Ionic Layer Research Articles

Facile SILAR deposited SnS/NiS vertical heterojunction for high performance flexible broadband photodetector

Low-cost, flexible broadband photodetectors fabricated from two-dimensional transition metal chalcogenides have garnered attention because of their excellent absorption coefficient and photoconductivity. Likewise, vertical heterojunctions fabricated from two two-dimensional (2D) transition metal chalcogenides (TMCs) also have drawn major curiosity lately owing to their superior optical performance. This work reports a p-p type II vertical Van der Waal's heterojunction structure by depositing thin film of NiS over SnS on a flexible paper substrate. Morphological and structural characterization confirms presence of a rhombohedral β-NiS crystal structure along with traces of Ni(OH)2 on orthorhombic SnS nanoparticles. The device fabrication method made use of the inexpensive, clean room free SILAR (Successive Ionic Layer Adsorption and Reaction) technique. A purposeful modification of narrow bandgap property of NiS is done by depositing it in an alkaline environment. The fabricated device records optical responsivity of 0.92 mA/W under UV illumination, 5.32 mA/W under Visible illumination, and 0.8 mA/W under NIR illumination. A maximum EQE of 1.3 % is observed along with superior response times of 0.114 s (UV),0.103 s (Visible) and 1.34 s (NIR). The acquired photo response is due to superior absorption property of NiS in UV region and SnS in the visible and NIR region. The difference in fermi level between two materials causes efficient separation of the charge carriers that results in junctional electric field upon light illumination. The device underwent flexibility testing and shown exceptional resistance to bending force making it suitable for numerous applications like wearable healthcare monitoring, security purposes and flexible image sensors.

A Lanthanide-Incorporated Phospho(III)tungstate Aggregate Constructed from [HPIIIW8O31]10- and [W11O39]12- Building Blocks and Its Nanocomposite with CdS for Ultrasensitive Photoelectrochemical Detection of Oxytetracycline.

A novel tartronic acid decorated hexa-CeIII-incorporated phospho(III)tungstate aggregate (C4H12NO)6Na18H2[(HPW8O31)2[W11O39]2(H2TAD)4(H2O)4W4Ce6H2P2O14]·84H2O (1, H3TAD = tartronic acid) was synthesized by a one-step assembly strategy. Its main skeleton is constructed from two [W11O39]12- fragments, two [HPIIIW8O31]10- segments and one H2TAD--ornamented dodecanuclear heterometallic [W4Ce6H2PIII2O14(H2TAD)4(H2O)4]18+ cluster. In the structure, the [HPIIIO3]2- groups not only work as the heteroatom template to induce the formation of lacunary [HPIIIW8O31]10- segments but also function as the connector to bridge Ce3+ cations. With the help of a reaction strategy of combining ultrasonication treatment with the continuous ion layer adsorption method, the 1/CdS composite was constructed and exhibits prominent photoelectrochemical activity. The 1/CdS composite was used as a photoelectrochemical sensor for oxytetracycline detection at 0 V (vs Ag/AgCl), which displays excellent properties with quick response and low limit of detection (0.042 nM). This work can provide some helpful references in the construction of novel PIII-induced polyoxometalates consisting of different building blocks and can extend the applications of polyoxometalate-based nanocomposites into photoelectrochemical detection for antibiotics as well as biomolecules.

Electrostatic Clutches Based on Ionomer Heterojunctions for Low‐Voltage Switching of Stiffness and Strength

AbstractElectrostatic clutches offer electrically programmable control of system stiffness, providing significant advantages in various robotic and haptic applications. However, conventional dielectric‐based electrostatic clutches require high operating voltages, often surpassing several kilovolts, while most low‐voltage electro‐adhesives are unsuitable for electrostatic clutches due to their intrinsic tackiness, resulting in a low switching ratio and reversibility. Here, an electrostatic clutch based on ionomer heterojunctions on rigid electrodes, encased within soft elastomers, capable of switching the system stiffness more than 530‐fold at an operating voltage of just 1 V is presented. Under the reverse bias, the formation of an ionic double layer at the ionomer heterojunction interface enables strong electrostatic adhesion of stiff electrodes at low voltage, yet low tackiness of ionomers allows almost free sliding at the forward bias. The performance of these electrostatic clutches across various geometries and voltages based on the fracture mechanics model is explored. Within this framework, by adjusting the clutch compliance, a force capacity of 50 N cm−2, powered by a 1.5 V battery with an on/off ratio over 250 is achieved, outperforming the latest electrostatic clutches in operating voltage and switching ratio.

A self-powered photoelectrochemical and non-enzymatic glucose sensor based on ERGO/ZnONWs/CdS photoanode

We have developed an efficient, self-powered, non-enzymatic photoelectrochemical (PEC) glucose sensor operating in the visible spectrum. The sensor is based on electrochemically reduced graphene oxide (ERGO) and zinc oxide (ZnO) nanowalls (NWs) decorated with cadmium sulfide (CdS) quantum dots (QDs). We used a one-pot electrochemical process to grow vertically aligned ZnONWs on ERGO, followed by using the sequential ionic layer adsorption and reaction (SILAR) technique to decorate the ZnONWs with CdS QDs. The resulting ERGO/ZnONWs/CdS photoelectrode exhibits a three-dimensional hierarchical morphology, providing a large surface area for enhanced surface-substrate interactions and increased optical path length, leading to high absorptivity at visible light. Under one solar light illumination without a bias voltage, the electrode generated a significantly higher photocurrent density (1150 µAcm-2) in the presence of glucose (15.00 mM) than in the absence of glucose (150 µAcm-2). As a PEC glucose sensor, the ERGO/ZnONWs/CdS photoelectrode demonstrated two linear correlations in the glucose concentration range of 0.01–1.00 mM and 1.00–15.00 mM. The sensor has 430.06 and 25.75 µA cm-2mM-1 sensitivities and a low detection limit (1.1 µM). This novel visible light-mediated self-powered electrochemical sensing platform is cost-effective, reproducible, and stable for non-enzymatic glucose detection.

SILAR deposited Antiviral silver-doped Ceria nano-films

Amid the COVID-19 global pandemic, ceria nanomaterials (CN) have garnered renewed interest as potential antiviral agents due to their ability to generate reactive oxygen species (ROS) on their surfaces. Enhancing ROS generation through precise defect engineering is key to improving these antiviral properties. This can be achieved through various methods, such as altering nano-dimensions and doping. In this context, we report on silver-doped ceria thin films. We have employed a cost-effective SILAR (Successive Ionic Layer Adsorption and Reaction) method for ceria nano-film deposition, which offers excellent control over film thickness. Utilizing an Arduino-controlled layer-by-layer (LBL) setup, we achieved precise control over the deposition process. This method facilitated the easy doping of ceria nano-films with silver ions. The silver-doped SILAR ceria thin films of varying thicknesses were subjected to antibacterial testing against E. coli bacteria. The samples with the highest antibacterial activity were further tested for antiviral efficacy against Feline calicivirus. The 80 SILAR Layers Ag-Ceria sample exhibited the best activity, completely deactivating the viral titer (105). This sample, when further tested against OC43 coronavirus, demonstrated a >99% reduction in virus titer. The mechanisms underlying these antimicrobial properties were investigated using antioxidative testing assays.

Nanoparticle agglomeration in molten salt nanofluids: Free energy landscape and its impacts on thermal transport property degradation

The nanofluids consisting of molten salt and nanoparticles can gain enhanced thermal performance for heat transfer and energy storage processes. Agglomeration of nanoparticles is ubiquitous in this colloidal dispersion, deteriorating the dispersed states of the nanocomposite interiors, and its microscopic mechanisms are unsatisfactorily explored. In this work, molecular dynamics simulations combined with umbrella sampling technique to capture the relative dispersion state of nanoparticles in molten salts effectively were performed to reveal the free energy landscape of agglomeration and its influence on heat transport. The dominant deep minima in the free energy surface demonstrates that the agglomeration of MgO nanoparticles in the molten NaCl salt is principally induced by van der Waals attractions between MgO nanoparticles and aggravated by large surface area. The unstable dispersion of nanoparticles is the most fatal problem for enhanced thermal conductivity during agglomeration, and the relative distance of MgO nanoparticles has less impacts on the thermal conductivity of the melt. The stronger adsorption of ions around nanoparticles can improve their relative dispersion, and utilize interfacial effects to enhance the thermal conductivity. Combined with the benefit of ordered ionic layer on the surface, the MgO nanoparticles of 10 Å diameter (specific surface area of ∼ 938.80 m2/g) become the optimal choice for molten NaCl. With the mechanisms of interfacial microstructures preventing agglomerated nanoparticles and improving heat transfer of molten salts revealed, this work can enlighten the selection or feasible modification for nanoparticles in various high-temperature molten salts, since the mechanisms are universal to other nanofluids, especially for ionic liquid based nanofluids.

Cation valency in water-in-salt electrolytes alters the short- and long-range structure of the electrical double layer

Highly concentrated aqueous electrolytes (termed water-in-salt electrolytes, WiSEs) at solid-liquid interfaces are ubiquitous in myriad applications including biological signaling, electrosynthesis, and energy storage. This interface, known as the electrical double layer (EDL), has a different structure in WiSEs than in dilute electrolytes. Here, we investigate how divalent salts [zinc bis(trifluoromethylsulfonyl)imide, Zn(TFSI)2], as well as mixtures of mono- and divalent salts [lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) mixed with Zn(TFSI)2], affect the short- and long-range structure of the EDL under confinement using a multimodal combination of scattering, spectroscopy, and surface forces measurements. Raman spectroscopy of bulk electrolytes suggests that the cation is closely associated with the anion regardless of valency. Wide-angle X-ray scattering reveals that all bulk electrolytes form ion clusters; however, the clusters are suppressed with increasing concentration of the divalent ion. To probe the EDL under confinement, we use a Surface Forces Apparatus and demonstrate that the thickness of the adsorbed layer of ions at the interface grows with increasing divalent ion concentration. Multiple interfacial layers form following this adlayer; their thicknesses appear dependent on anion size, rather than cation. Importantly, all electrolytes exhibit very long electrostatic decay lengths that are insensitive to valency. It is likely that in the WiSE regime, electrostatic screening is mediated by the formation of ion clusters rather than individual well-solvated ions. This work contributes to understanding the structure and charge-neutralization mechanism in this class of electrolytes and the interfacial behavior of mixed-electrolyte systems encountered in electrochemistry and biology.

Performance evaluation of SILAR deposited Rb-Doped ZnO thin films for photodetector applications

ZnO-based photodetectors (PDs) compose a remarkable optoelectronic device field due to their high optical transmittance, electrical conductivity, wide band gap, and high binding energy. This study examined the visible light photodetector performance of the pristine and Rubidium (Rb)-doped ZnO thin films. The influence of Rb doping amount (2, 4, and 6 wt% in solution) on the electrical, optical, and structural properties of the ZnO-based thin films produced by the Successive Ion Layer Adsorption and Reaction (SILAR) technique was analyzed. Structural analyses showed that all peaks correspond to hexagonal wurtzite structure with no other peak from Rb-based phases, suggesting the high quality of the crystalline pristine and Rb-doped ZnO thin films. The morphology of the thin films shows homogenous layers formed of nanoparticles where particle size was first decreased and then increased with the increasing Rb doping according to Scanning Electron Microscope (SEM) morphology analysis. Besides that, Raman spectroscopy analyses indicate that the phonon lifetimes of the ZnO-based thin films slightly increased due to the improvement of the crystal quality with the increasing amount of Rb in the SILAR solution. Photosensor measurements of the nanostructured pristine and Rb-doped ZnO thin films were measured at different light power intensities under the visible light environment. Photosensor properties were examined depending on the doping amount and light power density. In light of the literature review, our study is the first to produce Rb-doped ZnO thin films via the SILAR method, which has a promising potential for photosensor applications.Graphical

Real‐Time Product Detection during CO2 Electroreduction on SCILL‐Modified Cu Catalysts

AbstractModifying the chemical environment of active surfaces with ionic liquids (IL) is an emerging strategy for tailoring novel electrocatalytic systems, including carbon dioxide reduction (CO2RR). Although copper (Cu) catalysts have recently gained more attention in this field, their modification with ILs is yet to be investigated. This work tested a range of common hydrophobic ILs impregnated into carbon‐supported Cu catalysts, following the “solid catalyst with ionic liquid layer” (SCILL) approach. The latter was used to showcase the applicability of real‐time product detection for CO2RR employing electrochemical mass spectrometry. The observed patterns of C1 to C3 product selectivity offered valuable insights into the intricate reaction mechanism. In addition, increasing the size of the IL cation showed an opposite and significant effect on the reaction selectivity. The obtained qualitative results were partially compared with conventional long‐term experiments.

Active microparticle propulsion pervasively powered by asymmetric AC field electrophoresis

HypothesisSymmetry breaking in an electric field-driven active particle system can be induced by applying a spatially uniform, but temporally non-uniform, alternating current (AC) signal. Regardless of the type of particles exposed to sawtooth AC signals, the unevenly induced polarization of the ionic charge layer leads to a major electrohydrodynamic effect of active propulsion, termed Asymmetric Field Electrophoresis (AFEP). ExperimentsSuspensions containing latex microspheres of three sizes, as well as Janus and metal-coated particles were subjected to sawtooth AC signals of varying voltages, frequencies, and time asymmetries. Particle tracking via microscopy was used to analyze their motility as a function of the key parameters. FindingsThe particles exhibit field-colinear active propulsion, and the temporal reversal of the AC signal results in a reversal of their direction of motion. The experimental velocity data as a function of field strength, frequency, and signal asymmetry are supported by models of asymmetric ionic concentration-polarization. The direction of particle migration exhibits a size-dependent crossover in the low frequency domain. This enables new approaches for simple and efficient on-chip sorting. Combining AFEP with other AC motility mechanisms, such as induced-charge electrophoresis, allows multiaxial control of particle motion and could enable development of novel AC field-driven active microsystems.

Interfacial Engineering of BiVO4/Bi2Mo2O9 Heterojunction Toward Photogenerated Carriers Anisotropic Transfer

Developing an advanced strategy to decrease the charge recombination of BiVO4 is a vital requirement to boost charge transfer for photoelectrochemical water oxidation. Herein, a type II BiVO4/Bi2Mo2O9 heterojunction is successfully synthesized on fluorine‐doped tin oxide substrate by successive ionic layer adsorption and reaction method. Thanks to the Fermi‐level energy difference of 275 mV between BiVO4 and Bi2Mo2O9, an outward built‐in electric filed pointing from Bi2Mo2O9 to BiVO4 is induced, which accelerates the directional flowing of photogenerated electron and hole. Such a unique design structure fastens the electron migration from BiVO4 to Bi2Mo2O9, and the holes will transfer to the surface to participate in water oxidation. The longer lifetime (9.2 ns) by time‐resolved transient photoluminescence signifies that the Bi2Mo2O9 can boost interfacial carriers’ anisotropic migration; the surface charge transfer rate of BiVO4/Bi2Mo2O9 is up to 387.6 s−1 (1.4 V vs reversible hydrogen electrode (RHE)). The BiVO4/Bi2Mo2O9 heterojunction exhibits a remarkable charge separation efficiency of 64% and outstanding photocurrent density of 0.9 mA cm−2 at 1.23 V versus RHE.

Enhanced ionic transport and performance with a built-in electric field impact in LSCF-LCP double layer electrolyte

The widely used cathode La0·7Sr0·3Co0·5Fe0·5O3-δ (LSCF) perovskite and excellent electrolyte LaPr-codoped ceria (LCP) are combined into a double-layer LSCF-LCP electrolyte. Leveraging the semiconductor-ion material nature, a built-in electric field (BIEF) is established at the junction between the semiconductor LSCF and ionic conductor LCP layers to enhance ionic transport, consequently improving fuel cell power output. Comparative research on the double-layer LCP with LSCF brushing thin films, varying LSCF thickness from 50 μm to 150 μm, reveals that the LSCF layer with 100 μm thickness yields the highest fuel cell power output, 567 mW/cm2 at 450 °C. Based on analysis of experimental results, we attribute these intriguing properties to the enhanced ion transport and delves into the BIEF effect. This study presents alternative avenues for advancing fuel cell technologies, offering insights valuable for research and development.

Effects of Rapid Heat Treatments on the Properties of Cu2O Thin Films Deposited at Room Temperature Using an Ammonia-Free SILAR Technique

We report herein the analysis of the properties of copper(I) oxide thin films deposited by an optimized ammonium-free successive ion layer adsorption and reaction (SILAR) technique. The Cu2O thin film deposition process was carried out at room temperature using copper acetate monohydrate, sodium citrate as complexing agent, and hydrogen peroxide as precursors of copper and oxygen ions, respectively. The harmless and easy-to-handle sodium citrate replaces the volatile NH4OH commonly employed as complexing agent in the SILAR technique for the deposition of metal oxide thin films. The optical, structural, morphological, and electrical properties of the as-deposited Cu2O thin films were studied as a function of the number of cycles during deposition, as well as their modifications produced by the effect of rapid thermal annealing (RTA) in vacuum in a temperature range of 200–250°C for 1 min, 3 min, and 5 min. The as-deposited thin films had cubic crystalline structure corresponding to the Cu2O phase as determined by x-ray diffraction (XRD), with a direct energy bandgap of 2.43–2.51 eV depending on the number of cycles, and electrical resistivity of the order of 103 Ω cm. The XRD and x-ray photoelectron spectroscopy (XPS) analysis of the Cu2O thin films treated by RTA demonstrated an increase of the crystal size with time and temperature of the RTA and reduction effects from Cu2+ to Cu1+ oxidation states. On the other hand, the RTA treatments also decreased their energy bandgap to 2.38 eV and electrical resistivity to 102 Ω cm. The high energy bandgap values of the Cu2O thin films were attributed to quantum confinement effects produced by their small crystal size in the range of 3.6–8.6 nm.Graphical

Impact of deposition parameters on the optical properties of Fe2O3 thin films prepared by SILAR method

In order to explore the structures, morphology, and optical features of Fe2O3 nanofilms, the successive ionic layer adsorption and reactions (SILARs) technique was utilized to deposit the nanofilms onto glassy slides at varying concentrations of the precursor. Three precursor concentrations (0.025, 0.05 and 0.075) M were used. Analysis using X-ray diffraction (XRD) presented the crystalline structure of the Fe2O3 thin films. Field emission-scanning electron microscopy (FE-SEM) was used to evaluate the morphological features of the films. The results demonstrate that the surfaces of the films are nonporous and that there is a good distribution for spherical nanosize particles. The number of cycles is another important parameter that has been tested and its effect on the optical properties of prepared films was evaluated. The optical properties like optical absorption and energy gaps are affected directionally by changing the concentration and cycle numbers during the preparation. The latest objective of our study is to determine the role of precursor concentrations and deposition cycles in preparing thin films that have electronic applications such as sensors and solar cells.

Operando-reconstructed polyatomic ion layers boost the activity and stability of industrial current–density water splitting

Metal–organic frameworks have garnered attention as highly efficient pre-electrocatalysts for the oxygen evolution reaction (OER). Current structure–activity relationships primarily rely on the assumption that the complete dissolution of organic ligands occurs during electrocatalysis. Herein, modeling based on NiFe Prussian blue analogs (NiFe-PBAs) show that cyanide ligands leach from the matrix and subsequently oxidize to corresponding inorganic ions (ammonium and carbonate) that re-adsorb onto the surface of NiFe OOH during the OER process. Interestingly, the surface-adsorbed inorganic ions induce the OER reaction of NiFe OOH to switch from the adsorbate evolution to the lattice-oxygen–mediated mechanism, thus contributing to the high activity. In addition, this reconstructed inorganic ion layer acting as a versatile protective layer can prevent the dissolution of metal sites to maintain contact between catalytic sites and reactive ions, thus breaking the activity–stability trade-off. Consequently, our constructed NiFe-PBAs exhibit excellent durability for 1250 h with an ultralow overpotential of 253 mV at 100 mA cm−2. The scale-up NiFe-PBAs operated with a low energy consumption of ∼4.18 kWh m−3 H2 in industrial water electrolysis equipment. The economic analysis of the entire life cycle demonstrates that this green hydrogen production is priced at US$2.59 kg-1H2, meeting global targets (<US$2.5 kg-1H2).

Pd-N-doped carbons for chemoselective hydrogenation of cinnamaldehyde: Unravelling the influence of particle size and support in multiphase batch and continuous-flow systems

The chemoselective hydrogenation of the CC bond of cinnamaldehyde (CAL) was investigated under batch and continuous flow conditions, by comparing the performance of two ad-hoc prepared palladium-based catalysts supported on N-doped carbons to that of a commercial Pd/C system. An impregnation (I) and a solution-mediated (S) protocols were used for the synthesis of the catalytic materials, Pd-N/Ci and Pd-N/Cs, respectively, in the presence of chitin as a precursor of the support. The S method afforded palladium nanoparticles of 2.0±0.5 nm, while by impregnation, a wider size distribution was achieved with particles mostly belonging to two groups displaying a mean radius of 3.0±0.5 nm and 8.4±0.5 nm, respectively. A parametric analysis of the hydrogenation reaction showed that both the reaction conditions and the nature of the catalysts played a role to steer the selectivity towards the formation of the desired product, 3-phenylpropanal (hydrocinnamaldehyde, HCAL). At 50 °C and 1 bar H2, in a triphasic (liquid-liquid-liquid) batch reactor where the catalyst was compartmentalized in an ionic liquid layer, Pd-N/Ci and commercial Pd/C were almost equally active and allowed to obtain HCAL in a 90–96 % selectivity at complete conversion. On the other hand, at the same T and p (50 °C/1 bar), Pd-N/Cs was more effective in the continuous-flow mode: the process was quantitative yielding HCAL with a selectivity and a productivity of 91 % of 16 mmol (gcat h)−1, respectively, while the catalyst proved highly stable showing no loss of activity over 300 min of time on-stream. The reaction environment, the size and dispersion of the metal active sites, and the nature of the catalyst support were major contributors to such results, acting synergistically to each other to tune the energetics of adsorption/desorption of reactants/products, of the interfacial interactions/ barriers, and in the last analysis, of the process kinetics/selectivity.

Synthesis of Bi2S3-sensitized TiO2 photoanodes for enhanced photovoltaic performance in solar cell application

The synthesis of Bi2S3 nanoparticles for sensitizing TiO2 photoanodes were synthesized through a cost-effective and straightforward approach using modified chemical bath deposition (M-CBD) or successive ionic atomic layer adsorption reactions (SILAR) at room temperature. Initially, a TiO2 seed layer was synthesized at room temperature via the chemical bath deposition method, followed by deposition of a mesoporous TiO2 layer using the doctor blade method. This study investigated the influence of the number of SILAR cycles and the choice of counter electrodes on the performance of Bi2S3/TiO2-based photoelectrodes. Characterization of the prepared Bi2S3/TiO2 photoanode involved various techniques, including X-ray diffraction, UV–Vis spectroscopy, scanning electron microscopy, and Raman spectroscopy, enabling the analysis of its structural, optical, and morphological properties. The Bi2S3/TiO2-based cell exhibits a maximum conversion efficiency of 0.8%, demonstrating the potential of this combination for photovoltaic applications. This study contributes to the field of solar cell technology by presenting a novel approach for sensitizing TiO2 photoanodes with Bi2S3 nanoparticles, offering insights into the optimization of fabrication parameters and performance enhancement strategies for future device design and development.

Effect of Precursors Concentration on The Optical and Photoelectrochemical Properties of Bi₂S₃/TiO₂ Nanotubes Arrays Photoanode Synthesized by the SILAR Technique

The use of robust solar energy-driven photocatalysis materials to address the global energy and environmental crisis has gained significant attention in recent years. However, the wide band gaps in many robust semiconductor photocatalysts hinder their absorption of visible light from the solar spectrum. To address this issue, the modification of the large band gap semiconductor with the lower band gap material using the Successive Ionic Layers Adsorption and Reaction (SILAR) technique has emerged as an economical, accessible, and reproducible method for depositing nanoscale materials onto semiconductor substrates. This research aims to know how the concentration variation of cation and anion precursors in the SILAR technique affects the optical and photoelectrochemical properties of the resulting composite materials. Bi₂S₃ serves as a modifier for TiO₂ nanotube arrays (NTAs). The result shows that the cation-anion concentration ratio of 1:1.5 mM with five SILAR cycles gives the best photoelectrochemical performance, with a stable current density of 0.12 mA/cm², compared to pristine TiO₂ NTAs the current density of Bi₂S₃/TiO₂ NTAs is 15-fold. In addition, at each variation, the concentration ratio of cation and anion precursors decreases bandgap energy with each increase in the SILAR cycle.

Influence of solution pH dependency on structure, optical with photoelectrochemical characteristics of SILAR deposited copper oxide thin films

Photoelectrochemical (PEC) technology is a promising approach for converting solar energy into chemical energy, offering significant potential for renewable energy applications. In this work, the CuO thin film was fabricated with different pH value in between 8.5 ± 0.1 and 10.5 ± 0.1 via Successive Ionic Layer Adsorption and Reaction (SILAR) method. The Effect of pH on thickness, structural, morphological, elemental composition and optical properties were investigated by using stylus profilometry, XRD, SEM, TEM, EDX, UV–vis and PL. The XRD results showed that as the pH increased, the crystallite size increased from 19.24 nm to 25.62 nm, with a monoclinic phase along the (111) direction. The CuO film deposited at pH value 10.5 ± 0.1 exhibit well defined identical particle with its size in the range between 200 and 300 nm was confirmed by SEM and TEM analysis. As the pH increased from 8.5 ± 0.1 to 10.5 ± 0.1, the CuO film bandgap (Eg) value reduced from 1.52 eV to 1.42 eV with indirect transition. The CuO photocathode deposited at pH 10.5 ± 0.1 shows maximum photocurrent density of 1.45 mA/cm2 at −0.1 V vs. RHE in 0.5 M Na2SO4 solution. Furthermore, the Electrochemical Impedance Spectroscopy (EIS) analysis shows, the CuO (pH 10.5 ± 0.1) electrode have higher conductivity value of 0.6862 S/cm compared CuO at pH 8.5 ± 0.1 (0.2779 S/cm) and CuO at pH 9.5 ± 0.1 (0.4646 S/cm) electrodes.

Facile preparation of CoFe-MnO2@titania nanotube array bifunctional electrodes for high-current-density water splitting at industrial temperatures

The development of bifunctional electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) at high current density under industrial temperatures is crucial for large-scale industrial hydrogen production from water splitting. In this work, M-MnO2@TNTA composite electrodes were prepared by depositing various metal ion-doped manganese oxide nanoparticles on the titania nanotube array (TNTA) by successive ionic layer adsorption reaction (SILAR) method, and their HER and OER electrocatalytic performances were investigated in 1 M KOH. Results show that the CoFe-MnO2@TNTA composite electrode prepared by simultaneous doping of Co3+ and Fe3+ in MnO2 exhibits optimal catalytic performance. Compared with MnO2@TNTA without ion doping, the overpotentials of CoFe-MnO2@TNTA at 10 mA cm−2 (η10) for HER and OER are reduced by 571 and 665 mV. In addition, the electrode performance can be significantly enhanced by increasing the test temperature, and the porous array structure enables CoFe-MnO2@TNTA to exhibit better performance at high current densities. At 50 °C, which is the common industrial electrolytic water temperature, the η10 of CoFe-MnO2@TNTA for HER is almost equal to that of the Pt/C electrode. The η100 of CoFe-MnO2@TNTA for HER is reduced by 35 mV compared with the Pt/C electrode. Moreover, η200 of CoFe-MnO2@TNTA for OER is significantly lowered by 111 and 184 mV compared with IrO2 and RuO2 electrodes. Utilizing CoFe-MnO2@TNTA as both the cathode and anode for overall water splitting, the electrolysis voltage is merely 2.33 V under the current density of 200 mA cm−2, much lower than that of IrO2 (+)||Pt/C (–) (2.68 V). The present work may provide a valuable reference for the development of self-supporting bifunctional electrodes suitable for high-current-density water splitting at industrial temperatures.