Preparation and characterization of sulfonated poly(tetra phenyl ether ketone sulfone)s for proton exchange membrane fuel cell

Sulfonated poly(tetra phenyl ether ketone sulfone)s SPTPEKS were successfully synthesized for proton exchange membrane. Poly(tetra phenyl ether ketone sulfone)s PTPEKS were prepared by the 4,4′-dihydroxydiphenylsulfone with 1,2-bis(4-fluorobenzoyl)-3,4,5,6-tetraphenylbenzene (BFBTPB) and 4,4′-difluorodiphenylsulfone, respectively, at 210 °C using potassium carbonate in sulfolane. PTPEKS were followed by sulfonation using chlorosulfonic acid and concentrated sulfuric acid at two stage reactions. Different contents of sulfonated unit of SPTPEKS (17, 20, 23 mol% of BFBTPB) were studied by FT-IR, ¹H NMR spectroscopy, and thermo gravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymers with water. The ion exchange capacity (IEC) and proton conductivity of SPTPEKS were evaluated with increase of degree of sulfonation. The water uptake of synthesized SPTPEKS membranes exhibit 25–61% compared with 28% of Nafion 211^®. The SPTPEKS membranes exhibit proton conductivities (25 °C) of 11.7–25.3 × 10⁻³ S/cm compared with 33.7 × 10⁻³ S/cm of Nafion 211^®.     

High efficiency of proton transport by clustering nanochannels in multi-sulfonated propeller-like nonplanar hexaphenylbenzene poly(ether sulfone)s

The propeller-like nonplanar building unit containing poly(aryl ether ketone)s were synthesized from 1,2-bis(4-hydroxyphenyl)-3,4,5,6-tetraphenyl-benzene (BHPTPB) and bis(4-fluorophenyl) sulfone with bis(4-hydroxydiphenyl) sulfone in NMP. New structures and/or morphologies for existing materials need to be considered in case if increased benefits are desired. The sulfonation was taken selectively on hydrophilic block segment as well as para position of the pendent phenyl groups with concentrated sulfuric acid. The stoichiometry mole ratios were changed with hydrophilic blocks of 12, 15, 17, 20, and 23 mol% of BHPTPB monomer to control the ion exchange capacity. The structural properties of polymer membranes (HP-12, 15, 17, 20, and 23) were studied by FT-IR, ¹H NMR spectroscopy, thermogravimetric analysis (TGA), and atomic force microscope (AFM). The water uptakes were 8.1–69.4% at 75 °C with changing the ion exchange capacities. The resulted proton conductivities were 66.58–103.73 mS/cm at 80 °C with 90% relative humidity. The highest power density of a fuel cell using HP-23 and Nafion 211 was 0.47 and 0.45 W/cm², respectively, at 0.6 V.     

Synthesis and properties of cis/trans mixtures of bis(4-hydroxyphenyl)-1,2-diphenylethylene containing sulfonated poly(ethersulfone)s proton exchange membranes

Conjugated cis/trans isomer-based polymer membranes were prepared with 15–25 mol% of bis(4-hydroxyphenyl)-1,2-diphenylethylene (BHDPE). BHDPE has a conjugated nonplanar conformation structure containing the peripheral four aromatic rings which facilitate the formation of π-π interactions. A series of sulfonated poly(ethersulfone)s (S-PBHDPE) was synthesized with concentrated sulfuric acid. The sulfonation took place selectively on the BHDPE unit, and simultaneously on the side-chain and main-chain phenyl groups. The S-PBHDPEs consisted of a 4:6 ratio of cis and trans form mixtures. The S-PBHDPE membrane structures and characteristics were evaluated by ¹H NMR spectroscopy, and their thermal stabilities evaluated. The ion exchange capacity (IEC), water uptake (WU) and proton conductivity of the membranes were evaluated as a function of the molar percentage of the sulfonic acid group. The WU of the synthesized S-PBHDPE membranes ranged from 21 to 52%, compared with 28% for Nafion 211^®. The S-PBHDPE membranes exhibited proton conductivities (80 °C, RH100) of 42.7–125.6 mS/cm, compared with 137.4 mS/cm for Nafion 211^®. The surface morphologies of S-PES 40 and S-PBHDPE 20 membranes were studied by AFM images.     

Quinoxaline-based crosslinked membranes of sulfonated poly(arylene ether sulfone)s for fuel cell applications

A series of crosslinkable sulfonated poly(arylene ether sulfone)s (SPAESs) were synthesized by copolymerization of 4,4′-biphenol with 2,6-difluorobenzil and 3,3′-disulfonated-4,4′-difluorodiphenyl sulfone disodium salt. Quinoxaline-based crosslinked SPAESs were prepared via the cyclocondensation reaction of benzil moieties in polymer chain with 3,3′-diaminobenzidine to form quinoxaline groups acting as covalent and acid-base ionic crosslinking. The uncrosslinked and crosslinked SPAES membranes showed high mechanical properties and the isotropic membrane swelling, while the later became insoluble in tested polar aprotic solvents. The crosslinking significantly improved the membrane performance, i.e., the crosslinked membranes had the lower membrane dimensional change, lower methanol permeability and higher oxidative stability than the corresponding precursor membranes, with keeping the reasonably high proton conductivity. The crosslinked membrane (CS1-2) with measured ion exchange capacity of 1.53 mequiv. g⁻¹ showed a reasonably high proton conductivity of 107 mS/cm with water uptake of 48 wt.% at 80 °C, and exhibited a low methanol permeability of 2.3 × 10⁻⁷ cm² s⁻¹ for 32 wt.% methanol solution at 25 °C. The crosslinked SPAES membranes have potential for PEFC and DMFCs.     

A copper based metal-organic framework as single source for the synthesis of electrode materials for high-performance supercapacitors and glucose sensing applications

The article describes the conversion of MOF-199 to Cu–Cu₂O–CuO/C 700 (1) and Cu–Cu₂O–CuO/C 800 (2) nanostructures by simple pyrolysis at 700 and 800 °C under inert atmosphere. The X-ray photoelectron spectroscopy analysis reveals that the nanostructures Cu–Cu₂O–CuO/C consist of graphitic carbon functionalized with carboxylic, carbonyl and hydroxyl functional groups with copper/copper oxide particles on surfaces. The electrochemical properties of 1 and 2 are evaluated as electrode material for supercapacitors using cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy. The results for the capacitive performance from cyclic voltammetry and galvanostatic charge/discharge reveal that both the samples have gravimetric capacitance greater than 750 F g⁻¹ at a scan rate of 2 mV s⁻¹ and current density of 2 mA cm⁻². The samples retain about 43% of their initial capacitance even at high scan rate of 75 mV s⁻¹. The cycling performance of the nanostructures illustrate that there is 5.5% capacitance loss after 3000 cycles. The sample 1 and 2 are washed with 1 mol L⁻¹ HCl solution to obtain copper oxide free materials Cu/C 700 (3) and Cu/C 800 (4). Samples 3 and 4 are tested as electrocatalysts for glucose sensing and the cyclic voltammetry measurement shows enhanced current densities compared to the literature values.     

Two-dimensional regioregular polythiophenes with conjugated side chains for use in organic solar cells

We have prepared two two-dimensional polythiophenes (2D-PTs; P1 and P2) possessing alkyl-thiophene side chains by Stille coupling reactions. Optical measurements indicate that the bandgaps of P1 and P2 being 1.98 and 1.77 eV, respectively. P2 displayed a red-shift in its absorption spectrum because of the longer length of its conjugated side chains. Desirable highest occupied molecular orbital (HUMO) and lowest unoccupied molecular orbital (LUMO) energy levels were obtained from electrochemical studies, which suggested that these systems would exhibit high open-circuit voltages when blended with fullerene as electron acceptors. The hole mobility (thin film transistor (TFT) measurement) of P1 and P2 are 3.5×10⁻⁴ and 4.6×10⁻³ cm² V⁻¹ s⁻¹, respectively. A power conversion efficiency of 2.5% is obtained under simulated solar illumination (AM 1.5G, 100 mW cm⁻²) from a polymer solar cell comprising an active layer containing 25 wt% P1 and 75 wt% [6,6]-phenyl-C₇₁ butyric acid methyl ester (PC₇₁BM).     

Electrochemical and chemical enrichment methods of a sodic–saline inoculum for microbial fuel cells

In microbial fuel cells (MFCs) efficient extracellular electron transfer microbes, also known as anode-respiring bacteria, play an important role on cell performance. This type of microbes can be developed by application of enrichment procedures. The objective of this study was to compare a chemical (only C, final terminal electron acceptor Fe(III)), an electrochemical (only E), and a hybrid method (H, i.e., E followed by 3 serial transfers in iron (III) citrate medium) enrichment methods departing from a saline–sodic soil inoculum. In the electrochemical enrichment procedure in an electrolysis cell, the inoculum was subjected to a continuous electrical stress continually by posing the cell at −150 mV/SCE (+94 mV/SHE). The only C enrichment method delivered powers superior to the only E one (higher values of P_An,max = 49 mW m⁻² and P_V,max = 558 mW m⁻³ of C compared to 33 and 379 of only E). Interestingly, overall resistance as determined by EIS was lower for only E (1240 Ω) than for only C (1632 Ω). Yet, the hybrid H method, showed electrochemical characteristics consistently superior to both only C and only E methods (higher P_An,max and P_V,max, lower internal resistance). Further detailed electrochemical studies of only E-method showed that the anodic resistance decreased with the time of operation of the electrolysis cell that would be consistent with the adaptability/enrichment purpose of the method. Also, Cyclic voltammetry peaks with values close to those reported for bacterial cytochromes appeared with time of cell operation.     

Gas and vapor adsorption in octacyanometallate-based frameworks Mn2[M(CN)8] (M = W,Mo) with exposed Mn sites

Dehydration of the isostructural three-dimensional (3D) octacyanometallate-based materials Mn₂M(CN)₈·7H₂O (M = Mo, 1·7H₂O; W, 2·7H₂O) generates robust porous frameworks (1 and 2). In the structure, the [M(CN)₈]⁴⁻ units are linked via octahedral Mn²⁺ centers to form an open 3D framework with 1D channels, in which the non-coordinated and coordinated water molecules are involved. The permanent porosities have been confirmed by thermogravimetric analysis, variable-temperature X-ray diffraction and Raman spectra, and adsorption (H₂O, N₂ and H₂) measurements. H₂ adsorption at 1.1 bar and 77 K was 0.60 wt% for 1 and 0.49 wt% for 2. At initial loading ΔH_ads has the value of ca. 10.0 kJ mol⁻¹ for both materials, which represents the highest value reported for any cyanide-based assemblies. The high enthalpy can be attributed to the presence of coordinatively-unsaturated Mn²⁺ sites left exposed by the removal of coordinated water molecules in the structure.     

The structural characterization of (NH4)2B10H10 and thermal decomposition studies of (NH4)2B10H10 and (NH4)2B12H12

The structure of (NH₄)₂B₁₀H₁₀ (1) was determined through powder XRD analysis. The thermal decomposition of 1 and (NH₄)₂B₁₂H₁₂ (2) was examined between 20 and 1000 °C using STMBMS methods. Between 200 and 400 °C a mixture of NH₃ and H₂ evolves from both compounds; above 400 °C only H₂ evolves. The dihydrogen bonding interaction in 1 is much stronger than that in 2. The stronger dihydrogen bond in 1 resulted in a significant reduction by up to 60 °C, but with a corresponding 25% decrease in the yield of H₂ in the lower temperature region and a doubling of the yield of NH₃. The decomposition of 1 follows a lower temperature exothermic reaction pathway that yields substantially more NH₃ than the higher temperature endothermic pathway of 2. Heating of 1 at 250 °C resulted in partial conversion of B₁₀H₁₀²⁻ to B₁₂H₁₂²⁻. Both 1 and 2 form an insoluble polymeric material after decomposition. The elements of the reaction network that control the release of H₂ from the B₁₀H₁₀²⁻ can be altered by conducting the experiment under conditions in which pressures of NH₃ and H₂ are either near, or away from, their equilibrium values.     

Sulfonated poly(fluorenyl ether ketone) ionomers containing aliphatic functional segments for fuel cell applications

A series of Sulfonated Poly (fluorenyl ether ketone) ionomers containing aliphatic functional segments were synthesized and characterized. The monomer 4,4′-Dihydroxy-α, ω-diphenoxydecane with aliphatic group was conveniently prepared from hydroquinone and 1,10-dibromodecane. A series of sulfonated aliphatic functional groups containing poly(fluorenyl ether ketone)s with different aliphatic group content were successfully synthesized and characterized in detail, in particular with respect to properties relevant for their application as membrane materials in proton exchange membrane (PEM) fuel cells. Tough and transparent membranes were formed by casting from their solutions. The effects of alkyl groups were investigated by comparison of the PEM properties of the copolymers with different content of aliphatic component on the copolymer chain. The introduction of aliphatic segments can provide an enhanced water uptake, increased proton conductivities, but worse oxidative stability. Transmission electron microscope (TEM) images of j and f revealed an improved phase separation structure under the effect of aliphatic groups. The as-made membranes can also exhibit comparable or much better single cell performance than Nafion^@ 117 at 75 °C–95 °C under full or partial relative humidification.     

Crosslinked sulfonated poly(arylene ether ketone) membranes bearing quinoxaline and acid-base complex cross-linkages for fuel cell applications

A series of crosslinkable sulfonated poly(arylene ether ketone)s (SPAEKs) were synthesized by copolymerization of 4,4′-biphenol with 2,6-difluorobenzil and 5,5′-carbonyl-bis(2-fluorobenzene-sulfonate). A facile crosslinking method was successfully developed, based on the cyclocondensation reaction of benzil moieties in polymer chain with 3,3′-diaminobenzidine to form quinoxaline groups acting as covalent and acid-base ionic crosslinking. The uncrosslinked and crosslinked SPAEK membranes showed high mechanical properties and the isotropic membrane swelling, while the later became insoluble in tested polar aprotic solvents. The crosslinking significantly improved the membrane performance, i.e., the crosslinked membranes had the lower membrane dimensional change, lower methanol permeability and higher oxidative stability than the corresponding precursor membranes, with keeping the reasonably high proton conductivity. The crosslinked membrane (C-B4) with an ion exchange capacity of 2.02 mequiv. g⁻¹ showed a reasonably high proton conductivity of 111 mS cm⁻¹ with a low water uptake of 42 wt% at 80 °C. C-B4 exhibited a low methanol permeability of 0.55 × 10⁻⁶ cm² s⁻¹ for 32 wt% methanol solution at 25 °C. The crosslinked SPAEK membranes have potential for PEFC and DMFC applications.     

A new photosensitive coordination compound [RuL(bpy)2](PF6)2 and its application in photocatalytic H2 production under the irradiation of visible light

A new organic–inorganic photosensitive coordination compound [RuL(bpy)₂](PF₆)₂ (to represent by TM1) had been synthesized by reaction of L (L = 2-hydroxyl-5-(imidazo-[4,5-f]-1,10-phenanthrolin) benzoic acid) with bipyridyl ruthenium, and further characterized by UV–vis, IR, NMR MS and CV. The target photocatalyst 6 wt% TM1-0.5 wt% Pt-TiO₂ (Ⅰ) was obtained by sensitization of Pt-loaded TiO₂ with TM1. The H₂ production activity of target photocatalyst Ⅰ was systematically evaluated by the reaction of photocatalytic H₂ production from water under visible light irradiation. The maximum H₂ evolution of 386.7 μmol in irradiation 3 h and H₂ production rate of 2578 μmol · h⁻¹ · g⁻¹ was detected under the optimal conditions with pH 5, target photocatalyst Ⅰ 50 mg and 5% sacrificial reagent TEOA (v/v).     

Synthesis and characterization of novel cardo poly(aryl ether sulfone) bearing zwitterionic side groups for proton exchange membranes

A novel series of sulfonated poly(aryl ether sulfone)s with zwitterionic groups ([-CH₂CH₂CH₂N⁺CH₃(CH₂CH₂SO₃⁻)₂]) have been prepared by the copolycondensation of a secondary amine-containing biphenol monomer with 4,4′-biphenol and 4,4′-dichlorodiphenylsulfone, and this was followed by the reaction with sodium 2-bromoethanesulfonate. All the resulting copolymers can form uniform and tough membranes by simple solution casting. The investigation of ion exchange capacity (IEC) values indicated that each ammonium group interacted with one sulfonate group. Because of strong intermolecular interaction, the increased packing density of chain formed that resulted in polymer membranes with lower water uptake and swelling ratio, and better oxidative stability compared with side-chain-type sulfonated poly(aryl ether sulfone)s with the close IEC values. The polymer membranes bearing zwitterionic groups kept intact in Fenton’s reagent at 80 °C for 20 h. Furthermore, these membranes demonstrated higher proton conductivity than the side-chain-type sulfonated polymer membranes at the same measurement conditions.     

Low band gap dyes based on 2-styryl-5-phenylazo-pyrrole: Synthesis and application for efficient dye-sensitized solar cells

A new series of low band gap dyes, C1, C2 and S, based on 2-styryl-5-phenylazo-pyrrole was synthesized. These dyes contain one carboxy, two carboxy and one sulfonic acid anchoring groups, respectively. They were soluble in common organic solvents, showed long-wavelength absorption maximum at ∼620 nm and optical band gap of 1.66-1.68 eV. The photophysical and electrochemical properties of these dyes were investigated and found to be suitable as photosensitizers for dye sensitized solar cells (DSSCs). The quasi solid state DSSCs with dye S showed a maximum monochromatic incident photon to current efficiency (IPCE) of 78% and an overall power conversion efficiency (PCE) of 4.17% under illumination intensity of 100 mW cm⁻² (1.5 AM), which is higher than the other dyes (3.26% for C2 and 2.59% for C1). Even though dye S contains one sulfonic acid anchoring group, the higher PCE for the DSSCs based on this dye has been attributed to the higher dye loading at the TiO₂ surface and enhanced electron lifetime in the device, as indicated by absorption spectra and electrochemical impedance spectra measurements. Finally, by increasing the molecular weight of poly(ethylene oxide) (PEO) in electrolyte, the PCE also increases up to 4.8% for the electrolyte with PEO molecular weight of 2.0 × 10⁶. This improvement has been attributed to the enhancement in iodide ions diffusion due to the increase in free volume of polymer gel electrolyte.     

Novel iminocoumarin dyes as photosensitizers for dye-sensitized solar cell

Novel iminocoumarin dyes (2a-c and 3a-c) having carboxyl and hydroxyl anchoring groups onto the dyes skeletons have been designed and synthesized for the application of dye-sensitized nanocrystalline TiO₂ solar cells (DSSCs). The photophysical and electrochemical studies showed that these iminocoumarin dyes are suitable as light harvesting sensitizers in DSSC application. The dyes having carboxyl and hydroxyl anchoring groups (2a-c) showed better efficiency when compared to the dyes having carboxyl group (3a-c) alone. The cell consisted of dye 2a generated the highest solar-to-electricity conversion efficiency (η) of 0.767% (open circuit voltage (V_oc) = 0.491 V, short circuit photocurrent density (J_sc) = 2.461 mA cm⁻², fill factor (ff) = 0.635) under simulated AM 1.5 irradiation (1000 W m⁻²) with a total semiconductor area of 0.25 cm². The corresponding incident photon-to-current conversion efficiency (IPCE) of the above cell was 21.38%. The overall low efficiency of the dyes is ascribed to the lack of light harvesting ability at longer wavelength region.     

Design,synthesis and properties of polyaromatics with hydrophobic and hydrophilic long blocks as proton exchange membrane for PEM fuel cell application

A series of the poly(ether ether ketone)s with hydrophobic and hydrophilic long blocks were successfully synthesized by nucleophilic displacement condensation. The polyaromatics with different size of sulfonic acid group clusters were cast from their solutions to produce accordingly membranes. The comprehensive properties of these membranes were then fully characterized by determining the ion-exchange capacity, water uptake, proton conductivity, dimensional stabilities and mechanical properties. The experimental results show that the main properties of the membrane can be tailored by changing the cluster size of sulfonic acid groups or the length of hydrophilic units. The membrane of Block-6c has good mechanical, oxidative and dimensional stabilities together with high proton conductivity (2.09 × 10⁻² S cm⁻¹) at 80 °C under 100% relative humidity. The membranes also possess excellent thermal and dimensional stabilities, therefore, these polymers are potential and promising proton conducting membrane material for PEM full cell applications.     

Novel symmetric squaraine chromophore containing triphenylamine for solution processed small molecule bulk heterojunction solar cells

New symmetrical low band-gap small molecule materials, SQ-bis[HP-HT2-TPA] and SQ-bis[HP-HT2-BT] incorporating as novel derivative of squaraine-pyrrole framework and π-extended thiophene with triphenyamine (TPA) and benzothiophene (BT) end group, have been synthesized and characterized. The effects of TPA moiety were investigated. Compared to SQ-bis[HP-HT2-BT], SQ-bis[HP-HT2-TPA] exhibited three times improved transporting property of hole carrier and four times enhanced absorptivity by more efficient intermolecular π−π interaction for high-efficiency bulk heterojunction (BHJ) device, suggesting that TPA contributes to a better hole mobility. The bulk-heterojunction photovoltaic devices fabricated with SQ-bis[HP-HT2-TPA]/C₇₁-PCBM BHJ film had an average power-conversion efficiency of 1.83%(±0.12) under 100 mW/cm², with a short-circuit current (J_sc) of 9.32 mA/cm², fill factor (FF) of 0.30, and open-circuit voltage (V_oc) of 0.65 V, which has ∼42% higher efficiency compared to SQ-bis[HP-HT2-BT]/C₇₁-PCBM BHJ films.     

Local measurements of the time-dependent heat release rate and equivalence ratio using chemiluminescent emission from a flame

Chemiluminescent emissions from OH^⋅, CH^⋅, and C^⋅₂ and continuous emissions from CO^⋅₂ have been measured in natural-gas-fuelled, premixed, counterflow flames operating with an equivalence ratio between 0.7 and 1.3 and strain rates between 80 and 400 s⁻¹, achieved by varying the exit velocity of the jet between 1 and 5 m s⁻¹. Cassegrain receiving optics coupled to a high-performance spectroscopic unit allowed local, temporally resolved measurements of intensity of chemiluminescence in flat flames, which were compared with measurements along a line of sight obtained from flame spectra. This study allowed independent evaluation of the effects of strain rate and equivalence ratio on intensity of chemiluminescence and the ability of intensity of chemiluminescence to indicate heat release rate. Results suggest that intensities of chemiluminescence from OH^⋅ and CH^⋅ and background intensity from CO^⋅₂ are good indicators of heat release rate, whereas that from C^⋅₂ is not. The study also evaluated the ability to measure equivalence ratio of the reacting mixture using intensity of chemiluminescence and found that the intensity ratio OH^⋅/CH^⋅ has a monotonic decrease with equivalence ratio for lean and stoichiometric mixtures, while remaining independent of flame strain rate. The results indicate that the intensity ratio OH^⋅/CH^⋅ can measure with uncertainties of 5% the equivalence ratio up to values of 1.1 and with uncertainties of 20% for richer mixtures due to the low sensitivity of the intensity ratio OH^⋅/CH^⋅ for rich mixtures. The intensity ratios of C^⋅₂/OH^⋅ and C^⋅₂/CH^⋅ have a non-monotonic dependence on equivalence ratio and a dependence on strain rate and are thus not suitable for measurements of equivalence ratio. An approach to measuring the time-dependent equivalence ratio of the reacting mixture is suggested and data processing methods and associated uncertainties are presented. The potential of the technique for local measurements in practical burners is discussed and further evaluation of the spatial resolution is required in such flames. However, suggestions have been provided on how the spatial resolution can be improved in practical flames.     

Bulk heterojunction organic photovoltaic devices based on low band gap small molecule BTD-TNP and perylene-anthracene diimide

Bulk heterojunction (BHJ) photovoltaic devices were fabricated from the blends of compounds BTD-TNP (electron donor) and P-A (electron acceptor) and characterized through current-voltage measurements under illumination. Compound BTD-TNP contains dithyenyl-benzothiadiazole central unit and cyanovinylene-p-nitrophenyl terminal moieties. Compound P-A is a symmetrical perylene-anthracene diimide with tert-butylphenoxy side groups at the 1,7-bay positions. Both the absorption spectra and the incident photon to the current conversion efficiency (IPCE) spectra of the device were extended up to 800 nm. A power conversion efficiency of 2.85% with short-circuit current density of 6.8 mA/cm², open-circuit voltage of 0.88 V and fill factor of 0.47 were obtained. It was found that the hole and electron mobility in the active layer were about 4.6×10⁻⁵ and 8.8×10⁻⁴ cm²/Vs, respectively, which indicates the fairly balanced charge transport in the device.