Instant formation of excellent oxygen evolution catalyst film via controlled spray pyrolysis for electrocatalytic and photoelectrochemical water splitting

The retarded kinetics of oxygen evolution on electrodes is a bottleneck for electrochemical energy conversion and storage systems.NiFe-based electrocatalysts provide a cost-effective choice to confront this challenge.However,there is a lack of facile techniques for depositing compact catalytic films of high coverage and possessing a state-of-the-art performance,which is especially desired in photoelectrochemical(PEC)systems.Herein,we demonstrate a spray pyrolysis(SP)route to address this issue,featuring the kinetic selective preparation towards the desired catalytic-active material.Differing from reported SP protocols which only produce inactive oxides,this approach directly generates a unique composite film consisting of NiFe layered oxyhydroxides and amorphous oxides,exhibiting an overpotential as small as 255 mV(10 mA cm^(−2))and a turnover frequency of∼0.4 s^(−1)per metal atom.By using such a facile protocol,the surface rate-limiting issue of BiVO_(4)photoanodes can be effectively resolved,resulting in a charge injection efficiency of over 90%.Considering this deposition directly start from simple nitrates but only takes several seconds to complete,we believe it can be developed as a widely applicable and welcomed functionalization technique for diverse electrochemical devices.

Characteristics of SnO_(2):F Thin Films Deposited by Ultrasonic Spray Pyrolysis:Effect of Water Content in Solution and Substrate Temperature

Fluorine doped tin oxide, SnO2:F, thin films were deposited by ultrasonic chemical spray starting from tin chloride and hydrofluoric acid. The physical characteristics of the films as a function of both water content in the starting solution and substrate temperature were studied. The film structure was polycrystalline in all cases, showing that the intensity of (200) peak increased with the water content in the starting solution. The electrical resistivity decreased with the water content, reaching a minimum value, in the order of 8 × 10-4 Ωcm, for films deposited at 450℃ from a starting solution with a water content of 10 ml per 100 ml of solution;further increase in water content increased the corresponding resistivity. Optical transmittances of SnO2:F films were high, in the order of 75%, and the band gap values oscillated around 3.9 eV. SEM analysis showed uniform surface morphologies with different geometries depending on the deposition conditions. Composition analysis showed a stoichiometric compound with a [Sn/O] ratio around 1:2 in all samples. The presence of F into the SnO2 lattice was detected, within 2 at % respect to Sn.

Transparent conductive stannic oxide coatings employing an ultrasonic spray pyrolysis technique:The relevance of the molarity content in the aerosol solution for improvement the electrical properties

Highly transparent conductive stoichiometric nanocrystalline stannic oxide coatings were deposited onto Corning®EAGLE XG®slim glass substrates.Including each coating,it was deposited for various concentrations in the aerosol solution with the substrate temperature maintained at 623.15 K by an ultrasonic spray pyrolysis(USP)technique.Nitrogen was em-ployed both as the solution carrier in addition to aerosol directing gas,maintaining its flow rates at 3500.0 and 500.0 mL/min,respectively.The coatings were polycrystalline,with preferential growth along the stannic oxide(112)plane,irrespective of the molarity content in the spray solution.The coating prepared at 0.2 M,a concentration in the aerosol solution,showed an average transmission of 60%in the visible light region spectrum with a maximum conductivity of 24.86 S/cm.The coatings deposited exhibited in the general photoluminescence spectrum emission colors of green,greenish white,and bluish white calculated on the intensities of the excitonic and oxygen vacancy defect level emissions.

Characterization of CeO_(2)microspheres fabricated by an ultrasonic spray pyrolysis method

CeO_(2) is one of the main catalysts for solid oxide fuel cell(SOFC).It is critical to find a green and costeffective fabrication method for CeO_(2) at scale.In this study,the CeO_(2) microspheres were prepared by one-step ultrasonic spray pyrolysis of cerium chloride solution at700℃.Scanning electron microscopy(SEM)and transmission electron microscopy(TEM)study demonstrate that the prepared CeO_(2) microspheres exhibit a particle size of0.01-1.08μm with a mean particle size of 0.23μm,and more than 94%of the particles have a diameter less than0.5μm.But the presence of residual Cl in the fabricated CeO_(2) microspheres blocks the active sites and leads to the significant degradation of SOFC performance.The formation mechanism and distribution of residual Cl in the fabricated CeO_(2) microspheres were systemic ally studied.The water washing method was shown to effectively reduce the residual Cl in the CeO_(2) microspheres.Overall,this work provides a clean manufacturing process for the preparation of SOFC electrode/electrolyte materials.

Novel continuous single-step synthesis of nitrogen-modified TiO_2 by flame spray pyrolysis for photocatalytic degradation of phenol in visible light

A novel rapid and continuous process has developed for the synthesis of nitrogen-doped TiO_2(N-TiO_2)with flame spray pyrolysis(FSP) method. The nitrogen incorporation into TiO_2 was achieved by a facile modification(addition of dilute nitric acid) in the precursor for the synthesis. The catalysts were characterized by X-ray diffraction, Raman spectroscopy, transmission electron microscopy, diffuse reflectance spectroscopy, and X-ray photoelectron spectroscopy. The doping of nitrogen into the TiO_2 was confirmed by X-ray photoelectron spectroscopy(XPS) and energy dispersive X-ray(EDX) spectroscopy. The UV-vis spectra of the modified catalysts(with primary N source) exhibited band-gap narrowing for 4 N-TiO_2 with band gap energy of 2.89 eV, which may be due to the presence of nitrogen in TiO_2 structure. The introduction of secondary N-source(urea) into TiO_2 crystal lattice results in additional reduction of the band gap energy to 2.68 eV and shows a significant improvement of visible light absorption. The N-TiO_2 nanoparticles modified by using secondary N-source showed significant photocatalytic activity under visible light much higher than TiO_2. The higher activity is attributed to the synergetic interaction of nitrogen with the TiO_2 lattice. The lowering of the band-gap energy for the flame made N-doped TiO_2 materials implies that the nitrogen doping in TiO_2 by aerosol method is highly effective in extending the optical response of TiO_2 in the visible region. The nitrogen atomic percentage has increased monotonically(0.09%-0.15%)with the increase in primary nitrogen source(nitric acid), and significantly boosted to 0.97% when secondary nitrogen source(urea) was introduced. The highest rate of phenol degradation was obtained for catalysts with secondary N source due to increase in N content in the catalyst.

High-performance spherical LiVPO4F/C cathode enabled by facile spray pyrolysis

LiVPO4F suffers problems of difficulty in synthesis and poor conductivity. To solve these,herein sub-micro spherical LiVPO4F/C is synthesized from a highly-reactive hollow VPO4/C sphere that is derived from a facile and fast spray pyrolysis for the first time. Uniform carbon coating layer with a thickness of 5–8 nm is observed on the surface of the particles,helping to improve the electronic conductivity,suppress the particle growth and protect the particles from corrosion by the electrolyte. The particles are shaped as fine sub-micro spheres,which are beneficial for shortening the distance for Li+ transport. Rietveld refinement for the X-ray diffraction pattern of as-prepared sample shows high-purity triclinic LiVPO4F with an enlarged lattice volume,enabling faster Li+ transport in the prepared material. Accordingly,the resulted LiVPO4F/C demonstrates superior electrochemical properties,delivering 135.4,91.1 mA hg-1 at 1,40 C respectively,and remaining the capacity of 93.3 mA hg-1 after 500 cycles at 20 C with the retention of 95.0%. The method introduced here provides an efficient way to address the serious problems of preparing high-purity Li VPO4F with good conductivity.

Electrical properties of Cu_4ZnSnS_2/ZnS heterojunction prepared by ultrasonic spray pyrolysis

Cu_2ZnSnS_4(CZTS)/ZnS heteroj unctions have been prepared by a successive deposition of ZnS and CZTS thin films by ultrasonic spray pyrolysis technique on glass substrates.The cupric chloride concentration has been varied in the starting solution in order to investigate its influence on device properties.CZTS/ZnS heterojunctions were characterized by recording their current-voltage characteristics at different temperatures.The obtained results exhibit a good rectifying behavior of the realized heterojunction.Analysis of these results yields saturation current,series resistance and ideality factor determination.From the activation energy of saturation current we inferred that the thermal emission through the barrier height is the dominant mechanism of the reverse current rather than the defects contribution.

Synthesis of indium tin oxide nano-polycrystalline powders by ultrasonic spray pyrolysis

Indium tin oxide(ITO) nano-polycrystalline powders were prepared by ultrasonic spray pyrolysis(USP) method using a precursor solution of indium and tin chlorides in a simple one-step process without any post-heat treatment,additives and other complex operations.The morphology and crystal structure of ITO powders were studied by thermogravimetric and differential thermal analysis(TG-DTA),X-ray diffraction(XRD),energy-dispersive spectrometer(EDS),scanning electron microscopy(SEM),laser particle size analyzer(LPSA),transmission electron microscope(TEM),high-resolution transmission electron microscopy(HRTEM) and selected area electron diffraction(SAED),respectively.The results indicate that pure cubic ITO solid solution could be obtained at and above the pyrolysis temperature of 600℃.Through adjusting the size of atomized precursor droplets,the particles with regular spherical shape and smooth surface are also obtained.The spherical particles have a narrow size distribution with a dominant diameter size in the range of 0.52-1.28 μm,and the average value is 1.01 μm.The clear lattice fringes in HRTEM image confirm a polycrystalline structure of ITO particles with the growth direction along(222) direction.

Texture coefficient and band gap tailoring of Fe-doped SnO_(2) nanoparticles via thermal spray pyrolysis

An investigation of Fe-doping effect on SnO_(2) thin films was performed in this study using thermal spray pyrolysis(TSP) method.The surface morphology and structural,optical and electrical properties were studied by field energy scanning electron microscope(FESEM),X-ray diffraction(XRD),ultraviolet-visible(UV-Vis) spectroscopy and four-point probe method.FES EM images demonstrate that the surface morphology of the as-deposited films varies when Fe-doping content varies.XRD studies reveal that crystallite size and preferential growth orientations of the films are dependent on Fe-doping concentrations.The grain size is found to decrease with the increase in Fe content.These studies also specify that the films have tetragonal rutile-type structure with mixed secondary phases.The texture coefficient value of(110) plane increases with the concomitant in-plane(220) decrease in higher doping concentrations.The resistivity and the optical absorbance are found to increase with Fe concentration.The direct optical band gap decreases from 3.94 to3.52 eV with increasing Fe content.

Humidity sensing properties of spray deposited Fe doped TiO_(2)thin film

In the present work,ferrite(Fe)doped TiO_(2)thin films with different volume percentage(vol%)were synthesized using a spray pyrolysis technique.The effect of Fe doping on structural properties such as crystallite size,texture coefficient,microstrain,dislocation densities etc.were evaluated from the X ray diffratometry(XRD)data.XRD data revealed a polycrystalline anatase TiO_(2)phase for sample synthesized up to 2 vol%and mixed anatase and rutile crystalline phase for sample synthesized at 4 vol%Fe doped TiO_(2).The crystalline size was observed to decrease with increase in Fe dopant vol%and also other structural parameters changes with Fe dopant percentage.In the present work,electrical resistance was observed to decrease with a rise in Fe dopant vol%and temperature of the sample.Thermal properties like temperature coefficient of resistance and activation energy also showed strong correlation with Fe dopant vol%.Humidity sensing properties of the synthesized sample altered with a change in Fe dopant vol%.In the present paper,maximum sensitivity of about 88.7%for the sample synthesized with 2 vol%Fe doped TiO_(2)and also the lowest response and recovery time of about 52 and 3 s were reported for the same sample.

Spray Pyrolyzed TiO2 Embedded Multi-Layer Front Contact Design for High-Efficiency Perovskite Solar Cells

The photovoltaic performance of perovskite solar cells(PSCs)can be improved by utilizing efficient front contact.However,it has always been a significant challenge for fabricating high-quality,scalable,controllable,and cost-effective front contact.This study proposes a realistic multi-layer front contact design to realize efficient single-junction PSCs and perovskite/perovskite tandem solar cells(TSCs).As a critical part of the front contact,we prepared a highly compact titanium oxide(TiO2)film by industrially viable Spray Pyrolysis Deposition(SPD),which acts as a potential electron transport layer(ETL)for the fabrication of PSCs.Optimization and reproducibility of the TiO2 ETL were discreetly investigated while fabricating a set of planar PSCs.As the front contact has a significant influence on the optoelectronic properties of PSCs,hence,we investigated the optics and electrical effects of PSCs by three-dimensional(3D)finite-difference time-domain(FDTD)and finite element method(FEM)rigorous simulations.The investigation allows us to compare experimental results with the outcome from simulations.Furthermore,an optimized single-junction PSC is designed to enhance the energy conversion efficiency(ECE)by>30% compared to the planar reference PSC.Finally,the study has been progressed to the realization of all-perovskite TSC that can reach the ECE,exceeding 30%.Detailed guidance for the completion of high-performance PSCs is provided.

Optical, Structural and Morphological Properties of Photocatalytic ZnO Thin Films Deposited by Pray Pyrolysis Technique

Photocatalytic ZnO thin films have been deposited onto glass substrate by spray pyrolysis technique. The sprayed solution consists of 0.1 M of zinc acetate dihydrate dissolved in double distilled water and sprays onto ultrasonically cleaned glass substrates maintained at 350°C, through an air-atomizing nozzle. The X-ray diffraction (XRD), scanning electron microscopy (SEM), EDX and UV-VIS spectrophotometer were applied to describe the structural, morphological, compositional and optical properties of ZnO catalyst. XRD analysis confirms that the films were found to be single phase hexagonal wurtzite structure. The SEM micrograph of the films is shown highly uniform, crack free and found to be fiber like structures. The optical transmittance spectra of the ZnO thin films were found to be transparent to visible light and the average optical transmittance was greater than 85%. The direct optical band gap energy values of the films shift towards the lower energy as a consequence of the thermal annealing. The Urbach energy of the films was found to increase with annealing temperature. The refractive index of the films was calculated and the refractive index dispersion curve of the films obeys the single oscillator model. The values of oscillatory energy Eo, dispersion energy Ed, and static dielectric constant εs for the ZnO thin films were determined. The films were evaluated for their ability to degrade methylene blue. The Langmuir-Hinshelwood kinetic model was used to interpret quantitatively the observed kinetic experimental result. The photocatalytic activity of ZnO thin films was enhanced by annealing temperature.

Diluted low concentration electrolyte for interphase stabilization of high-voltage LiNi_(0.5)Mn_(1.5)O_(4) cathode

The Co-free Li Ni_(0.5)Mn_(1.5)O_(4)(LNMO)is a promising cathode for lithium-ion batteries owing to its high operating voltage and low costs.However,the synthesis of LNMO is generally time and energy consuming,and its practical application is hindered by the lack of a compatible electrolyte.Herein,a spray pyrolysis-based energy-saving synthesis method as well as a diluted low concentration electrolyte(0.5 M LiPF_(6) in a mixture of fluoroethylene carbonate/dimethyl carbonate/1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether(FEC:DMC:TTE,1:4:5 by volume))are proposed to address these challenges.Owing to the unique features of the precursor prepared by spray pyrolysis,well-crystallized LNMO single-crystal can be obtained within 1 h calcination at 900℃.Besides,the fluorinated interphases derived from the diluted low concentration electrolyte not only mitigate the Mn dissolution and Al corrosion at the cathode side,but also suppresses dendritic Li deposition at the anode side,thus enabling stable cycling of both LNMO and Li metal anode.Thus,30μm Li|LNMO(1.75 m A h cm^(-2))cells achieve a high capacity retention(90.9%)after 168 cycles in the diluted low concentration electrolyte.

TiO2-based materials for photocatalytic hydrogen production

Hydrogen, the cleanest and most promising energy vector, can be produced by solar into chemical energy conversion, either by the photocatalytic direct splitting of water into H_2 and O_2, or, more efficiently,in the presence of sacrificial reagents, e.g., in the so-called photoreforming of organics. Efficient photocatalytic materials should not only be able to exploit solar radiation to produce electron–hole pairs, but also ensure enough charge separation to allow electron transfer reactions, leading to solar energy driven thermodynamically up-hill processes. Recent achievements of our research group in the development and testing of innovative TiO_2-based photocatalytic materials are presented here, together with an overview on the mechanistic aspects of water photosplitting and photoreforming of organics. Photocatalytic materials were either(i) obtained by surface modification of commercial photocatalysts, or produced(ii) in powder form by different techniques, including traditional sol gel synthesis, aiming at engineering their electronic structure, and flame spray pyrolysis starting from organic solutions of the precursors, or(iii) in integrated form, to produce photoelectrodes within devices, by radio frequency magnetron sputtering or by electrochemical growth of nanotube architectures, or photocatalytic membranes, by supersonic cluster beam deposition.

Photoelectrocatalytic activity of immobilized Yb doped WO3 photocatalyst for degradation of methyl orange dye

Pure WO_3 and Yb:WO_3 thin films have been synthesized by spray pyrolysis technique. Effect of Yb doping concentration on photoelectrochemical, structural, morphological and optical properties of thin films are studied. X-ray diffraction analysis shows that all thin films are polycrystalline nature and exhibit monoclinic crystal structure. The 3 at% Yb:WO_3 film shows superior photoelectrochemical(PEC) performance than that of pure WO_3 film and it shows maximum photocurrent density(Iph= 1090 μA/cm^2) having onset potentials around +0.3 V/SCE in 0.01 M HClO_4. The photoelectrocatalytic process is more effective than that of the photocatalytic process for degradation of methyl orange(MO) dye. Yb doping in WO_3 photocatalyst is greatly effective to degrade MO dye. The enhancement in photoelectrocatalytic activity is mainly due to the suppressing the recombination rate of photogenerated electron-hole pairs. The mineralization of MO dye in aqueous solution is studied by measuring chemical oxygen demand(COD) values.

Grain size regulation for balancing cycle performance and rate capability of LiNi_(0.9)Co_(0.055)Mn_(0.045)O_(2) single crystal nickel-rich cathode materials

It is challenging to balance the cyclability and rate capability of single crystal nickel-rich cathode materials(Ni>0.8).Multicomponent oxides by spray pyrolysis shows potential as highly-reactive precursors to synthesize single crystal nickel-rich cathode at lower temperature,yet Ni^(2+)will severely inhibit particle growth when Ni content exceeds 0.9.Herein,lithium nitrate(LiNO_(3))with low melting point and strong oxidation is introduced as collaborate lithium salts for fabrication of well-dispersed submicron and micron single crystal LiNi_(0.9)Co_(0.055)Mn_(0.045)O_(2)(NCM90)cathode without extra unit operation.By changing amount of LiNO_(3),particle size regulation is realized and cation disorder can be diminished.The as-prepared material with optimal content of 4 wt%LiNO_(3)(NCM90-4 LN)displays the most appropriate particle size(1μm)with approximately stoichiometric structure,and presents better kinetics characterization of lithium-ion diffusion(15%higher than NCM90)and good electrochemical performance with specific discharge capacity of 220.6 and 173.8 mAh g^(-1) at 0.1 C and 10 C at room temperature,respectively.This work broadens the conventional research methodology of size regulation for single crystal Ni-rich cathode materials and is indispensable for the development of designing principal of nickel-rich cathode materials for lithium-ion batteries.

Porous Microspheres Comprising CoSe2 Nanorods Coated with N-Doped Graphitic C and Polydopamine-Derived C as Anodes for Long-Lived Na-Ion Batteries

Metal–organic framework-templated nitrogen-doped graphitic carbon(NGC)and polydopaminederived carbon(PDA-derived C)-double coated one-dimensional CoSe_(2) nanorods supported highly porous threedimensional microspheres are introduced as anodes for excellent Na-ion batteries,particularly with long-lived cycle under carbonate-based electrolyte system.The microspheres uniformly composed of ZIF-67 polyhedrons and polystyrene nanobeads(φ=40 nm)are synthesized using the facile spray pyrolysis technique,followed by the selenization process(P-CoSe_(2)@NGC NR).Further,the PDA-derived C-coated microspheres are obtained using a solution-based coating approach and the subsequent carbonization process(P-CoSe_(2)@PDA-C NR).The rational synthesis approach benefited from the synergistic effects of dual carbon coating,resulting in a highly conductive and porous nanostructure that could facilitate rapid diffusion of charge species along with efficient electrolyte infiltration and effectively channelize the volume stress.Consequently,the prepared nanostructure exhibits extraordinary electrochemical performance,particularly the ultra-long cycle life stability.For instance,the advanced anode has a discharge capacity of 291(1000th cycle,average capacity decay of 0.017%)and 142 mAh g^(-1)(5000th cycle,average capacity decay of 0.011%)at a current density of 0.5 and 2.0 A g^(-1),respectively.

Coral-Like Yolk–Shell-Structured Nickel Oxide/Carbon Composite Microspheres for High-Performance Li-Ion Storage Anodes

In this study, coral?like yolk–shell?structured NiO/C composite microspheres(denoted as CYS?NiO/C) were prepared using spray pyrolysis. The unique yolk–shell structure was characterized, and the formation mechanism of the structure was proposed. Both the phase separation of the polyvinylpyrrolidone and polystyrene(PS) colloidal solution and the decompo?sition of the size?controlled PS nanobeads in the droplet played crucial roles in the formation of the unique coral?like yolk–shell structure. The CYS?NiO/C microspheres delivered a reversible discharge capacity of 991 mAh g^(-1) after 500 cycles at the current density of 1.0 A g^(-1). The dis?charge capacity of the CYS?NiO/C microspheres after the 1000 th cycle at the current density of 2.0 A g^(-1) was 635 mAh g^(-1), and the capacity retention measured from the second cycle was 91%. The final discharge capacities of the CYS?NiO/C microspheres at the current densities of 0.5, 1.5, 3.0, 5.0, 7.0, and 10.0 A g^(-1) were 753, 648, 560, 490, 440, and 389 mAh g^(-1), respectively. The synergetic e ect of the coral?like yolk–shell structure with well?defined interconnected mesopores and highly conductive carbon resulted in the excellent Li+?ion storage properties of the CYS?NiO/C microspheres.

Carbon-Coated Three-Dimensional MXene/Iron Selenide Ball with Core–Shell Structure for High-Performance Potassium-Ion Batteries

Two-dimensional(2D)MXenes are promising as electrode materials for energy storage,owing to their high electronic conductivity and low diffusion barrier.Unfortunately,similar to most 2D materials,MXene nanosheets easily restack during the electrode preparation,which degrades the electrochemical performance of MXene-based materials.A novel synthetic strategy is proposed for converting MXene into restacking-inhibited three-dimensional(3D)balls coated with iron selenides and carbon.This strategy involves the preparation of Fe_(2)O_(3)@carbon/MXene microspheres via a facile ultrasonic spray pyrolysis and subsequent selenization process.Such 3D structuring effectively prevents interlayer restacking,increases the surface area,and accelerates ion transport,while maintaining the attractive properties of MXene.Furthermore,combining iron selenides and carbon with 3D MXene balls offers many more sites for ion storage and enhances the structural robustness of the composite balls.The resultant 3D structured microspheres exhibit a high reversible capacity of 410 mAh g^(−1) after 200 cycles at 0.1 A g^(−1) in potassium-ion batteries,corresponding to the capacity retention of 97% as calculated based on 100 cycles.Even at a high current density of 5.0 A g^(−1),the composite exhibits a discharge capacity of 169 mAh g^(−1).

Band gap tuning and p to n-type transition in Mn-doped CuO nanostructured thin films

Here we discuss the synthesis of copper(II)oxide(CuO)and manganese(Mn)-doped CuO thin films varying with 0 to 8 at%Mn using the spray pyrolysis technique.As-deposited film surfaces comprised of agglomerated spherical nanoparticles and a semi-spongy porous structure for 4 at%Mn doping.Energy dispersive analysis of X-rays confirmed the chemical composi-tion of the films.X-ray diffraction spectra showed a polycrystalline monoclinic structure with the predominance of the(11)peak.Optical band gap energy for direct and indirect transitions was estimated in the ranges from 2.67-2.90 eV and 0.11-1.73 eV,respectively.Refractive index and static dielectric constants were computed from the optical spectra.Electrical resistivity of CuO and Mn-doped CuO(Mn:CuO)thin films was found in the range from 10.5 to 28.6Ω·cm.The tiniest electron effective mass was calculated for 4 at%Mn:CuO thin films.P to n-type transition was observed for 4 at%Mn doping in CuO films.Carrier con-centration and mobility were found in the orders of 10^(17)cm^(-3)and 10^(-1)cm^(2)/(V·s),respectively.The Hall coefficient was found to be between 9.9 and 29.8 cm^(3)/C.The above results suggest the suitability of Mn:CuO thin films in optoelectronic applications.