In-suitgrowth of Cu4SnS4nanoplates on reduced graphene oxide (rGO) with ligand exchange exhibiting enhanced photodegradation property.

In the present study, a novel Cu4SnS4/reduced graphene oxide (CTS/rGO) composite was successfully prepared using a simple one-pot heat-up method. Post-synthetic ligand exchange (LE) and annealing process were performed to further increase the dispersibility and the conductivity of the prepared composite. An unexpected phase transformation from CTS to Cu3SnS4with an enhanced absorption in the near-infrared (NIR) region were observed after LE. Furthermore, the photodegradation of Rhodamine B (RhB) by the CTS/rGO composite was investigated. The CTS nanoplates with 10 wt% rGO treated through LE (CTS-10%rGO-LE) exhibited the highest (99.92%) degradation rate of RhB after 90 min of visible-light irradiation, which is approximately 10 and 1.28 times that of the pure CTS and the CTS-10%rGO treated using annealing (CTS-10%rGO-A). The enhancement of the photodegradation activity could be ascribed to the in-suit growth of CTS on rGO and the subsequent LE treatment, which effectively reduced the agglomeration of CTS and increased the electron-transfer ability of the composite materials. The CTS/rGO composite also exhibited high chemical stability of the photodegradation of RhB after four recycles. The electron paramagnetic resonance spectra reveal that ·OH and h+are the main active species in the photocatalytic degradation of RhB with CTS-LE and CTS-10%rGO-LE photocatalysts. The in-suit growth of the CTS/rGO composite with a subsequent LE treatment has the potential to serve as an efficient photocatalysts for the degradation of organic pollutants.

Microfluidic Fabrication of Hierarchical-Ordered ZIF-L(Zn)@Ti3 C2 Tx Core-Sheath Fibers for High-Performance Asymmetric Supercapacitors.

We report hierarchical-ordered ZIF-L(Zn)@Ti3 C2 Tx MXene core-sheath fibers, in which a ZIF-L(Zn) nanowall array sheath is grown vertically on an anisotropic Ti3 C2 Tx core by Ti-O-Zn/Ti-F-Zn chemical bonds. Through highly efficient microfluidic assembly and microchannel reactions, ZIF-L(Zn)@Ti3 C2 Tx exhibits well-developed micro-/mesoporosity, ordered ionic pathways, fast interfacial electron conduction and large-scale fabrication, significantly boosting charges dynamic transport and intercalation. The resultant ZIF-L(Zn)@Ti3 C2 Tx fiber presents large capacitance (1700 F cm-3 ) and outstanding rate performance in a 1 M H2 SO4 electrolyte. Additionally, ZIF-L(Zn)@Ti3 C2 Tx fiber-based solid-state asymmetric supercapacitors deliver high energy density (19.0 mWh cm-3 ), excellent capacitance (854 F cm-3 ), large deformable/wearable capabilities and long-time cyclic stability (20 000 cycles), which realize natural sunlight-induced self-powered applications to drive water level/earthquake alarm devices.

Synergistic Interfacial Bonding in Reduced Graphene Oxide Fiber Cathodes Containing Polypyrrole@sulfur Nanospheres for Flexible Energy Storage.

Flexible lithium sulfur batteries with high energy density and good mechanical flexibility are highly desirable. Here, we report a synergistic interface bonding enhancement strategy to construct flexible fiber-shaped composite cathodes, in which polypyrrole@sulfur (PPy@S) nanospheres are homogeneously implanted into the built-in cavity of self-assembled reduced graphene oxide fibers (rGOFs) by a facile microfluidic assembly method. In this architecture, sulfur nanospheres and lithium polysulfides are synergistically hosted by carbon and polymer interface, which work together to provide enhanced interface chemical bonding to endow the cathode with good adsorption ability, fast reaction kinetics, and excellent mechanical flexibility. Consequently, the PPy@S/rGOFs cathode shows enhanced electrochemical performance and high-rate capability. COMSOL Multiphysics simulations and density functional theory (DFT) calculations are conducted to elucidate the enhanced electrochemical performance. In addition, a flexible Li-S pouch cell is assembled and delivers a high areal capacity of 5.8 mAh cm-2 at 0.2 A g-1 . Our work offers a new strategy for preparation of advanced cathodes for flexible batteries.

Covalently Aligned Molybdenum Disulfide-Carbon Nanotubes Heteroarchitecture for High-Performance Electrochemical Capacitors.

Advanced two-dimensional nanosheets that promote the dynamic transportation and storage capacity of ions are significant for high-performance electrochemical capacitors (ECs). However, such materials often possess a low energy density. We have developed an ordered heteroarchitecture of molybdenum disulfide-carbon nanotubes (MoS2 -CNTs) in which CNTs are vertically grafted within a MoS2 framework by C-Mo covalent bonds. Benefiting from this in situ vertical bridge, high-speed interlaminar conductivity, unimpeded ion-diffusion channels and sufficient pseudocapacitive reactivity, the MoS2 -CNTs presents ultralarge capacitance (5485 F g-1 ) and good structural stability in potassium hydroxide electrolyte. Moreover, the all-unified solid-state flexible ECs obtained through direct-write printing construction deliver high energy density (226 mWh g-1 ), good capacitance (723 F g-1 ) and stable high/low-temperature operating ability, which can power a wearable health-monitoring device.

Light-Driven Self-Oscillating Actuators with Phototactic Locomotion Based on Black Phosphorus Heterostructure.

Developing self-oscillating soft actuators that enable autonomous, continuous, and directional locomotion is significant in biomimetic soft robotics fields, but remains great challenging. Here, an untethered soft photoactuators based on covalently-bridged black phosphorus-carbon nanotubes heterostructure with self-oscillation and phototactic locomotion under constant light irradiation is designed. Owing to the good photothermal effect of black phosphorus heterostructure and thermal deformation of the actuator components, the new actuator assembled by heterostructured black phosphorus, polymer and paper produces light-driven reversible deformation with fast and large response. By using this actuator as mechanical power and designing a robot configuration with self-feedback loop to generate self-oscillation, an inchworm-like actuator that can crawl autonomously towards the light source is constructed. Moreover, due to the anisotropy and tailorability of the actuator, an artificial crab robot that can simulate the sideways locomotion of crabs and simultaneously change color under light irradiation is also realized.

A Covalent Black Phosphorus/Metal-Organic Framework Hetero-nanostructure for High-Performance Flexible Supercapacitors.

We develop hetero-nanostructured black phosphorus/metal-organic framework hybrids formed by P-O-Co covalent bonding based on a designed droplet microfluidic strategy consisting of confined and ultrafast microdroplet reactions. The resulting hybrid exhibits large capacitance (1347 F g-1 ) in KOH electrolytes due to its large specific-surface-area (632.47 m2 g-1 ), well-developed micro-porosity (0.38 cm3 g-1 ), and engineered electroactivity. Furthermore, the proposed 3D printing method allows to construct all-integrated solid-state supercapacitor, which maintains interconnected porous network, good interfacial adhesion, and robust flexibility for short-path diffusion and excessive accommodation of ions. Consequently, the fabricated flexible supercapacitor delivers ultrahigh volumetric energy density of 109.8 mWh cm-3 , large capacitance of 506 F cm-3 , and good long-term stability of 12000 cycles.

One-Pot Synthesis of Pomegranate-Structured Fe3 O4 /Carbon Nanospheres-Doped Graphene Aerogel for High-Rate Lithium Ion Batteries.

A unique hierarchically nanostructured composite of iron oxide/carbon (Fe3O4/C) nanospheres-doped three-dimensional (3D) graphene aerogel has been fabricated by a one-pot hydrothermal strategy. In this novel nanostructured composite aerogel, uniform Fe3O4 nanocrystals (5-10 nm) are individually embedded in carbon nanospheres (ca. 50 nm) forming a pomegranate-like structure. The carbon matrix suppresses the aggregation of Fe3O4 nanocrystals, avoids direct exposure of the encapsulated Fe3O4 to the electrolyte, and buffers the volume expansion. Meanwhile, the interconnected 3D graphene aerogel further serves to reinforce the structure of the Fe3O4/C nanospheres and enhances the electrical conductivity of the overall electrode. Therefore, the carbon matrix and the interconnected graphene network entrap the Fe3O4 nanocrystals such that their electrochemical function is retained even after fracture. This novel hierarchical aerogel structure delivers a long-term stability of 634 mA h g(-1) over 1000 cycles at a high current density of 6 A g(-1) (7 C), and an excellent rate capability of 413 mA h g(-1) at 10 A g(-1) (11 C), thus exhibiting great potential as an anode composite structure for durable high-rate lithium-ion batteries.

Bovine Serum Albumin Adsorption in Mesoporous Titanium Dioxide: Pore Size and Pore Chemistry Effect.

Understanding the mechanism of protein adsorption and designing materials with high sensitivity, high specificity and fast response are critical to develop the next-generation biosensing and diagnostic platforms. Mesoporous materials with high surface area, tunable pores, and good thermal/hydrostatic stabilities are promising candidates in this field. Because of the excellent biocompatibility, titanium dioxide has received an increasing interest in the past decade for biomedical applications. In this work, we synthesized mesoporous titanium dioxide with controlled pore sizes (7.2-28.0 nm) and explored their application for bovine serum albumin (BSA) adsorption. Scanning electron microscopy (SEM), X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and nitrogen adsorption/desorption experiments were performed to characterize the mesoporous TiO2 samples before and after BSA adsorption. Isothermal microcalorimetry was applied to measure both the adsorption heat and conformation rearrangement heat of BSA in those mesopores. We also carried out thermogravimetry measurements to qualitatively estimate the concentration of hydroxyl groups, which plays an important role in stabilizing BSA in-pore adsorption. The adsorption stability was also examined by leaching experiments. The results showed that TiO2 mesopores can host BSA adsorption when their diameters are larger than the hydrodynamic size of BSA (∼9.5 nm). In larger mesopores studied, two BSA molecules were adsorbed in the same pores. In contrast to the general understanding that large mesopores demonstrate poor stabilities for protein adsorptions, the synthesized mesoporous TiO2 samples demonstrated good leaching stabilities for BSA adsorption. This is probably due to the combination of the mesoporous confinement and the in-pore hydroxyl groups.

Ligand exchange induced crystal structure and morphology evolution of copper-tin-sulfur binary and ternary compounds.

In this manuscript, a simple one-pot heat-up method has been used to prepare multi-component copper-tin-sulfur nanomaterials, including binary Cu1.94S, ternary Cu4SnS4, and Cu1.94S/Cu4SnS4 nanocrystals by varying the reaction temperature, reaction time, and the type of copper source. Post-synthetic ligand exchange (LE) has further been introduced to replace the long-chain ligands originating from 1-dodecanethiol. It has been found that the LE process not only changes the surface ligands but also significantly affects the crystal structure and optical properties of nanocrystals. After LE, the crystal structures of Cu1.94S and Cu4SnS4 transformed to Cu7S4 and Cu3SnS4, respectively, with the Cu1.94S/Cu4SnS4 nanocrystals showing the same trend. This phenomenon could be ascribed to the loss of Cu+ originating from the strong complexation of Cu+ and ammonia with the formation of [Cu(NH3)n]2+ ions under aerobic conditions. Proton nuclear magnetic resonance (1H NMR) has been used to characterize the ligands on the surface before and after LE, which further demonstrated that the -SH was replaced during LE. Meanwhile, the band gaps of the obtained nanocrystals after LE show an obvious shift in the near-infrared region due to the evolution of crystal structures. This study will provide useful guidance for the LE of nanocrystals and the application of copper-based sulfide nanomaterials in optoelectronics and other fields.

Janus GO/BTA/PMMA Microcapsules for Biobased Self-Healing Anticorrosion Coatings with Ultrahigh Performance.

The giant reduction of the barrier properties due to self-healing microcapsules and the lack of real-time protection during the healing remained the main challenges in self-healing anticorrosion coatings. Herein, a facile strategy using Janus graphene oxide (GO) as a dense and flexible shell has been proposed to synergistically solve these challenges. Benzotriazole (BTA) was used to synthesize Janus GO at the oil-water interface, and Janus GO/BTA/poly(methyl methacrylate) microcapsules were prepared. Energy-dispersive X-ray spectroscopy, Fourier infrared spectroscopy, Raman spectroscopy, and ultraviolet spectrophotometer analysis confirmed the formation of a Janus GO structure with one surface hydrophilic and the other hydrophobic. The surface morphology of J-GO-capsules with a high GO coverage rate was observed by scanning electron microscopy. The high biobased content coating containing J-GO-capsules showed a low-frequency impedance value above 1010 as assessed by electrochemical impedance spectroscopy after being immersed in 3.5 wt % NaCl solution for 60 days. In addition, the low-frequency impedance values of the coating were maintained after being scratched due to the self-healing properties of the J-GO-capsules as well as the real-time protective effect of the BTA. Biobased coatings with the best overall properties among all of the self-healing anticorrosion coatings were prepared.

Juice Vesicles Bioreactors Technology for Constructing Advanced Carbon-Based Energy Storage.

The construction of high-quality carbon-based energy materials through biotechnology has always been an eager goal of the scientific community. Herein, juice vesicles bioreactors (JVBs) bio-technology based on hesperidium (e.g., pomelo, waxberry, oranges) is first reported for preparation of carbon-based composites with controllable components, adjustable morphologies, and sizes. JVBs serve as miniature reaction vessels that enable sophisticated confined chemical reactions to take place, ultimately resulting in the formations of complex carbon composites. The newly developed approach is highly versatile and can be compatible with a wide range of materials including metals, alloys, and metal compounds. The growth and self-assembly mechanisms of carbon composites via JVBs are explained. For illustration, NiCo alloy nanoparticles are successfully in situ implanted into pomelo vesicles crosslinked carbon (PCC) by JVBs, and their applications as sulfur/carbon cathodes for lithium-sulfur batteries are explored. The well-designed PCC/NiCo-S electrode exhibits superior high-rate properties and enhanced long-term stability. Synergistic reinforcement mechanisms on transportation of ions/electrons of interface reactions and catalytic conversion of lithium polysulfides arising from metal alloy and carbon architecture are proposed with the aid of DFT calculations. The research provides a novel biosynthetic route to rational design and fabrication of carbon composites for advanced energy storage.

Colloidal synthesis of wurtzite Cu2CoSnS4 nanocrystals and the photoresponse of spray-deposited thin films.

Monodisperse nanocrystals of a new wurtzite phase of Cu(2)CoSnS(4) (CCTS) have been synthesized using a simple solution-based method. The wurtzite CCTS nanocrystals grow in the shape of nanorods with an average length of 32 ± 2.0 and width of 16 ± 1.5 nm. The more stable stannite phase of CCTS has also been synthesized by increasing the reaction temperature or by a post-high-temperature annealing process. The band gap of wurtzite CCTS nanocrystals is determined to be 1.58 eV. Thin films prepared from the nanocrystal suspension display photoresponse behaviour with white light from a solar simulator, suggesting the potential use of CCTS as an active layer in low-cost thin-film solar cells.

Synthesis of Single Crystal 2D Cu2FeSnS4 Nanosheets with High-Energy Facets (111) as a Pt-Free Counter Electrode for Dye-Sensitized Solar Cells.

Two-dimensional Cu2FeSnS4 (CFTS) nanosheets with exposed high-energy facets (111) have been synthesized by a facile, scalable, and cost-effective one-pot heating process. The CFTS phase formation is confirmed by both X-ray diffraction and Raman spectroscopy. The formation mechanism of exposed high-energy facet CFTS growth is proposed and its electrochemical and photoelectrochemical properties are investigated in detail to reveal the origin of the anisotropic effect of the high-energy facets. Dye-sensitized solar cells (DSSC) achieve a favorable power conversion efficiency of 5.92% when employing CFTS thin film as a counter electrode, suggesting its potential as a cost-effective substitute for Pt in DSSCs.

Microfluidic-Assembled Covalent Organic Frameworks@Ti3 C2 Tx MXene Vertical Fibers for High-Performance Electrochemical Supercapacitors.

The delicate design of innovative and sophisticated fibers with vertical porous skeleton and eminent electrochemical activity to generate directional ionic pathways and good faradic charge accessibility is pivotal but challenging for realizing high-performance fiber-shaped supercapacitors (FSCs). Here, hierarchically ordered hybrid fiber combined vertical-aligned and conductive Ti3 C2 Tx MXene (VA-Ti3 C2 Tx ) with interstratified electroactive covalent organic frameworks LZU1 (COF-LZU1) by one-step microfluidic synthesis is developed. Due to the incorporation of vertical channels, abundant redox active sites and large accessible surface area throughout the electrode, the VA-Ti3 C2 Tx @COF-LZU1 fibers express exceptional gravimetric capacitance of 787 F g-1 in a three-electrode system. Additionally, the solid-state asymmetric FSCs deliver a prominent energy density of 27 Wh kg-1 , capacitance of 398 F g-1 and cycling life of 20 000 cycles. The key to high energy storage ability originates from the decreased ions adsorption energy and ameliorative charge density distribution in vertically aligned and active hybrid fiber, accelerating ions transportation/accommodation and interfacial electrons transfer. Benefiting from excellent electrochemical performance, the FSCs offer sufficient energy supply to power watches, flags, and digital display tubes as well as be integrated with sensors to detect pulse signals, which opens a promising route for architecting advanced fiber toward the carbon neutrality market beyond energy-storage technology.

Hierarchical 3D Porous Hydrogen-Substituted Graphdiyne for High-Performance Electrochemical Lithium-Ion Storage.

Graphdiyne (GDY) has realized significant achievements in lithium-ion batteries (LIBs) because of its unique π-conjugated skeleton with sp- and sp2-hybridized carbon atoms. Enriching the accessible surface areas and diffusion pathways of Li ions can realize more storage sites and rapid transport dynamics. Herein, three-dimensional porous hydrogen-substituted GDY (HsGDY) is developed for high-performance Li-ion storage. HsGDY, fabricated via a versatile interface-assisted synthesis strategy, exhibits a large specific surface area (667.9 m2 g-1), a hierarchical porous structure, and an expanded interlayer space, which accelerate Li-ion accessibility and lithiation/delithiation. Owing to this high π-conjugated, conductive, and porous framework, HsGDY exhibits a large reversible capacity (930 mA h g-1 after 100 cycles at 1 A g-1), superior cycle (720 mA h g-1 after 300 cycles at 1 A g-1), and rate (490 mA h g-1 at 5 A g-1) performances. Density functional theory calculations of the low diffusion barrier in the lamination and vertical directions further reveal the fast Li-ion transport kinetics of HsGDY. Additionally, a LiCoO2-HsGDY full cell is constructed, which exhibits a good practical charge/discharge capacity of 128 mA h g-1 and stable cycling behavior. This study highlights the advanced design of next-generation LIBs to sustainably develop the new energy industry.

Nanostructured WO3/BiVO4 heterojunction films for efficient photoelectrochemical water splitting.

We report on a novel heterojunction WO(3)/BiVO(4) photoanode for photoelectrochemical water splitting. The heterojunction films are prepared by solvothermal deposition of a WO(3) nanorod-array film onto fluorine-doped tin oxide (FTO) coated glass, with subsequent deposition of a low bandgap, 2.4 eV, visible light responding BiVO(4) layer by spin-coating. The heterojunction structure offers enhanced photoconversion efficiency and increased photocorrosion stability. Compared to planar WO(3)/BiVO(4) heterojunction films, the nanorod-array films show significantly improved photoelectrochemical properties due, we believe, to the high surface area and improved separation of the photogenerated charge at the WO(3)/BiVO(4) interface. Synthesis details are discussed, with film morphologies and structures characterized by field emission scanning electron microscopy and X-ray diffraction.

Implanting an Electron Donor to Enlarge the d-p Hybridization of High-Entropy (Oxy)hydroxide: A Novel Design to Boost Oxygen Evolution.

High-entropy (HE) electrocatalysts are becoming a research hotspot due to their interesting "cocktail effect" and have great potential for tailored catalytic properties. However, it is still a great challenge to illustrate their inherent catalytic mechanism for the "cocktail effect", and there is also a paucity of quantitative descriptors to characterize the specific catalytic activity and give logical design strategies for HE systems. Herein, the unexpected activation of all metal sites in HE Cu-Co-Fe-Ag-Mo (oxy)hydroxides for the oxygen evolution reaction (OER) is reported, and it is found that metal-oxygen d-p hybridization, as an effective descriptor, can indicate the intrinsic activity of each metal site. According to the quantitative hybridization, introducing an electron donor (e.g., Ag) is raised and verified to reinforce the electrocatalytic activity of the HE system. Consequently, Ag-decorated Co-Cu-Fe-Ag-Mo (oxy)hydroxide (Ag@CoCuFeAgMoOOH) electrocatalysts are constructed by an electrochemical reconstruction method, and their OER performances are thoroughly characterized. The Ag@CoCuFeAgMoOOH is verified with a low overpotential (270 mV at 100 mA cm-2 ) and a small Tafel slope (35.3 mV dec-1 ), as well as good electrochemical stability. The favorable activity of the electron donor and underlying synergistic "cocktail effect" are demonstrated and disclosed. This work opens up a new strategy to guide the design/fabrication of advanced HE electrocatalysts.

Two-Dimensional Hybrid Nanosheet-Based Supercapacitors: From Building Block Architecture, Fiber Assembly, and Fabric Construction to Wearable Applications.

Fiber-based supercapacitors (F-SCs) have inspired widespread interest in the fields of wearable technology, energy, and carbon neutralization due to their highly deformable flexibility, fast charging/discharging capability, long-term stability, and energy conservation ability. In this review, we summarize the latest developments for fabricating fibrous electrodes of F-SCs where advanced micro two-dimensional (2D) building blocks (e.g., MXene and graphene) are chemically assembled and constructed into ordered mesofibers and multifunctional macrofabrics. Diverse fundamental principles of 2D hybrid nanosheets with respect to surface controls, pseudocapacitive modifications, and microstructural manipulations, promoting rapid electron transfer and charge conduction, are introduced. Additionally, various spinning methods for assembling and fabricating sophisticated fibers with advanced nano/microstructures, including hierarchical skeletons, anisotropic backbones, surface/entire porous frameworks, and vertical-aligned networks, for boosting ionic kinetic transport/storage are presented. Likewise, the structure-activity relationships between the porous structure and electrochemical performance are clarified. Moreover, multifunctional fabrics in terms of high flexibilities/strengths, superior electrical conductivities, and stabilized operations, which realize large energy density, deformable capability, and robust stability under harsh conditions, are emphasized. In particular, the potential power-supply applications, including flexible electronic devices, self-powered functions, and energy-sensor systems, are highlighted. Finally, a short conclusion and outlook, along with the current challenges and future opportunities of next-generation F-SCs, are proposed.

Synthesis of shape-controlled monodisperse wurtzite CuIn(x)Ga(1-x)S2 semiconductor nanocrystals with tunable band gap.

Monodisperse wurtzite CuIn(x)Ga(1-x)S(2) nanocrystals have been synthesized over the entire composition range using a facile solution-based method. Depending on the chemical composition and synthesis conditions, the morphology of the nanocrystals can be controlled in the form of bullet-like, rod-like, and tadpole-like shapes. The band gap of the nanocrystals increases linearly with increasing Ga concentration, with band gap values for the end members being close to those observed in the bulk. Colloidal suspensions of the nanocrystals are attractive for use as inks for low-cost fabrication of thin film solar cells by spin or spray coating.

Top-Level Design Strategy to Construct an Advanced High-Entropy Co-Cu-Fe-Mo (Oxy)Hydroxide Electrocatalyst for the Oxygen Evolution Reaction.

High-entropy materials are new-generation electrocatalysts for water splitting due to their excellent reactivity and highly tailorable electrochemical properties. Herein, a powerful top-level design strategy is reported to guide and design advanced high-entropy electrocatalysts by establishing reaction models (e.g., reaction energy barrier, conductivity, adsorption geometries for intermediates, and rate-determining step) to predict performance with the help of density functional theory (DFT) calculations. Accordingly, novel high-entropy Co-Cu-Fe-Mo (oxy)hydroxide electrocatalysts are fabricated by a new low-temperature electrochemical reconstruction method and their oxygen evolution reaction (OER) properties are thoroughly characterized. These as-prepared quaternary metallic (oxy)hydroxides present much better OER performance than ternary Co-Cu-Mo (oxy)hydroxide, Co-Fe-Mo (oxy)hydroxide, and other counterparts, and are demonstrated with a low overpotential of 199 mV at a current density of 10 mA cm-2 and a 48.8 mV dec-1 Tafel slope in 1 m KOH and excellent stability without decay over 72 h. The performance enhancement mechanism is also unraveled by synchrotron radiation. The work verifies the usefulness of high-entropy design and the great synergistic effect on OER performance by the incorporation of four elements, and also provides a new method for the construction of advanced high-entropy materials for energy conversion and storage.