Evaporation-induced Self-assembly Approach Research Articles

Fuel flexible SOFC with a Mo-doped CeO2/YSZ mesoporous anode fabricated by the evaporation induced self-assembly (EISA) method

The design and extension of the triple phase boundary (TPB) in fuel cell electrodes play a key role in electric power generation, TPB enhancement can be achieved by direct growth of mesoporous anode structures on the electrolyte of a SOFC. In this study, we present a novel approach to enhance the performance of solid oxide fuel cells (SOFCs) by designing and extending the TPB through direct growth of mesoporous anode structures on the electrolyte. Mesoporous Mo-doped CeO2/YSZ anodes were successfully grown directly on a commercial YSZ substrate via the EISA method. These anodes exhibited remarkable stability over 60 h of testing when fueled with H2 or syngas, highlighting their fuel-flexibility. Our results show that these SOFCs achieved their highest power densities when fueled with H2, achieving a remarkable 135 % increase in electrical power density compared to previously reported values for the same anode material without microstructure control. Moreover, compared to SOFCs with mesoporous nanoparticles-based anodes, the EISA approach resulted in a 74 % higher electrical power density. Although this method improves the performance of the SOFC, there is evidence of an increase in its polarization resistance attributed to mass transport limitations through the mesoporous structure.

Enhanced Visible-Light Photocatalytic Activity of Bismuth Ferrite Hollow Spheres Synthesized via Evaporation-Induced Self-Assembly.

Semiconductor hollow spheres have garnered significant attention in recent years due to their unique structural properties and enhanced surface area, which are advantageous for various applications in catalysis, energy storage, and sensing. The present study explores the surfactant-assisted synthesis of bismuth ferrite (BiFeO3) hollow spheres, emphasizing their enhanced visible-light photocatalytic activity. Utilizing a novel, facile, two-step evaporation-induced self-assembly (EISA) approach, monodisperse BiFeO3 hollow spheres were synthesized with a narrow particle size distribution. The synthesis involved Bi/Fe citrate complexes as precursors and the triblock copolymer Pluronic P123 as a soft template. The BiFeO3 hollow spheres demonstrated outstanding photocatalytic performance in degrading the emerging pollutants Rhodamine B and metronidazole under visible-light irradiation (100% degradation of Rhodamine B in <140 min and of metronidazole in 240 min). The active species in the photocatalytic process were identified through trapping experiments, providing crucial insights into the mechanisms and efficiency of semiconductor hollow spheres. The findings suggest that the unique structural features of BiFeO3 hollow spheres, combined with their excellent optical properties, make them promising candidates for photocatalytic applications.

Nanoporous aluminosilicate mediated synthesis of 2- and 2,2-substituted 2,3-dihydroquinazolin-4(1H)-ones

Nanoporous silicate materials, made by an operationally simple evaporation-induced self-assembly (EISA) approach, efficiently catalyze the formation of 2-substituted 2,3-dihydroquinazolin-4(1H)-ones from aldehydes and dimethyl acetals. This methodology can be extended to encompass the reaction of ketones and ketals to provide facile access to 2,2-disubstituted and spiro dihydroquinazolin-4(1H)-ones in high yields and short reaction times.

Liquid Crystal Cellulose Nanocrystal/ Polyvinylpyrrolidone Pigments Engineered from Agro‐Waste Sugarcane Bagasse

AbstractBio‐inspired iridescent materials can possibly replace organic dyes and pigments, however, fabricating materials that resemble the appearance of absorbing pigments is challenging. Extracting cellulose nanocrystals (CNCs) from waste biomass is a sustainable practice in light of socio‐economic and environmental concerns. In an attempt, CNCs from sugarcane bagasse are isolated through acid hyrdolysis. Stable anisotropic dispersions of CNCs are doped with polyvinylpyrrolidone (PVP). Iridescent composite films are cast from these suspensions through evaporation–induced self‐assembly approach (EISA). The physicochemical properties of the films are studied at different loadings of PVP. These iridescent CNC/PVP composite films are then ball‐milled to produce iridescent red and blue tone color pigments. The morphology and optical properties of pigments are studied through Field emission scanning electron microscopy (FE‐SEM) and Hot‐stage Polarized Optical Microscopy (POM). These pigments are then re‐dispersed in a transparent polar polymer matrix to visually observe the color induced by them using solvent casting approach.

Cerium and carbon-sulfur codoped mesoporous TiO2 nanocomposites for boosting visible light photocatalytic activity

Ce and C–S codoped mesoporous TiO2 nanocomposites were synthesized via a sol-gel method integrated with an evaporation-induced self-assembly approach. The basic physicochemical characteristics of the synthetic samples were analyzed via a series of characterization techniques. The results reveal that C–S and Ce codoping on mesoporous TiO2 enhances the photocatalytic activity owing to the synergistic effect caused by narrowing the band gap, enhancing adsorption, trapping and transferring the excited e–/h+ pairs and suppressing the recombination of e–/h+ pairs. Furthermore, the obtained C,S–TiO2/CeO2 materials exhibit large specific surface areas and numerous pores which not only effectively improve the adsorption-enrichment capability, but also supply multi-dimensional mass and electron transfer channels. The photodegradation efficiency of RhB by C,S–TiO2/CeO2 within 40 min is nearly 100%, and its degradation efficiency is 6.63 times that of undoped TiO2. Recycling experiments show that mesoporous C,S–TiO2/CeO2 shows excellent recoverability and stability. Furthermore, by trapping experiments, •O2–, h+ and •OH are the predominant active species and a possible reaction mechanism is proposed.

Facile synthesis of Co-Rh bimetallic catalysts for methane decomposition: Effect of support morphology

In this study, the performance of 10 wt.% Co -1 wt. % Rh/TiO2 catalysts with varying textural properties have been investigated to produce the hydrogen and carbon nanotubes via the methane decomposition process. An improved evaporation-induced self-assembly approach synthesized the mesoporous TiO2 supports, and Co-Rh nanoparticles over the as-synthesized TiO2 supports were created by the co-impregnation method. XRD, BET, TGA, SEM, and TEM studies characterized the fresh and used catalysts. The findings revealed that the texture of TiO2 support has an important influence on catalytic performance. With the increase in calcination temperature, the specific surface area of the catalysts decreases while the anatase content of TiO2 species increases. The catalyst prepared with TiO2 calcined at 600 °C displayed superior catalytic activity and stability due to the better metal dispersion and higher anatase phase content in support. The initial activity depended on the specific surface area, whereas the stability or the hydrogen productivity for the equal deactivation level was related to the anatase composition of the catalyst. The nature of deposited carbon varies due to the phase composition of TiO2. The SEM and TEM images revealed that anatase TiO2 generated smaller multi-walled carbon nanotubes (MWCNTs) with a more consistent diameter distribution than the other catalysts. Catalysts with an amorphous composition increase the formation of CHx carbon species. The apparent activation energies for various Co-Rh catalysts varied between 65 and 85 kJ mol−1. The Co-Rh bimetallic combination had more significant activity than the Ni metal.

Aerosol-phase synthesis of bimetallic NiCu oxide-decorated CeO2 nanoparticle cluster for catalytic methane combustion

• Successful aerosol synthesis of NiCuOx@CeO2 for catalytic methane combustion. • Composition and crystalline of the hybrid nanostructure were tunable. • Superior catalytic activity (TOFCH4: 0.483 s −1 at 400 °C) was achievable. • Ni-preferred adsorption and dissociation of methane was rate-determining step. A raspberry-structured hybrid nanocatalyst composed of spherical NiCu bimetallic oxide nanoparticle decorated on ceria nanoparticle cluster (NiCuO x @CeO 2 ) was successfully synthesized via a gas-phase evaporation-induced self-assembly approach. Chemical composition and crystalline of the NiCuO x @CeO 2 were tunable during the gas-phase synthesis. The NiCuO x @CeO 2 demonstrates superior catalytic performance toward methane combustion, showing low light-off temperature (∼350 °C), high conversion ratio, high turnover frequency (0.483 s −1 at 400 °C) and sufficiently high 8-h operation stability were achievable by adjusting the composition of the catalysts. The results show that 1Ni0CuO x @CeO 2 (i.e., the sample without CuO) demonstrated the highest catalytic activity, implying adsorption and dissociation of CH 4 (i.e., preferably on NiO) was rate-determining step. Significant higher activity, especially under a low temperature range (<380 °C), was identified for the hybrid NiCuO x @CeO 2 samples under an oxygen-lean condition than in oxygen-rich condition, indicating the addition of CuO promoted redox ability of NiCuO x in the hybrid nanostructure. The stability was shown to be proportional to the ratio of NiO in the catalysts, indicating that increase of NiO amount was beneficial for thermal stability. The prototype study demonstrates the development of bimetallic-based hybrid nanostructured catalysts nanoparticle clusters. The mechanistic understanding developed in this study shows promise for the tuning of the abilities in methane dissociation versus its redox properties to achieve an optimal performance in methane-based energy applications.

Photo-Oxidation of Glycerol Catalyzed by Cu/TiO2

In the present study, glycerol was oxidized by photocatalysis to glyceraldehyde, formaldehyde, and formic acid. Copper-doped TiO2 was synthesized by the evaporation-induced self-assembly approach and it was used as catalyst during the glycerol photo-oxidation reactions. The prepared mesoporous material exhibited high specific surface area (242 m2/g) and band gap energy reduction of 2.55 eV compared to pure titania (3.2 eV) by the synthesis method due to the presence of copper cations (Cu2+ identified by XPS). The catalyst showed only anatase crystalline phase with nanocrystals around 8 nm and irregular agglomerates below 100 μm. The selectivity and formation rate of the products were favored towards formaldehyde and glyceraldehyde. The variables studied were catalyst amount, reaction temperature, and initial glycerol concentration. The response surface analysis was used to evaluate the effect of the variables on the product’s concentration. The optimized conditions were 0.4 g/L catalyst, 0.1 mol/L glycerol, and temperature 313.15 K. The response values under optimal conditions were 3.23, 8.17, and 1.15 mM for glyceraldehyde, formaldehyde, and formic acid, respectively. A higher selectivity towards formaldehyde was observed when visible light was used as the radiation source. This study is useful to evaluate the best reaction conditions towards value-added products during the oxidation of glycerol by photocatalysis using Cu/TiO2.

On the design of mesostructured acidic catalysts for the one-pot dimethyl ether production from CO2

Dimethyl ether (DME) production from hydrogenation of CO2 based on two-function (redox and acidic) catalysts is receiving increasing attention due to the high demand for alternative and green fuels. In this work, we propose different mesostructured acidic metal oxides as methanol dehydration catalysts to be used as physical mixtures in combination with a commercial Cu-based redox catalyst (CZA) for the CO2-to-DME one-pot production. Al-MCM-41, TiO2 and TiO2-ZrO2 mixed oxides, obtained through Sol-Gel methods, either in a conventional or Evaporation-Induced Self-Assembly approach were selected as mesostructured acidic systems and compared with a commercial zeolite (ferrierite). The regular mesoporous structure should render the active sites of the acidic catalyst easily accessible for CO2 and H2 and allow a homogeneous dispersion of the redox phase inside the mesopores in view of a possible development of bifunctional catalysts (redox + acidic). With the aim of understanding how the textural and acidic properties can be correlated with the performances and eventually design efficient dehydration catalysts, a careful study on the acidic sites was performed by both adsorption microcalorimetry with ammonia and FTIR-monitored adsorption of pyridine. The results of the performances highlighted a higher activity toward methanol dehydration for catalysts featured by Brønsted sites (zeolite and Al-MCM-41); as for catalysts with Lewis sites only (TiO2, Ti0.77Zr0.23O2) better performances were shown in case of systems presenting sites of moderate strength (Ti0.77Zr0.23O2). In the light of the above, Al-MCM-41 and TiO2-ZrO2 demonstrated to be the most promising mesostructured dehydration catalysts in terms of selectivity to DME.

Highly thermally conductive yet mechanically robust composites with nacre-mimetic structure prepared by evaporation-induced self-assembly approach

Highly thermally conductive and mechanically strong nanocomposites for efficient thermal management have received wide attention because of the rapid development of modern electronics. Boron nitride nanosheet (BNNS) with combined benefits of high thermal conductivity (TC) and good electrical insulation has been considered a promising filler to fabricate thermally conductive nanocomposites. Herein, inspired by biological systems, large-scale and high-performance artificial nacre-like composite composed of BNNS and oxidized cellulose nanocrystal (OCNC) is fabricated through simple evaporation-induced self-assembly (EISA) approach for the first time. Thanks to the template effect of OCNC host, BNNS and OCNC are self-assembled to form an artificial layer-by-layer nacre structure, where OCNC combined with the epoxy-based adhesive agent (AA) serves as the mortar to form a stiff and dense structure. The resulting BNNS-OCNC-AA composite at a relative low BNNS loading of 11.6 vol% exhibits a high in-plane thermal conductivity of 10.9 W/mK as well as the excellent tensile strength of 197.3 MPa, which are prominent compared to other composites fabricated via the various currently established methods under higher filler loadings (13.4 ~ 95 vol%). From the characterization results, we could attribute the multiple properties to the construction of the unique nacre-like structure and the robust interfacial interaction. The artificial nacre-like BNNS composite with excellent thermal and mechanical properties simultaneously has significant potential application for thermal management in flexible and wearable electronics fields.

Inhibited combustion of graphene paper by in situ phosphorus doping and its application for fire early-warning sensor

Although traditional fire detectors are widely used in many occasions, they still show some limitations, such as slow fire response and poor resistance to severe conditions. Thus, it is urgent to design and exploit early fire-warning device with ultrafast response and flame-retardant ability to provide timely and fast alarm. Herein, graphene oxide paper functionalized with phosphoric acid (GO-PA) is fabricated by a facile and environmentally friendly water evaporation-induced self-assembly approach. Based on the flame-induced electrical resistance transformation characteristic of GO-PA, a fire-warning detector is designed to reliably monitor early fire. Fire alarm can be triggered within 0.5 s when GO-PA samples are attacked by fire. The GO-PA composite paper is more sensitive than GO-based fire sensors reported in the literature. Phosphorus atoms are in situ doped into graphene structure during flame exposure. Combustion reaction of GO is significantly retarded by the incorporated PA, thus fire duration time of GO is greatly improved. This work paves a new way to improve fire detection performance of GO-based sensors. This work provides a guide for the development of advanced fire detection and early-warning sensors to provide reliable and continuous alarm signals.

Nacre-inspired Polymer Nanocomposites with High-performance and Multifunctional Properties Realized by a Facile Evaporation-induced Self-assembly Approach

A bioinspired polymer-based nanocomposite consisting of hierarchically oriented 2D nanomaterials and polymers exhibits extraordinary properties in various applications. However, it is still a great...

Ordered mesoporous Fe-Al2O3 based-catalysts synthesized via a direct "one-pot" method for the dry reforming of a model biogas mixture

Biogas plays a vital role in the emerging renewable energy sector and its efficient utilization is attracting significant attention as an alternative energy carrier to non-renewable fossil fuel resources. Since biogas consists mainly of CH4 and CO2, dry reforming of methane arises as an appropriate process enabling its chemical conversion to high-quality synthesis gas (syngas: H2 and CO mixtures). In this study, we synthesized via a direct "one-pot" method following an evaporation-induced self-assembly approach, ordered mesoporous Fe10%, Ni5% and Fex%Ni(1-x) (x: 2.5, 5 or 7.5%) in Al2O3 as catalysts for syngas production via dry reforming of a model biogas mixture (CH4/CO2 = 1.8, at a temperature of 700 °C). Monometallic Fe10%Al2O3 catalyst presented lower reactivity levels and slightly deactivated during catalysis compared to stable Ni5%Al2O3. According to physico-chemical characterization techniques, the incomplete reduction of Fe2O3 into Fe3O4 rather than Fe0 nanoparticles (catalytically active) coupled with the segregation of Fe3O4 oxides were the main factors leading to the low performance of mesoporous Fe10%Al2O3. These drawbacks were overcome upon the partial substitution of Fe by Ni (another transition metal) forming specifically bimetallic Fe5%Ni5%Al2O3 displaying reactivity levels close to thermodynamic expected ones. The formation of Fe-Ni alloys stabilized iron inside alumina matrix and protected it from segregation. Along with the confinement effect, spent catalyst characterizations showed high resistance towards coke deposition.

Large-pore ordered mesoporous carbon as solid-phase microextraction coating for analysis of polycyclic aromatic hydrocarbons from aqueous media

In this study, large pore ordered mesoporous carbon (LP-OMC) material was first applied as solid-phase microextraction (SPME) coating for the extraction of polycyclic aromatic hydrocarbons (PAHs) from aqueous media. The LP-OMC SPME fiber was prepared via the dip-coating method in-combination with evaporation-induced self-assembly (EISA) approach. The LP-OMC coating material possessed large specific surface area with the BET surface area of 629 m2 g−1 and uniform large pore size at the mean value of 13.5 nm with a narrow pore-size distribution. The extraction performance of LP-OMC fiber for PAHs was compared with another kind of OMC fiber with pore diameter of 4.1 nm. The results implied that the LP-OMC fiber showed better extraction capability towards PAHs. The developed LP-OMC-SPME method for PAHs exhibited wide linear ranges (0.01–50 μg L−1), low detection limits (1.6–10.0 ng L−1) and good repeatabilities (3.9–7.4% for one fiber, 6.7–11.7% for fiber-to-fiber). The method was successfully applied for the analysis of PAHs in real environmental water samples with satisfactory recovery ranging from 82.6% to 112.1%.

Arsenate adsorption on iron-impregnated ordered mesoporous carbon: Fast kinetics and mass transfer evaluation

Removal of arsenic (As) from drinking water sources is much needed worldwide, and point-of-use (POU) treatment could be an effective solution for residential applications. Adopting existing removal technologies that are successful in large-scale treatment to POU units, however, is rather ineffective due to the short hydraulic residence time in POU systems. In this study, we investigated the use of iron-containing ordered mesoporous carbon (FeOMC) for rapid arsenate [As(V)] sorption in batch reactors. The OMC was prepared by an evaporation-induced self-assembly approach followed by impregnation of iron oxides, which was identified mainly as maghemite (γ-Fe2O3) by coupled high-resolution transmission electron microscopy and electron energy loss spectroscopy microanalysis. A rapid kinetics of As(V) adsorption was observed, showing that at an initial concentration of 52.1 μg As/L and solid loading of 2.0 g/L, 84.8% of As(V) was removed within 90 s at pH 6.1. The kinetics was satisfactorily modelled according to the mass transfer of As(V) in a single FeOMC grain; and the results suggested that the intraparticle diffusion along the mesoporous channels could be hindered by adsorption. In summary, this study has not only developed ordered mesoporous materials for rapid arsenic adsorption, but also gained insights into the factors controlling the sorption kinetics by evaluating the mass transfer inside the straight and uniform channels of surface-functionalized OMC.

One-pot synthesis of mesoporous Al2O3-supported Pt-Pd catalysts for toluene combustion

Mesoporous Al2O3-supported Pt-Pd catalyst was prepared via a one-step evaporation-induced self-assembly (EISA) process and employed for toluene combustion. It was found that the T90 (160 °C) and activation energy (43 kJ/mol) of the one-pot prepared Pt-Pd-Al2O3 catalyst are lower than the conventional Al2O3- supported Pt-Pd catalyst prepared by the wet impregnation method (250 °C, 49.8 kJ/mol). Moreover, the one-pot prepared Pt-Pd-Al2O3 catalyst shows the presence of nano Pt-Pd particles in the mesochannels. In terms of the one-pot EISA approach, the bi-metallic Pt-Pd-Al2O3 catalyst exhibits reduced noble-metal mean particle size (6.1 nm) and T90 than the mono-metallic Pt-Al2O3 and Pd-Al2O3 catalysts. It was demonstrated that the present Pt-Pd-Al2O3 catalytic system exhibits the lowest T90 and T50 parameter values and apparent activation energy at comparable space velocities and toluene feed composition compared to several best performed catalysts reported in the literature.

Solvothermal-assisted evaporation-induced self-assembly of ordered mesoporous alumina with improved performance

A solvothermal-assisted evaporation-induced self-assembly (SA-EISA) approach has been developed for the synthesis of ordered mesoporous alumina (OMA) materials with high thermal stability and improved performance in catalysis. In conventional EISA process, the evaporation step is accompanied by the hydrolysis of organic aluminum precursors, thus the evaporation conditions have significant influences on the reaction and the final structure of OMA. In our approach, the solvothermal treatment step promotes the complete hydrolysis of aluminum precursors and produces partially condensed cluster-like aluminum hydroxyl species, which allows the formation of OMA in a broad range of evaporation conditions. Compared to mesoporous alumina obtained by conventional EISA process, OMA materials prepared by SA-EISA approach exhibit higher specific surface area, pore volume and thermal stability. When used as supporting materials for vanadium oxide catalyst, OMA materials obtained by the SA-EISA approach exhibit excellent activity, selectivity and stability for ethylbenzene dehydrogenation with carbon dioxide as a mild oxidant. Our contribution has provided new understanding in the synthesis of OMA materials with improved performance for catalytic applications.

Mesoporous titanium dioxide photoanodes decorated with gold nanoparticles for boosting the photoelectrochemical alkali water oxidation

This work reports the photo-electrochemical enhancement of alkali water oxidation at mesoporous TiO2 (m-TiO2) photoanode prepared by evaporation-induced self-assembly (EISA) approach and photomodified with Au nanoparticle (Au/m-TiO2). The physicochemical characterizations of the modified photoanodes showed the uniform incorporation of gold nanoparticles having a diameter range of 3–5 nm into the mesoporous TiO2 substrate. The photo-electrochemical investigations demonstrate that the Au/m-TiO2 modified catalysts under the simulated solar light illumination exhibit excellent photoelectrochemical activity for alkali water oxidation and photocurrent density of 1.30 mA/cm2 has been achieved within the potential window of 0.1–1.7 V vs. reference hydrogen electrode (RHE), which is a 2.5 times higher photocurrent than that observed at bare m-TiO2 anode. An apparent oxygen evolution rate of 45.80 mmol/mg h was observed at a potential of 1.25 V vs RHE for Au/m-TiO2 which is significantly higher than that obtained for bare m-TiO2 (12.5 mmol/mg h). The mesoporous TiO2 materials modified with suitable metal nanoparticles via ex-situ photodeposition have shown substantial current gain during the photo-electrochemical water splitting reaction due to the boosting effect of the plasmonic nanostructure.

Investigation of the Na Storage Property of One-Dimensional Cu2- xSe Nanorods.

In this study, one-dimensional Cu2- xSe nanorods synthesized by a simple water evaporation-induced self-assembly approach are served as the anode material for Na-ion batteries for the first time. Cu2- xSe electrodes express outstanding electrochemical properties. The initial discharge capacity is 149.3 mA h g-1 at a current density of 100 mA g-1, and the discharge capacity can remain at 106.2 mA h g-1 after 400 cycles. Even at a high current density of 2000 mA g-1, the discharge capacity of the Cu2- xSe electrode still remains at 62.8 mA h g-1, showing excellent rate performance. Owing to the excellent electronic conductivity and one-dimensional structure of Cu2- xSe, the Cu2- xSe electrodes manifest fast Na+ ion diffusion rate. Moreover, detailed Na+ insertion/extraction mechanism is further investigated by ex situ measurements and theoretical calculations.

Thermal Stability of Metal-Organic Frameworks and Encapsulation of CuO Nanocrystals for Highly Active Catalysis.

We report an aerosol-based approach to study the thermal stability of metal-organic frameworks (MOFs) for gas-phase synthesis of MOF-based hybrid nanostructures used for highly active catalysis. Temperature-programmed electrospray-differential mobility analysis (TP-ES-DMA) provides the characterization of temperature-dependent morphological change directly in the gas phase, and the results are shown to be highly correlated with the structural thermal stability of MOFs determined by the traditional measurements of porosity and crystallinity. The results show that MOFs underwent thermal decomposition via simultaneous disassembly and deaggregation. Trimeric Cr-based MIL-88B-NH2 exhibited a higher temperature of decomposition ( Td), 350 °C, than trimeric Fe-based MIL-88B-NH2, 250 °C. For UiO-66, a significant decrease of Td by ≈100 °C was observed by using amine-functionalized ligands in the MOF structure. Copper oxide nanocrystals were successfully encapsulated in the UiO-66 crystal (Cu xO@UiO-66) by using a gas-phase evaporation-induced self-assembly approach followed by a suitable thermal treatment below Td (i.e., determined by TP-ES-DMA). Cu xO@UiO-66 demonstrated a very high catalytic activity and stability to CO oxidation, showing at least a 3-time increase in CO conversion compared to the bare CuO nanoparticle samples. The study demonstrates a prototype methodology (1) to determine structural thermal stability of MOFs using a gas-phase electrophoretic method (TP-ES-DMA) and (2) to gas-phase synthesize CuO nanocrystals encapsulated in MOFs.