoliation at both graphite electrodes enables a high production rate exceeding 20 g h-1 in laboratory tests. As a cathode material for lithium storage, graphene-wrapped LiFePO4 particles deliver a high capacity of 167 mAh g-1 at 1 C rate after 500 cycles.

Nanoporous and highly active silicon carbide supported CeO2-catalysts for the methane oxidation reaction.

CeOx @SiO2 nanoparticles are used for the first time for the generation of porous SiC materials with tailored pore diameter in the mesopore range containing encapsulated and catalytically active CeO2 nanoparticles. The nanocasting approach with a preceramic polymer and subsequent pyrolysis is performed at 1300 °C, selective leaching of the siliceous part results in CeOx /SiC catalysts with remarkable characteristics like monodisperse, spherical pores and specific surface areas of up to 438 m(2) ·g(-1) . Porous SiC materials are promising supports for high temperature applications. The catalysts show excellent activities in the oxidation of methane with onset temperatures of the reaction 270 K below the onset of the homogeneous reaction. The synthesis scheme using core-shell particles is suited to functionalize silicon carbide with a high degree of stabilization of the active nanoparticles against sintering in the core of the template even at pyrolysis temperatures of 1300 °C rendering the novel synthesis principle as an attractive approach for a wide range of catalytic reactions.

Graphene Coating of Nafion Membranes for Enhanced Fuel Cell Performance.

Electrochemically exfoliated graphene (e-G) thin films on Nafion membranes exhibit a selective barrier effect against undesirable fuel crossover. This approach combines the high proton conductivity of state-of-the-art Nafion and the ability of e-G layers to effectively block the transport of methanol and hydrogen. Nafion membranes are coated with aqueous dispersions of e-G on the anode side, making use of a facile and scalable spray process. Scanning transmission electron microscopy and electron energy-loss spectroscopy confirm the formation of a dense percolated graphene flake network, which acts as a diffusion barrier. The maximum power density in direct methanol fuel cell (DMFC) operation with e-G-coated Nafion N115 is 3.9 times higher than that of the Nafion N115 reference (39 vs 10 mW cm-2@0.3 V) at a 5M methanol feed concentration. This suggests the application of e-G-coated Nafion membranes for portable DMFCs, where the use of highly concentrated methanol is desirable.

Scalable one-step production of electrochemically exfoliated graphene decorated with transition metal oxides for high-performance supercapacitors.

Graphene and related materials have been widely studied due to their superior properties in a wide range of applications. However, large-scale production remains a critical challenge to enable commercial acceptance. Here, we present a facile, scalable, one-step electrochemical method for producing hybrid transition metal oxide (V, Fe, Ti, or Mn)/graphene materials (TMO-EGs) as active materials for supercapacitors. Therein, we have designed and developed a continuous flow reactor with a high production rate (>4 g h-1) of TMO-EGs, where the TMO accounts for 36 weight%. TMO-EG flakes demonstrate a moderate lateral size of up to 5 µm and a specific surface area of 64 m2 g-1. Notably, TMO-EGs present a capacitance of up to 188 F g-1 as single electrodes in 4 M LiCl. The most promising material, MnOx-EG, has been used for the large-scale production of thin-film supercapacitor devices (40 × 40 × 0.25 mm) in a commercial pilot line. Using 1 M Na2SO4 as the electrolyte, the as-fabricated devices deliver a capacitance of 52 mF cm-2, with 83% capacitance retention after 6000 charge-discharge cycles, comparable to recent reports of similar devices. The simplicity, scalability, and versatility of our method are highly promising to promote the commercial applications of graphene-based materials and can be further developed for the upscalable production of other 2D materials, such as transition metal dichalcogenides and MXenes.

Monitoring adsorption-induced switching by (129)Xe NMR spectroscopy in a new metal-organic framework Ni(2)(2,6-ndc)(2)(dabco).

The synthesis and structure of a new flexible metal-organic framework Ni(2)(2,6-ndc)(2)(dabco) (DUT-8(Ni), DUT = Dresden University of Technology, 2,6-ndc = 2,6-naphthalenedicarboxylate, dabco = 1,4-diazabicyclo[2.2.2]octane) as well as its characterization by gas adsorption and (129)Xe NMR spectroscopy is described. The compound shows reversible structural transformation without loss of crystallinity upon solvent removal and physisorption of several gases. Xenon adsorption studies combined with (129)Xe NMR spectroscopy turn out to be favorable methods for the detection and characterization of the so-called "gate-pressure" effect in this novel MOF material. The linewidth and chemical shift of the (129)Xe NMR signal are shown to be very sensitive parameters for the detection of this structural transition from a narrow pore system with low porosity to a wide pore state. The transition and threshold temperature is clearly detected.

Ultrafast Electrochemical Synthesis of Defect-Free In2 Se3 Flakes for Large-Area Optoelectronics.

Because of its thickness-dependent direct bandgap and exceptional optoelectronic properties, indium(III) selenide (In2 Se3 ) has emerged as an important semiconductor for electronics and optoelectronics. However, the scalable synthesis of defect-free In2 Se3 flakes remains a significant barrier for its practical applications. Here, a facile electrochemical strategy is presented for the ultrafast delamination of bulk layered In2 Se3 crystals in nonaqueous media, resulting in high-yield (83%) production of defect-free In2 Se3 flakes with large lateral size (up to 26 µm). The intercalation of tetrahexylammonium (THA+ ) ions mainly creates stage-3 intercalated compounds in which every three layers of In2 Se3 are occupied by one layer of THA molecules. The subsequent exfoliation leads to a majority of trilayer In2 Se3 nanosheets. As a proof of concept, solution-processed, large-area (400 µm × 20 µm) thin-film photodetectors embedded with the exfoliated In2 Se3 flakes reveal ultrafast response time with a rise and decay of 41 and 39 ms, respectively, and efficient responsivity (1 mA W-1 ). Such performance surpasses most of the state-of-the-art thin-film photodetectors based on transition metal dichalcogenides.

Wetting Properties of Graphene Aerogels.

Graphene hydrophobic coatings paved the way towards a new generation of optoelectronic and fluidic devices. Nevertheless, such hydrophobic thin films rely only on graphene non-polar surface, rather than taking advantage of its surface roughness. Furthermore, graphene is typically not self-standing. Differently, carbon aerogels have high porosity, large effective surface area due to their surface roughness, and very low mass density, which make them a promising candidate as a super-hydrophobic material for novel technological applications. However, despite a few works reporting the general super-hydrophobic and lipophilic behavior of the carbon aerogels, a detailed characterization of their wetting properties is still missing, to date. Here, the wetting properties of graphene aerogels are demonstrated in detail. Without any chemical functionalization or patterning of their surface, the samples exhibit a super-lipophilic state and a stationary super-hydrophobic state with a contact angle up to 150 ± 15° and low contact angle hysteresis  ≈ 15°, owing to the fakir effect. In addition, the adhesion force of the graphene aerogels in contact with the water droplets and their surface tension are evaluated. For instance, the unique wettability and enhanced liquid absorption of the graphene aerogels can be exploited for reducing contamination from oil spills and chemical leakage accidents.

Glial cell responses on tetrapod-shaped graphene oxide and reduced graphene oxide 3D scaffolds in brain in vitro and ex vivo models of indirect contact.

Brain implants are promising instruments for a broad variety of nervous tissue diseases with a wide range of applications, e.g. for stimulation, signal recording or local drug delivery. Recently, graphene-based scaffold materials have emerged as attractive candidates as neural interfaces, 3D scaffolds, or drug delivery systems due to their excellent properties like flexibility, high surface area, conductivity, and lightweight. To date, however, there is a lack of appropriate studies of the foreign body response, especially by glial cells, towards graphene-based materials. In this work, we investigated the effects of macroscopic, highly porous (>99.9%) graphene oxide (GO) and reduced graphene oxide (rGO) (conductivity ∼1 S m-1) scaffolds with tailorable macro- and microstructure on human astrocyte and microglial cell viability and proliferation as well as expression of neuroinflammation and astrogliosis associated genes in an indirect contact approach. In this in vitro model, as well as ex vivo in organotypic murine brain slices, we could demonstrate that both GO and rGO based 3D scaffolds exert slight effects on the glial cell populations which are the key players of glial scar formation. These effects were in most cases completely abolished by curcumin, a known anti-inflammatory and anti-fibrotic drug that could in perspective be applied to brain implants as a protectant.

Wet-Chemical Assembly of 2D Nanomaterials into Lightweight, Microtube-Shaped, and Macroscopic 3D Networks.

Despite tremendous efforts toward fabrication of three-dimensional macrostructures of two-dimensional (2D) materials, the existing approaches still lack sufficient control over microscopic (morphology, porosity, pore size) and macroscopic (shape, size) properties of the resulting structures. In this work, a facile fabrication method for the wet-chemical assembly of carbon 2D nanomaterials into macroscopic networks of interconnected, hollow microtubes is introduced. As demonstrated for electrochemically exfoliated graphene, graphene oxide, and reduced graphene oxide, the approach allows for the preparation of highly porous (> 99.9%) and lightweight (<2 mg cm-3) aeromaterials with tailored porosity and pore size as well as tailorable shape and size. The unique tubelike morphology with high aspect ratio enables ultralow-percolation-threshold graphene composites (0.03 S m-1, 0.05 vol%) which even outperform most of the carbon nanotube-based composites, as well as highly conductive aeronetworks (8 S m-1, 4 mg cm-3). On top of that, long-term compression cycling of the aeronetworks demonstrates remarkable mechanical stability over 10 000 cycles, even though no chemical cross-linking is employed. The developed strategy could pave the way for fabrication of various macrostructures of 2D nanomaterials with defined shape, size, as well as micro- and nanostructure, crucial for numerous applications such as batteries, supercapacitors, and filters.

Scalable Fabrication and Integration of Graphene Microsupercapacitors through Full Inkjet Printing.

A simple full-inkjet-printing technique is developed for the scalable fabrication of graphene-based microsupercapacitors (MSCs) on various substrates. High-performance graphene inks are formulated by integrating the electrochemically exfoliated graphene with a solvent exchange technique to reliably print graphene interdigitated electrodes with tunable geometry and thickness. Along with the printed polyelectrolyte, poly(4-styrenesulfonic acid), the fully printed graphene-based MSCs attain the highest areal capacitance of ∼0.7 mF/cm2, substantially advancing the state-of-art of all-solid-state MSCs with printed graphene electrodes. The full printing solution enables scalable fabrication of MSCs and effective connection of them in parallel and/or in series at various scales. Remarkably, more than 100 devices have been connected to form large-scale MSC arrays as power banks on both silicon wafers and Kapton. Without any extra protection or encapsulation, the MSC arrays can be reliably charged up to 12 V and retain the performance even 8 months after fabrication.

New-Generation Graphene from Electrochemical Approaches: Production and Applications.

Extensive research suggests a bright future for the graphene market. However, for a long time there has been a huge gap between laboratory-scale research and commercial application due to the challenging task of reproducible bulk production of high-quality graphene at low cost. Electrochemical exfoliation of graphite has emerged as a promising wet chemical method with advantages such as upscalability, solution processability and eco-friendliness. Recent progress in the electrochemical exfoliation of graphite and prospects for the application of exfoliated graphene, mainly in the fields of composites, electronics, energy storage and conversion are discussed.

Imine-linked polymer-derived nitrogen-doped microporous carbons with excellent CO2 capture properties.

A series of nitrogen-doped microporous carbons (NCs) was successfully prepared by direct pyrolysis of high-surface-area microporous imine-linked polymer (ILP, 744 m(2)/g) which was formed using commercial starting materials based on the Schiff base condensation under catalyst-free conditions. These NCs have moderate specific surface areas of up to 366 m(2)/g, pore volumes of 0.43 cm(3)/g, narrow micropore size distributions, and a high density of nitrogen functional groups (5.58-8.74%). The resulting NCs are highly suitable for CO2 capture adsorbents because of their microporous textural properties and large amount of Lewis basic sites. At 1 bar, NC-800 prepared by the pyrolysis of ILP at 800 °C showed the highest CO2 uptakes of 1.95 and 2.65 mmol/g at 25 and 0 °C, respectively. The calculated adsorption capacity for CO2 per m(2) (µmol of CO2/m(2)) of NC-800 is 7.41 µmol of CO2/m(2) at 1 bar and 25 °C, the highest ever reported for porous carbon adsorbents. The isosteric heats of CO2 adsorption (Qst) for these NCs are as high as 49 kJ/mol at low CO2 surface coverage, and still ~25 kJ/mol even at high CO2 uptake (2.0 mmol/g), respectively. Furthermore, these NCs also exhibit high stability, excellent adsorption selectivity for CO2 over N2, and easy regeneration and reuse without any evident loss of CO2 adsorption capacity.

A new route for the preparation of mesoporous carbon materials with high performance in lithium-sulphur battery cathodes.

A novel method for the preparation of highly mesoporous carbon materials (Kroll-Carbons; KCs) is described based on reactive carbochlorination etching of titania nanoparticles inside a dense carbon matrix leading to mesoporous carbons with precisely controllable porosity and high performance as cathode materials for lithium-sulphur (Li-S) batteries.

Magnetic mesoporous bioactive glass scaffolds: preparation, physicochemistry and biological properties.

The magnetic 10Fe5Ca MBG scaffolds (Fe3O4-CaO-SiO2-P2O5 system) have been prepared by a combination of polyurethane sponge and P123 as co-templates and an evaporation-induced self-assembly (EISA) process through the substitution of Fe3O4 for CaO in the 15Ca MBG scaffolds (CaO-SiO2-P2O5 system). The structure, magnetic heating, drug release, physicochemical and biological properties were systematically investigated. The results showed that the 10Fe5Ca MBG scaffolds had the interconnected macroporous structure with pore sizes ranging from 200 to 400 µm and the mesoporous wall with a peak pore size of ca. 3.34 nm. Also, the 10Fe5Ca MBG scaffolds exhibited similar mechanical strength, apatite-forming ability and sustained drug release behavior compared to the 15Ca MBG scaffolds. Importantly, the substitution of Fe3O4 for CaO in the MBG scaffolds induced a slower ion dissolution rate and more significant potential to stabilize the pH environment, and facilitated osteoblast cell proliferation, alkaline phosphatase (ALP) activity and osteogenic expression. In particular, the 10Fe5Ca MBG scaffolds could generate heat in an alternating magnetic field. Therefore, the magnetic 10Fe5Ca MBG scaffolds have potential for the regeneration of the critical-size bone defects caused by bone tumors by a combination of magnetic hyperthermia and local drug delivery therapy.