Simple Redox Reaction Research Articles

Lithiophilic Reduced Graphene Oxide/Carbonized Zeolite Imidazolate Framework-8 Composite Host for Stable Li Metal Anodes.

Lithium (Li) metal is regarded as a next-generation anode material owing to its high energy density. However, issues such as dendritic growth and volume changes during charging and discharging pose significant challenges for commercialization. We propose using lithiophilic reduced graphene oxide (rGO) and carbonized zeolite imidazolate framework-8 (C-ZIF-8) composites as host materials for Li to address these problems. The rGO/C-ZIF-8 composites are synthesized through a simple redox reaction followed by carbonization and are characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The roles of chemical composition, characteristics, and morphology are demonstrated. As a result of these favorable structural and functional properties, the Li symmetric cell with rGO/C-ZIF-8 exhibits a stable voltage profile for more than 100 h at 1 mA cm-2 without short-circuiting. A relatively low Li plating/stripping overpotential of ~101.5 mV at a high current density of 10 mA cm-2 is confirmed. Moreover, a rGO/C-ZIF-8-Li full cell paired with a LiFePO4 cathode demonstrates good cyclability and rate capability.

Polymerization-induced aramid nanofiber in-situ loaded poly-pyrrole for construction of ultra-strong microwave absorption aerogel

Increasing electromagnetic (EM) radiation and EM pollution have driven extensive attention for high efficiency EM wave absorbing materials, especially aerogel-based composite absorbing materials, which are lightweight, flexible, and heat-insulating. Here, highly efficient absorbing poly-pyrrole@aramid nanofibers (Ppy@ANF) aerogels were assembled using Ppy@ANF nanofibers with core-shell structure. Ppy@ANF nanofibers were constructed for the first time by introducing a Ppy capping layer on the surface of ANF induced by ambient polymerization through a simple redox reaction. Benefit from the macroscopic porous structure of the aerogel and the microscopic core-shell structure design. The Ppy@ANF aerogels achieved an ultra-broadband absorption of 8.27 GHz at 3.43 mm, amd strong absorption characteristic with a reflection loss of −59.63 dB. Meanwhile, it had excellent thermal insulation and mechanical properties. Ppy@ANF aerogels are looked bright to be applied as flexible, lightweight, heat-insulating, and highly efficient absorbing material in wearable electronics, artificial intelligence and other high-tech fields.

Unusual reactivity of 2,2-diphenyl-1-picrylhydrazyl (DPPH) with Fe3+ controlled by competing reactions.

2,2-Diphenyl-1-picrylhydrazyl (DPPH) is a stable organic free radical widely used in various fields as a model free radical. There is scarce information about the stability of this compound in the chemical environments in which it is used. Side reactions between DPPH and other species can alter the precision of experiments that use DPPH, such as the evaluation of antioxidant properties amongst others. Following recent investigations highlighting reactions between DPPH and metal cations or Lewis acids, a quantitative reaction between DPPH and Fe3+ in acetonitrile was studied in the present work. UV-Vis spectroscopy and electrochemistry were used to monitor the reaction. The results obtained indicate a fast and multistep reaction between Fe3+ and DPPH that can be simplified as a simple redox reaction with the formation of Fe2+ and DPPH+. The reaction mechanism proposed follows complex steps involving two competing phenomena: a disproportionation which accelerates the reaction and an oxidation process that slows it down through DPPH regeneration.

Construct Ni–SnO2 core coated amorphous Ni(BO2)2 shell boosts water splitting for hydrogen production

Through a simple redox reaction, the precursor of Ni (OH)2 mixed with SnO2 was in situ transformed into a core-shell structure with elemental Ni blend SnO2 as the core and nickel metaborate as the shell. The metaborate shell is an excellent adsorption site for water molecules, which paves the way for subsequent hydride adsorption. When a small amount of SnO2 is mixed with elemental Ni, the electronic structure is optimized, and the electron enrichment of Ni is realized, making the hydrogen adsorption performance better. This core-shell synergy promotes the Vomer step in HER, thereby enhancing HER performance. In addition, Ni–Sn@NiBO/NF possesses larger electrochemical surface area and smaller charge transfer resistance. Only an overpotential of 22 mV is needed to drive a current density of 10 mA cm−2, indicating the excellent HER performance of the Ni–Sn@NiBO/NF catalyst. At high current density of 50 mA cm−2, the overpotential is only 79 mV. When Ni–Sn@NiBO/NF is used as the bifunctional catalyst for coupling HER and OER, the voltage is only 1.595 V at 10 mA cm−2. It shows that the catalyst has great application potential in electrocatalytic water decomposition to produce hydrogen.

A MnAl double adjuvant nanovaccine to induce strong humoral and cellular immune responses.

At present, the most widely used aluminum adjuvants have poor ability to induce effective Th1 type immune responses. Existing evidence suggests that manganese is a potential metal adjuvant by activating cyclic guanosine phospho-adenosine synthase (cGAS)-interferon gene stimulator protein (STING) signaling pathway to enhance humoral and cellular immune response. Hence, the effective modulation of metal components is expected to be a new strategy to improve the efficiency of vaccine immunization. Here, we constructed a manganese and aluminum dual-adjuvant antigen co-delivery system (MnO2-Al-OVA) to enhance the immune responses of subunit vaccines. Namely, the aluminum hydroxide was first fused on the surface of the pre-prepared MnO2 nanoparticles, which were synthesized by a simple redox reaction with potassium permanganate (KMnO4) and oleic acid (OA). The engineered MnO2-Al-OVA could remarkably promote cellular internalization and maturation of dendritic cells. After subcutaneous vaccination, MnO2-Al-OVA rapidly migrated into the lymph nodes (LNs) and efficiently activate the cGAS-STING pathway, greatly induced humoral and cellular immune responses. Of note, our findings underscore the importance of coordination manganese adjuvants in vaccine design by promoting the activation of the cGAS-STING-IFN-I pathway. With a good safety profile and facile preparation process, this dual-adjuvant antigen co-delivery nanovaccine has great potential for clinical translation prospects.

Cuprous Oxide-Based Cationic Hydrogel by the Integration of Enrichment and Immobilization of Radioiodine (I-, IO3-) in Aqueous Solution.

The efficient capture and immobilization of radioiodine (I-, IO3-) is of great importance in radioactive waste management. Here, a Cu2O-loaded three-dimensional bulk cationic hydrogel composite (Cu2O@CH) was successfully prepared by simple redox reactions and UV photopolymerization, which realized the rapid enrichment and efficient immobilization of I- and IO3-. The adsorption experiments showed that the maximum adsorption capacity of Cu2O@CH for I- in the solution at pH = 3 reached 416.5 mg/g, and the adsorption capacity of IO3- in the solution at pH = 6 could reach 313.4 mg/g. It exhibited extremely fast adsorption kinetics for I- and IO3-. In addition, Cu2O@CH also exhibited efficient I- and IO3- removal from simulated high-level liquid waste. The rapid capture and effective immobilization of radioiodine (I-, IO3-) were realized by the electrostatic interaction of -N+(CH3)3 groups in Cu2O@CH with I- and IO3-, as well as the chemical reactions between Cu2O and I-. The bulk cationic hydrogel composite explored the multifunctional role toward fast, high adsorption capability and easy handling, highlighting its superiority compared to the powder adsorbent, which renders it a potential adsorbent for the removal of radioactive iodine (I-, IO3-) in nuclear wastewater treatment.

Reducing Carbonaceous Salts for Facile Fabrication of Monolayer Graphene.

Novel methods and mechanisms for graphene fabrication are of great importance in the development of materials science. Herein, a facile method to directly convert carbonaceous salts into high-quality freestanding graphene via a simple one-step redox reaction, is reported. The redox couple can be a combination of sodium borohydride (reductant) and sodium carbonate (oxidant), which can readily react with each other when evenly mixed/calcined and yield gram-scale, high-quality, contamination-free, micron-sized, freestanding graphene. More importantly, this method is applicable to a variety of input reductants and oxidants that are low cost and easily accessible. An in-depth investigation reveals that the carbonaceous oxidants can not only provide reduced carbon mass for graphene formation but also act as a self-template to guide the polymerization of carbon atoms following the pattern of the monolayer, six-carbon rings. In addition, the direct formation of graphene exhibits theoretically lower energy barriers than that of other allotropes such as fullerene and carbon nanotube. This facile, low-cost, scalable, and applicable method for mass production of high-quality graphene is expected to revolutionize graphene fabrication technology and boost its practical application to the industry level.

A facile synthesis of a copper(I) thiourea sulphate complex and its application for highly efficient chalcopyrite solar cells.

The precursor compound plays a crucial role in the development of low-cost chalcogenide thin-film solar cells via a solution approach. In this work, we report on the synthesis of a new complex [Cu((NH2)2CS)3]2SO4·H2O through a simple redox reaction between inexpensive Cu(CH3COO)2·H2O and thiourea (TU) in water. Using this complex as a copper source, a stable dimethylformamide solution was made and copper indium sulfoselenide CuIn(S,Se)2 thin film solar cells with a high efficiency of 12.2% have been demonstrated.

MnO2 nanospheres integrated into hierarchical porous carbon as electrode for high performance asymmetrical supercapacitors

Hierarchical porous carbon (HPC) is considered as an ideal electrode material for supercapacitors on account of its high stability and developed pore structure. MnO2, possessing ultrahigh theoretical capacitance, can provides pseudocapacitance to facilitate electrochemical performances. Herein, HPC with large specific surface area (1153 m2 g−1) and abundant mesopores (95.76 % mesopore ratio) is prepared via ZnCl2 activation, which can act as the support and substrate for MnO2. Subsequently, in-situ synthesis of MnO2 nanospheres and preparation of MnO2/HPC composites (MnO2@HPCs) are realized simultaneously by a simple redox reaction. Benefiting from high conductivity of HPC (4.07 S m−1) and moderate size of MnO2 nanospheres (∼40–50 nm), MnO2@HPCs exhibit an excellent specific capacitance (521 F g−1 at 0.5 A g−1 and 468 F g−1 at 1 mV s−1) and pseudocapacitance effect in three-electrode system. Further, the asymmetric supercapacitor adopting MnO2@HPC160 and HPC as the cathode and anode delivers a superior capacitance value (74 F g−1 at 0.5 A g−1), outstanding rate performance (79.7 % at 10 A g−1) and remarkable energy density of 32.93 Wh kg−1 in 1 M Li2SO4 electrolyte. These results demonstrate that the MnO2/hierarchical porous carbon composite is a promising candidate as electrode material for high-performance supercapacitors.

Synthesis of Pd-Fe2O3 nanoflakes nanocomposite for superior energy storage device

BackgroundThe synthesized nanocomposites have enhanced stability due to the composite effect, high surface area, pore volume, and low charge transfer resistance of the nanocomposite. Moreover, the prepared nanocomposites reveal excellent specific capacitance, fast charge-discharge, and long-term durability. MethodThe Pd-Fe2O3 nanoflakes nanocomposite has been prepared by the simple redox reaction under hydrothermal conditions. Significant findingsThe as-synthesized Pd-Fe2O3 nanoflakes nanocomposite shows excellent capacitance of 531 F g−1 at a current density of 1 A g−1 under acidic electrolyte whereas, the commercial Fe2O3 shows only 215 F g−1. The charge-storage mechanism of as-synthesized nanocomposite shows the major capacitive contribution to store the total charge. Further, a solid-state asymmetric supercapacitor device fabricated and exhibits excellent capacitance of 137 F g−1 at 1 A g−1 current density using PVA-H2SO4 gel electrolyte along with a maximum energy density of 61.65 Wh kg−1 and power density of 3.5 kW kg−1. Interestingly, the as-synthesized Pd-Fe2O3 nanoflakes nanocomposite shows outstanding stability up to 8000 continuous charge-discharge cycles using the acidic electrolyte. The retention-specific capacitance of the nanocomposite is found to be 87% after cycles stability.

In situ precipitated NiCo nanoparticles synergize with metaborate to promote hydrogen evolution and couple with urea oxidation to reduce overall water splitting potential

A novel NiCo nanoparticles anchored on Ni(Co)(BO2)2 are constructed via a simple redox reaction of NiCo LDH (layered double hydroxide) with NaBH4 which method avoids the Ni foam deformation caused by high temperature reduction or pyrolysis. The experimental and DFT (density functional theory) investigation reveal metaborate (Ni(Co)(BO2)2) exhibits a stronger water adsorption capacity than that conventional metal LDH, which is conducive to the occurrence of hydrogen adsorption in the next step, while NiCo (ΔGH* is closer to 0) is a more suitable hydrogen reaction site than Ni or Co, this synergistic effect of the two substances greatly promotes Volmer step for HER (hydrogen evolution reaction), thereby fundamentally improving HER. The existence of Co0 helps to generate more Ni0, and Co plays an electronic auxiliary role. The Ni0(Co0)-Ni(Co)(BO2)2/NF catalyst possesses small charge transfer resistance, large electrochemical surface area and good hydrophilicity. The Ni0(Co0)-Ni(Co)(BO2)2/NF catalyst exhibits a great application prospect with an overpotential of only 25 mV at a current density of 10 mA cm−2. Even at a large current density of 100 mA cm−2, the overpotential is 107 mV. At a current density of 10 mA cm−2, the voltages of OER (oxygen evolution reaction) and UOR (urea oxidation reaction) are 1.561 V (vs. RHE) and 1.353 V, respectively. Using Ni0(Co0)-Ni(Co)(BO2)2/NF as a bifunctional catalyst for HER and UOR, only 1.47 V can drive a current density of 10 mA cm−2. It is shown that the catalyst will greatly reduce energy consumption and decompose urea when coupling HER and UOR.

Development of a simple analytical method for the determination of nitrite in waters using redox reaction and smartphone.

In this study, it was aimed to perform the colorimetric determination of nitrite in waters using the redox reaction of iodide in acidic conditions with smartphone. The simple redox reaction of iodide and nitrite in an acidic medium was used instead of the conventional nitrite methods based on the formation of azo dye. The quantitative relationship between the yellow-colored iodine formed because of the reaction and nitrite was determined by the digital image-based colorimetric method (DIC). In the optimal experimental conditions, detection limit and R2 values were determined as 0.02mg/L and 0.9925, respectively. New method (Redox-DIC method) was validated by the standard Griess Method for nitrite in lake waters. The perfect recovery results (94-112%) were calculated for lake, river, tap, and spring waters spiked at different concentrations, and very good (< 5.0%) percent relative standard deviation values were recorded. Unlike conventional nitrite methods, organic reagents and solvents were not used in this method. The method is fast, simple, and low cost.

Highly efficient ozone decomposition against harsh environments over long-term stable amorphous MnOx catalysts

Ground-level ozone causes great harm both to ecosystems and human health and should be strictly controlled. Manganese oxide (MnOx) is severely limited by catalyst deactivation due to environmental variations such as humidity and temperature. Herein, amorphous MnOx, prepared via a simple and mild redox reaction showed complete elimination of 40 ppm ozone at a high weight hourly space velocity of 600,000 mL·g−1 h−1, under the mild environmental condition with the relative humidity of 50 % and 25 °C. It also kept predominant activity and remarkable stability even at harsh environmental conditions of low temperature (0 °C) or high humidity (90 %). The superior ozone decomposition performance of MnOx resulted from the abundant grain boundaries and manganese redox pairs, which promoted oxygen vacancies generation and electron transfer. The findings may shed new light on the design of highly efficient and stable MnOx catalysts and are expected to drive great advances for large-scale practical applications.

MXene-copper oxide/sulfonated polyether ether ketone as a hybrid composite proton exchange membrane in electrochemical water electrolysis

Water electrolysis through a proton exchange membrane is one approach for hydrogen energy production via a simple redox reaction. This work focused on the development of a hybrid composite proton exchange membrane (PEM), MXene-Cu2O/SPEEK, which was used for proton transfer in a water electrolysis process. The sample of the 4%MXene-Cu2O/SPEEK membrane demonstrated the highest proton conductivity of 0.0105 Scm−1 at 30 °C. Further, the oxygen transmission rate of the 4%MXene-Cu2O/SPEEK was 33.67 cc m−2 day−1, whereas that of the commercially available Nafion 212 was 28.53 cc m−2 day−1. The flow rate of H2 gas evolution was 3.68 mL min−1 when using the 4%MXene-Cu2O/SPEEK composite PEM as the H+ ion exchange separator in the water electrolysis system; this flow rate is faster than that of a pristine SPEEK membrane. Interestingly, the addition of the MXene-Cu2O composite into the SPEEK polymer matrix promoted the oxidative stability of the composite PEM, which is vital for the long-term operation of the PEM water electrolysis. The 4%MXene-Cu2O/SPEEK composite membrane produced 0.083 μmol of H2 gas in 1 h, and it slightly reduced to 0.074 μmol after 8 h, which shows a stable H2 production and good efficiency of the membrane.

Enhanced pseudo-capacitance and rate performance of amorphous MnO2 for supercapacitor by high Na doping and structural water content

Owing to the advantages of high theoretical capacitance, low cost, and environmental friendliness, MnO2 shows a great potential as the electrode material for supercapacitors. However, its low conductivity and sluggish ion migration lead to the unsatisfied electrochemical performance especially at high rates. In this work, amorphous MnO2 with both high Na doping and structural water content (nw-MnO2) is synthesized via a simple redox reaction in the saturated sodium chloride solution. On the one hand, high Na doping can effectively improve the conductivity of MnO2; on the other hand, the charge shielding effect enabled by structural water facilitates the rapid ion migration in MnO2 lattice. In addition, the amorphous feature also provides more active sites and decreases the ion diffusion length. Benefitting from the above merits, the prepared nw-MnO2 electrode delivers superior rate performance (324.7 F g−1 at 0.5 A g−1 and 182.6 F g−1 even at an ultrahigh rate of 50 A g−1) and excellent cycle stability with 91% of capacitance retention over 10,000 cycles. Moreover, the assembled nw-MnO2//activated carbon asymmetric supercapacitor delivers a high energy density of 81.1 Wh kg−1 and superior capacity retention of 101% after 7000 cycles.

Fabrication of noble metal (Au, Ag, Pt)/polythiophene/reduced graphene oxide ternary nanocomposites for NH3 gas sensing at room temperature.

Room temperature NH3 gas sensors composed of noble metal (Au, Ag or Pt)/polythiophene/reduced graphene oxide (Au, Ag or Pt/PTh/rGO) ternary nanocomposite films were fabricated using a simple one-pot redox reaction. The surface morphology and composition of Au, Ag or Pt/PTh/rGO ternary nanocomposite films were analyzed using Fourier transform infrared spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM). Compared with Ag/PTh/rGO and Pt/PTh/rGO ternary nanocomposite films, obviously bright Au nanoparticles were observed on the surface of the massive lamination PTh film which wrapped the rGO, and encapsulated Au nanoparticles were observed in the Au/PTh/rGO film. Comparative gas sensing results showed that the Au/PTh/rGO ternary nanocomposite film had the highest response compared with Ag/PTh/rGO and Pt/PTh/rGO ternary nanocomposite films at room temperature, especially when the testing concentration of NH3 gas was below 5 ppm. The Au/PTh/rGO ternary nanocomposite film also had a fast response time and good reproducibility. The combination of the high catalytic activity of naked Au nanoparticles and the formation of effective carrier transfer channels by encapsulated Au nanoparticles was responsible for the improved response of the Au/PTh/rGO ternary nanocomposite film.

Enhanced Electromagnetic Wave Absorption Properties of Ultrathin MnO2 Nanosheet-Decorated Spherical Flower-Shaped Carbonyl Iron Powder.

In this work, spherical flower-shaped composite carbonyl iron powder@MnO2 (CIP@MnO2) with CIP as the core and ultrathin MnO2 nanosheets as the shell was successfully prepared by a simple redox reaction to improve oxidation resistance and electromagnetic wave absorption properties. The microwave-absorbing properties of CIP@MnO2 composites with different filling ratios (mass fractions of 20%, 40%, and 60% after mixing with paraffin) were tested and analyzed. The experimental results show that compared with pure CIP, the CIP@MnO2 composites have smaller minimum reflection loss and a wider effective absorption bandwidth than CIP (RL < −20 dB). The sample filled with 40 wt% has the best comprehensive performance, the minimum reflection loss is −63.87 dB at 6.32 GHz, and the effective absorption bandwidth (RL < −20 dB) reaches 7.28 GHz in the range of 5.92 GHz–9.28 GHz and 11.2 GHz–15.12 GHz, which covers most C and X bands. Such excellent microwave absorption performance of the spherical flower-like CIP@MnO2 composites is attributed to the combined effect of multiple beneficial components and the electromagnetic attenuation ability generated by the special spherical flower-like structure. Furthermore, this spherical flower-like core–shell shape aids in the creation of discontinuous networks, which improve microwave incidence dispersion, polarize more interfacial charges, and allow electromagnetic wave absorption. In theory, this research could lead to a simple and efficient process for producing spherical flower-shaped CIP@MnO2 composites with high absorption, a wide band, and oxidation resistance for a wide range of applications.

Surface reconstruction on silver nanoparticles decorated trimetallic hydroxide nanosheets to generate highly active oxygen-deficient (oxy)hydroxide layer for high-efficient water oxidation

The transition-metal (oxy)hydroxides have been considered as one of the promising electrocatalysts for oxygen evolution reaction (OER). Therefore, it is necessary to have in-depth study on the origin behind their favorable inherent OER activity and further improve their catalytic performance. Herein, nickel–cobalt-vanadium trimetallic (oxy)hydroxide nanosheets decorated with silver nanoparticles (Ag NPs) (Ag@NiV0.2Co0.2) are fabricated for OER by a simple spontaneous redox reaction. The Ag@NiV0.2Co0.2 can deliver an overpotential of only 255 mV at 10 mA cm−2 and a small Tafel slope of 38.3 mV dec-1 in alkaline solution. We accredit the outstanding catalytic performance to the following aspects: (1) the active (oxy)hydroxide layer on the surface of Ag@NiV0.2Co0.2 generated through the surface reconstruction, (2) the optimal local coordination induced by the interaction between Ag NPs and trimetallic system, (3) the extensively exposed active sites, and (4) the significantly improved charge-transfer ability due to the incorporation of Ag NPs. Our findings may provide deep understanding on the mechanism of OER and offers a novel strategy to design electrocatalysts with superior OER activity.

Hydrogen production from human and cow urine using in situ synthesized aluminium nanoparticles

Hydrogen production from wastewater system has the potential to add a new dimension to the energy economy. Urine is an abundant waste and contains about 90–96% of water. While there have been efforts to generate electricity from urine (using microbial fuel cells), direct hydrogen production from urine using any technique is less explored. We report human and cow urine pretreatment with simultaneous hydrogen production using a simple redox reaction. This is achieved via in situ formation of aluminium nanoparticles in urine through reduction of aluminum salt using sodium borohydride; the key novelty of the process is the use of Al salt/NaBH4. The in situ prepared aluminium nanoparticles instantly react with urine to produce hydrogen. The volume of hydrogen produced is observed to be sensitive to pH, amount of Al salt, and ageing (storage time of urine). Interestingly, ageing does not impact the kinetics of initial hydrolysis in cow urine as much as it affects in the case of human urine. Fresh urine is found to be better in both the cases. Total carbon, total organic carbon, total nitrogen and total phosphorus removal efficiencies are found to be a maximum of 69.93%, 71.88%, 64.16% and 50.9% respectively for human urine; these values are 67.8%, 70.1%, 61.3% and 48.9% for cow urine at pH 3.

Cu/Cu2O Interconnected Porous Aerogel Catalyst for Highly Productive Electrosynthesis of Ethanol from CO2

AbstractUse of Cu and Cu+ is one of the most promising approaches for the production of C2 products by the electrocatalytic CO2 reduction reaction (CO2RR) because it can facilitate CO2 activation and CC dimerization. However, the selective electrosynthesis of C2+ products on Cu0Cu+ interfaces is critically limited due to the low electrocatalytic production of ethanol relative to ethylene. In this study, a novel porous Cu/Cu2O aerogel network is introduced to afford high ethanol productivity by the electrocatalytic CO2RR. The aerogel is synthesized by a simple chemical redox reaction of a precursor and a reducing agent. CO2RR results reveal that the Cu/Cu2O aerogel produces ethanol as the major product, exhibiting a Faradaic efficiency (FEEtOH) of 41.2% and a partial current density (JEtOH) of 32.55 mA cm−2 in an H‐cell reactor. This is the best electrosynthesis performance for ethanol production reported thus far. Electron microscopy and electrochemical analysis results reveal that this dramatic increase in the electrosynthesis performance for ethanol can be attributed to a large number of Cu0Cu+ interfaces and an increase of the local pH in the confined porous aerogel network structure with a high‐surface‐area.