Laser‐Induced Graphene: From Discovery to Translation

Laser‐induced graphene (LIG) is a 3D porous material prepared by direct laser writing with a CO₂ laser on carbon materials in ambient atmosphere. This technique combines 3D graphene preparation and patterning into a single step without the need for wet chemical steps. Since its discovery in 2014, LIG has attracted broad research interest, with several papers being published per month using this approach. These serve to delineate the mechanism of the LIG‐forming process and to showcase the translation into many application areas. Herein, the strategies that have been developed to synthesize LIG are summarized, including the control of LIG properties such as porosity, composition, and surface characteristics, and the advancement in methodology to convert diverse carbon precursors into LIG. Taking advantage of the LIG properties, the applications of LIG in broad fields, such as microfluidics, sensors, and electrocatalysts, are highlighted. Finally, future development in biodegradable and biocompatible materials is briefly discussed.     

透明超疏水玻璃表面的制备及性能研究

目的研究透明超疏水玻璃的制备及性能。方法以纳米二氧化硅和无水乙醇为原料制成半透明乳液,然后将乳液喷涂在玻璃表面,再通过接触角测试、透光率测试仪等手段对玻璃表面的性能进行研究。结果在玻璃基材表面构建了与水滴接触角高达158°±2°,滚动角低至1°的透明超疏水表面。当喷涂液中纳米二氧化硅的质量分数为1.5%时,获得的超疏水玻璃表面具有优异的防水性、抗污易清洁性和透明性。结论在玻璃基底上制备透明超疏水表面可以大大提高玻璃表面的防水、防污性,并使玻璃表面更易于清洁,有利于减少玻璃包装材料清洗时的用水量和洗涤剂用量,从而增强玻璃包装材料的生态环保效应。     

UV‐Resistant and Thermally Stable Superhydrophobic CeO2 Nanotubes with High Water Adhesion

A novel type of sticky superhydrophobic cerium dioxide (CeO₂) nanotube material is prepared by hydrothermal treatment without any chemical modification. A water droplet on the material surface shows a static water contact angle of about 157° but the water droplet is pinned on the material surface even when the material surface is turned upside down. Interestingly, the as‐prepared CeO₂ nanotube material displays durable superhydrophobicity and enhanced adhesion to water under ultraviolet (UV) light irradiation. Importantly, this change in water adhesion can be reversed by heat treatment to restore the original adhesive value of 20 µL. Further, the maximum volume of the water droplet adhered on the material surface of CeO₂ nanotubes can be regulated without loss of superhydrophobicity during the heating treatment/UV‐irradiation cycling. Meanwhile, the superhydrophobic CeO₂ nanotube material shows remarkable thermal stability even at temperatures as high as 450 °C, long‐term durability in chemical environment, and air‐storage and good resistance to oily contaminant. Finally, the potential application in no‐loss water transportation of this sticky superhydrophobic CeO₂ material is demonstrated.     

Oxidized Laser‐Induced Graphene for Efficient Oxygen Electrocatalysis

An efficient metal‐free catalyst is presented for oxygen evolution and reduction based on oxidized laser‐induced graphene (LIG‐O). The oxidation of LIG by O₂ plasma to form LIG‐O boosts its performance in the oxygen evolution reaction (OER), exhibiting a low onset potential of 260 mV with a low Tafel slope of 49 mV dec^?1, as well as an increased activity for the oxygen reduction reaction. Additionally, LIG‐O shows unexpectedly high activity in catalyzing Li₂O₂ decomposition in Li‐O₂ batteries. The overpotential upon charging is decreased from 1.01 V in LIG to 0.63 V in LIG‐O. The oxygen‐containing groups make essential contributions, not only by providing the active sites, but also by facilitating the adsorption of OER intermediates and lowering the activation energy.     

Robust Flower‐Like TiO2@Cotton Fabrics with Special Wettability for Effective Self‐Cleaning and Versatile Oil/Water Separation

Inspired by the hierarchical structure of the mastoid on the micrometer and nanometer scale and the waxy crystals of the mastoid on natural lotus surfaces, a facile one‐step hydrothermal strategy is developed to coat flower‐like hierarchical TiO₂ micro/nanoparticles onto cotton fabric substrates (TiO₂@Cotton). Furthermore, robust superhydrophobic TiO₂@Cotton surfaces are constructed by the combination of hierarchical structure creation and low surface energy material modification, which allows versatility for self‐cleaning, laundering durability, and oil/water separation. Compared with hydrophobic cotton fabric, the TiO₂@Cotton exhibits a superior antiwetting and self‐cleaning property with a contact angle (CA) lager than 160° and a sliding angle lower than 5°. The superhydrophobic TiO₂@Cotton shows excellent laundering durability against mechanical abrasion without an apparent reduction of the water contact angle. Moreover, the micro/nanoscale hierarchical structured cotton fabrics with special wettability are demonstrated to selectively collect oil from oil/water mixtures efficiently under various conditions (e.g., floating oil layer or underwater oil droplet or even oil/water mixtures). In addition, it is expected that this facile strategy can be widely used to construct multifunctional fabrics with excellent self‐cleaning, laundering durability, and oil/water separation. The work would also be helpful to design and develop new underwater superoleophobic/superoleophilic materials and microfluidic management devices.     

Substitutional and defect doping effects on the photoelectrochemical properties of Fe2O3

Fe₂O₃ samples have been prepared using both substitutional and defect doping techniques. Defect doped samples were sintered in air at 1350° C for 20 hours, reduced in a H₂ atmosphere for various times at 300° C, and finally reoxidized at 700–900° C for short periods. Resulting resistivities ranged from .01 to 5000 ohm-cm. Such electrodes were found to have good photoelectrochemical properties, and to be quite sensitive to chemical etching. Substitutional doping of Fe₂O₃ with Si, Ca, Nb, Cu, Ru, Mg, and Zr was performed, with Si and Cu providing the best results. The effects of quenching time and temperature on the properties of these electrodes are discussed.     

Engineering High‐Performance MoO2‐Based Nanomaterials with Supercapacity and Superhydrophobicity by Tuning the Raw Materials Source

Herein, a simple self‐assembly method is proposed for the fabrication of MoO₂‐based superhydrophobic material with record high contact angles (contact angle up to about 173°) for conductive metal oxides on hard/soft substrates. The spin‐coated surface demonstrates excellent oil–water separation efficiency (>98%) after 50 cycles and robust corrosion resistance after immersion into different pH solutions for 20 d. These water‐resistant coatings retain excellent superhydrophobicity after oil immersion, knife‐scratch, and long‐cycle sandpaper abrasion, which is not observed on most artificial surfaces. Meanwhile, the functionality switching from superhydrophobicity to supercapacity, which have an inverse relationship in aqueous solutions because of poor electrode wettability, is achieved simply by editing the raw materials source. Tuning of the raw materials leads to the same product MoO₂/graphitic carbon with different morphologies and functionalities. Different from superhydrophobic MoO₂/carbon ball flowers, MoO₂ nanotubes with carbon exhibit excellent supercapacity with a large gravimetric capacitance and great cycling stability.     

Synthesis and Study of Structural,Morphological and Magnetic Properties of ZnFe2O4 Nanoparticles

Superparamagnetic zinc ferrite (ZnFe₂O₄) nanoparticles were prepared by a surfactant assisted hydrothermal method and subjected to the heat treatment. The structure, vibrational, morphology, and magnetic properties of synthesized product were characterized by XRD, FT-IR, HR-SEM, and VSM measurements. XRD result confirms the formation of regular spinel structured ZnFe₂O₄ with space group of Fd3m and an average crystalline size was calculated as 21 nm and 28 nm for the samples annealed in air atmosphere at 300 °C and 600 °C. The HR-SEM image shows that the particles are in spherical shape with small aggregation. A room temperature superparamagnetic behavior was observed for both samples. The saturation magnetization (M _s) of 12.0 emu/g and 9.10 emu/g were observed for the samples annealed in air atmosphere at 300 °C and 600 °C, respectively.     

A Combinatorial Library of Micro‐Topographies and Chemical Compositions for Tailored Surface Wettability

Surface modification of topography and chemistry in order to achieve a specific water contact angle (CA) has been explored by using a novel combinatorial screening platform. The screening arrays consisted of 507 distinct combinations of micro‐topographies and chemical compositions. By performing chemical modifications with 1H, 1H, 2H, 2H perfluoroethyltriethoxy‐silane (PFS) and n‐octadecyltriethoxysilane (ODS) on standard silicon wafers it was possible to include both superhydrophobic and very hydrophilic pad arrays in the same screening platform. Surfaces modified with PFS were more hydrophobic than surfaces modified with ODS, while the unmodified silicon surfaces were hydrophilic. For the PFS modified surfaces the largest CAs were achieved with a small pillar size of X = 1 µm and an intermediate inter‐pillar gap size of Y = 4 µm with superhydrophobic CAs over 170°. Surface analysis with X‐ray photoelectron spectroscopy (XPS) revealed that CF₃ groups were present at the surface, contributing to the superhydrophobic effect. The ODS modified surfaces had intermediate wettabilities with CAs between 100 and 150°, which were dependent on the pillar size, the inter‐pillar gap size, and the specific pillar pattern. The unmodified silicon topographical surfaces were very hydrophilic with CAs below 20° independent of specific topography. With this approach we have managed to fabricate 507 distinct surface areas covering a range of wettabilities, which is useful when screening these effects in several different applications. The measured CAs did not follow the simple Wenzel model. Furthermore, the adaptation of the Cassie model introduces Φ_s, the fraction of solid surface in contact with the liquid, which is difficult to estimate, thereby emphasizing the need for an experimental determination.     

Nanofibers Comprising Yolk–Shell Sn@void@SnO/SnO2 and Hollow SnO/SnO2 and SnO2 Nanospheres via the Kirkendall Diffusion Effect and Their Electrochemical Properties

Nanofibers with a unique structure comprising Sn@void@SnO/SnO₂ yolk–shell nanospheres and hollow SnO/SnO₂ and SnO₂ nanospheres are prepared by applying the nanoscale Kirkendall diffusion process in conventional electrospinning process. Under a reducing atmosphere, post‐treatment of tin 2‐ethylhexanoate‐polyvinylpyrrolidone electrospun nanofibers produce carbon nanofibers with embedded spherical Sn nanopowders. The Sn nanopowders are linearly aligned along the carbon nanofiber axis without aggregation of the nanopowders. Under an air atmosphere, oxidation of the Sn–C composite nanofibers produce nanofibers comprising Sn@void@SnO/SnO₂ yolk–shell nanospheres and hollow SnO/SnO₂ and SnO₂ nanospheres, depending on the post‐treatment temperature. The mean sizes of the hollow nanospheres embedded within tin oxide nanofibers post‐treated at 500 °C and 600 °C are 146 and 117 nm, respectively. For the 250th cycle, the discharge capacities of the nanofibers prepared by the nanoscale Kirkendall diffusion process post‐treated at 400 °C, 500 °C, and 600 °C at a high current density of 2 A g^?1 are 663, 630, and 567 mA h g^?1, respectively. The corresponding capacity retentions are 77%, 84%, and 78%, as calculated from the second cycle. The nanofibers prepared by applying the nanoscale Kirkendall diffusion process exhibit superior electrochemical properties compared with those of the porous‐structured SnO₂ nanofibers prepared by the conventional post‐treatment process.     

Tuning Surface Wettability and Adhesivity of a Nitrogen‐Doped Graphene Foam after Water Vapor Treatment for Efficient Oil Removal

An environment‐friendly water vapor treatment for realizing a highly hydrophobic (contact angle ≈147.5°) and oleophilic N‐doped graphene foam (NGF) for efficiently removing oil from oil/water emulsions is presented. 3D porous networks of NGF with high N content are prepared by subjecting a mixture of graphene oxide and 5 vol% pyrrole to a hydrothermal process; the mixture is then freeze‐dried and annealed under a N₂ atmosphere. The surface wettability and adhesivity are tuned through water vapor treatment by forming a low‐surface‐energy hydrocarbon layer, with no chemical modification. The effectiveness of the hydrophobic/oleophilic NGF in removing oil from an oil/water emulsion is demonstrated.     

Influence of pre-irradiation atmosphere on the properties of polymer electrolyte membranes prepared using radiation grafting method

The influence of pre-irradiation atmosphere, argon and air, on radiation grafting of styrene into poly(ethylene-co-tetrafluoroethylene) (ETFE) films and the properties of the ETFE-based radiation-grafted polymer electrolyte membranes were investigated. The preparation and properties of the membranes were found to be strongly influenced by the γ-ray pre-irradiation atmosphere. The proton conductivity was measured in its water-saturated state at 25 °C, and the membrane durability was tested in a 3% H₂O₂ aqueous solution at 60 °C. The proton conductivity of the membrane prepared by pre-irradiation under air was higher than that of the membrane prepared under argon with the same ion exchange capacity level. However, the durability of the former was considerably lower than that of the latter. For instance, the membrane with an ion exchange capacity of about 1.0 mmol g⁻¹ prepared under argon was twice as durable as that prepared under air. It was considered that the lower durability of the membrane prepared by pre-irradiation under air was because of the unstable ether bond introduced between the graft chains and the backbone chains.     

Facile synthesis,phase transition,optical switching and oxidation resistance properties of belt-like VO2(A) and VO2(M) with a rectangular cross section

Belt-like VO₂(A) with a rectangular cross section (VA-RCS) was successfully synthesized using V₂O₅, H₂C₂O₄·2H₂O and H₂O as the starting materials by a facile hydrothermal approach. Some synthetic parameters, such as, the reaction time, reaction temperature and concentration of H₂C₂O₄·2H₂O, were systematically investigated to control the fabrication of belt-like VA-RCS. The formation mechanism of belt-like VA-RCS was proposed. Subsequently, belt-like VO₂(M) with a rectangular cross section (VM-RCS) was prepared by the irreversible transformation of VA-RCS at 700 °C for 2 h under the inert atmosphere. The phase transition temperature (T_c) of VA-RCS and VM-RCS was evaluated by DSC test. The optical switching properties of VA-RCS and VM-RCS were studied by the variable-temperature infrared spectra, and it was found that the as-obtained VA-RCS and VM-RCS could be used as the optical switching materials. Furthermore, the oxidation resistance properties of VA-RCS and VM-RCS were investigated by TGA, indicating that they have good thermal stability and oxidation resistance below 400 °C in air.     

Graphene‐Based Nafion Nanocomposite Membranes: Enhanced Proton Transport and Water Retention by Novel Organo‐functionalized Graphene Oxide Nanosheets

Novel nanostructured organo‐modified layered materials based on graphene oxide carrying various hydrophilic functional groups (‐NH₂, ‐OH, ‐SO₃H) are prepared and tested as nanofillers for the creation of innovative graphene‐based Nafion nanocomposites. The hybrid membranes are characterized by a combination of analytical techniques, which show that highly homogeneous exfoliated nanocomposites are created. The pulsed field gradient NMR technique is used to measure the water self‐diffusion coefficients. Remarkable behavior at temperatures up to 140 °C is observed for some composite membranes, thereby verifying the exceptional water retention property of these materials. Dynamic mechanical analysis shows that hybrid membranes are much stiffer and can withstand higher temperatures than pure Nafion.     

Effect of Oxygen Partial Pressure on Phase Formation and Stability of LuBa2Cu3O7?x Compounds

Among the several R-123-type (R = rare-earth element) superconductors, it has been reported that LuBa₂Cu₃O_7?x (Lu-123) could not be prepared as single-phase superconducting ceramics at temperatures between 900 and 1000?°C both in air and in pure O₂. We present here the results of our investigations of the synthesis and structural stability of nearly phase-pure ceramic Lu-123 compounds prepared by a solid-state reaction route. It is found that the phase-pure Lu-123 compound can be formed within a narrow range of oxygen partial pressure in the temperature range of 880?C900?°C. It is also found that the Lu-123 phase becomes unstable due to the structural decomposition at temperature above 800?°C in N₂ and in pure O₂ of 1 atmosphere, and above 830?°C in air.     

Inside Front Cover: Towards Understanding Why a Superhydrophobic Coating Is Needed by Water Striders (Adv. Mater. 17/2007)

Gold threads modified with superhydrophobic or normal hydrophobic coatings are used as model system in the study of the contribution of a superhydrophobic coating of water striders to their floating and movement on water surfaces. After depositing Pt aggregates on one of its ends, the gold threads are able to move in the H₂O₂ aqueous solution. The superhydrophobic coating is proven to be able to decrease fluidic drag during motion, as described by Xi Zhang and co‐workers on p. 2257.     

Characterization of Ni nanowires after annealing

The effect of Ni nanowires, fabricated by electrodeposition in self-ordered AAO templates, was studied. NiO and Ni₂O₃ nanofibers were fabricated by simple heat-treatment in air and in an atmosphere of pure O₂. Ni nanowires after vacuum annealing exhibit pronounced preferential orientation of Ni (111) at 600 °C. Grain growth resulted in size effects and induced the transformation of NiO to Ni₂O₃ during annealing in air. Ni was oxidized to Ni₂O₃ (∼ 500 °C) in an atmosphere of pure O₂. The stable Ni-oxides Ni₂O₃ are formed during annealing at a higher temperature (∼ 900 °C) in air and in an atmosphere of pure O₂.     

Preparation and sintering properties in air of silver-coated copper powders and pastes

In this paper, uniform and well dispersed silver-coated copper powders were prepared by replacing reaction at first. The structure and properties of the bimetallic powders were investigated by XRD, SEM and TGA. It was found that anti-oxidization of the silver-coated copper powders increased with the increase of the silver content slightly and a dense coating surface was observed at Ag content of 53.9 wt%. Furthermore, the pastes with relatively low silver content which were prepared from silver-coated copper powders, displayed high conductivity similar to pure silver even after sintering in air. And their sintering properties were also investigated at different temperature in air atmosphere. The film exhibits good electrical properties at sintering temperature between 800 and 900 °C. When the paste from silver-coated copper powder with Ag content of 53.9 wt% was printed on Al₂O₃ substrate and sintered at 800 °C in air, the sheet resistance of the film is 0.036 Ω/□ only.     

Impedance spectroscopy studies of bulk electrical conduction in A-site acceptor (K)-doped BaTiO3

BaTiO₃ ceramics with different acceptor concentrations of potassium at A-site Ba_1?x K _x TiO_3?x/2 (BKT) were prepared by solid-state processes. The solution limit of potassium in BKT is determined to be 1 mol%. Furthermore, electrical conduction behaviours were investigated in the temperature range of 300–800 °C by analysing impedance spectra and were found extremely depending on processing and measurement conditions. When annealed at 800 °C and measured in an atmosphere of dry N₂, BKT is a mixed oxide ion/electron conductor and its ionic transference number decreases with increasing temperature. But when annealed at 800 °C and measured in an atmosphere of dry air and O₂, BKT is a p-type semiconductor with a transition from a trapped holes’ conduction to activated holes’ conduction as temperature increases. On exposure of BKT to an atmosphere of wet N₂, BKT is a proton conductor in the temperature of 300–550 °C; however, it reverts to a p-type semiconductor above 550 °C as water is lost from the sample.     

Fabrication of Millimeter‐Scale,Single‐Crystal One‐Third‐Hydrogenated Graphene with Anisotropic Electronic Properties

Periodically hydrogenated graphene is predicted to form new kinds of crystalline 2D materials such as graphane, graphone, and 2D C_xH_y, which exhibit unique electronic properties. Controlled synthesis of periodically hydrogenated graphene is needed for fundamental research and possible electronic applications. Only small patches of such materials have been grown so far, while the experimental fabrication of large‐scale, periodically hydrogenated graphene has remained challenging. In the present work, large‐scale, periodically hydrogenated graphene is fabricated on Ru(0001). The as‐fabricated hydrogenated graphene is highly ordered, with a √3 × √3/R30° period relative to the pristine graphene. As the ratio of hydrogen and carbon is 1:3, the periodically hydrogenated graphene is named “one‐third‐hydrogenated graphene” (OTHG). The area of OTHG is up to 16 mm². Density functional theory calculations demonstrate that the OTHG has two deformed Dirac cones along one high‐symmetry direction and a finite energy gap along the other directions at the Fermi energy, indicating strong anisotropic electrical properties. An efficient method is thus provided to produce large‐scale crystalline functionalized graphene with specially desired properties.