Anodic Oxidation Research Articles

Facile nanofabrication and simultaneous color-and-Raman hybrid mechanism of economic SERS substrate with tunable structure color for high enhancement factor

The conventional SERS technique utilizing metal nanoparticles (MNPs) is a powerful optical sensing method, relying on the inelastic collision between incident light and the analyte. However, the development of traditional color-tunable MNP-SERS substrates remains limited to two separate components of the color supporter for generating structure color and followed by the MNPs coating to generate the localized surface plasmonic resonance for SERS sensing. Here, a novel color-tunable SERS substrate without MNPs based on the economic one-step anodic aluminum oxide (AAO) coated with nanoporous Pt films was proposed to generate the color-and-Raman hybrid effect for high enhancement factor. This novel SERS substrate employs an economic method, that is a facile and low-cost one-step anodization process to fabricate the AAO with tunable structure color, enabling adaptation to excitation of laser sources. The substrate with the lowest reflectance to laser light exhibits the highest enhancement factor due to the coupling between the laser and the substrate. The resultant SERS substrate demonstrates a high enhancement factor (EF) of 5.27x105 to methylene blue with a good uniformity of the relative standard deviation (RSD) of 6.35 %. In a practical application, one of preservative, benzoic acid, was detected with a low concentration of 1 ppm in the extraction solution of tapioca balls. This innovative approach promotes limitations associated with traditional color-tunable SERS substrates and offers a promising path for sensitive and versatile trace substance detection.

Harnessing in-situ oxidation of nanostructured mxene to modulate the electronic structure for improved selectivity for electrochemical carbon dioxide reduction

The electrochemical CO2 reduction reaction (CO2RR) is a promising approach to valorizing CO2. Ti3C2TX as a support material has received significant interest in enhancing CO2RR performance for tuning the electronic structure. However, there has been relatively less focus on changes to the Ti3C2TX electronic structure induced by loading catalysts onto the Ti3C2TX. Because Ti3C2TX has an intrinsic activity for both CO2RR and the competitive hydrogen evolution reaction (HER), electronic structure changes can affect the balance between CO2RR and HER selectivity. Therefore, tuning the electronic structure of Ti3C2TX can control the competition between CO2RR and HER and tune the selectivity and activity. Herein, we report that Ti3C2TX’s electronic structure can be tuned by the Ag+ loading method via redox interactions, tuning the reaction selectivity and activity for CO2RR. To illustrate this effect, we compare the CO2RR performance of in-situ formed Ag nanoparticles (NPs) on Ti3C2TX (0.9Ag-IS-Ti3C2TX) with physically mixed Ag NPs and Ti3C2TX (0.9Ag/P/Ti3C2TX). Here, ‘0.9’ refers to the molar ratio between Ag precursor and Ti3C2Tx, and ‘IS’ vs. ‘P’ refers to in-situ formed vs. physically mixed Ag NPs. 0.9Ag-IS-Ti3C2TX demonstrates a higher oxidation state for Ti and a higher proportion of Ti-O bonds than 0.9Ag/P/Ti3C2TX. Compared to 0.9Ag/P/Ti3C2TX, 0.9Ag-IS-Ti3C2TX exhibits higher CO Faradaic efficiency (FE), rising from 8.1 % with a partial current density of −2.0 mA cm−2 to 49.6 % with a partial current density of −20.1 mA cm−2 at −1.4 V vs. RHE (reversible hydrogen electrode). To harness this effect, we demonstrate control over the CO: H2 ratio of syngas formed from CO2RR over our Ti3C2TX-supported catalysts. Further electrochemical anodic oxidation experiments reveal the critical oxidation potential of Ti3C2TX (0.8 V vs. RHE) and show that HER can be partially suppressed by partial oxidation of Ti3C2TX. This work highlights the importance of considering the changes in Ti3C2TX (and other) supports when supporting catalysts for CO2RR and other electrochemical reactions.

Oscillating Structural Transformations in the Electrochemical Synthesis of Graphene Oxide from Graphite.

Electrochemical synthesis of graphene oxide (GO) is known to occur with potential oscillations, but the structural changes underlying these oscillations have remained unclear. In situ time-resolved synchrotron radiation X-ray diffraction demonstrates that the electrochemical synthesis of GO in aqueous H2SO4 can be described as an oscillating reaction. The transformation from graphite to GO proceeds through periodic structural oscillations that correlate with potential cycles. Stage-1 graphite intercalation compound (GIC) is found only at the peak of the potential cycle, but not at the bottom of the cycle. Stage-1 GIC is formed in the first half-cycle from stage-2 GIC and then transforms into "pristine graphite oxide" (PGO) on the lower side of the potential cycle, after which the cycle restarts with the formation of a new portion of stage-1 GIC. Water-washing results in the transformation of PGO into water-swollen GO with d(001) ~11 Å. These periodic structural changes can be considered a new type of oscillating reaction. The presented results provide broad insights into the oscillating structural changes occurring during the anodic graphite oxidation in aqueous H2SO4 and allow to update of the mechanism of GO electrochemical formation.

Oscillating Structural Transformations in the Electrochemical Synthesis of Graphene Oxide from Graphite

AbstractElectrochemical synthesis of graphene oxide (GO) is known to occur with potential oscillations, but the structural changes underlying these oscillations have remained unclear. In situ time‐resolved synchrotron radiation X‐ray diffraction demonstrates that the electrochemical synthesis of GO in aqueous H2SO4 can be described as an oscillating reaction. The transformation from graphite to GO proceeds through periodic structural oscillations that correlate with potential cycles. Stage‐1 graphite intercalation compound (GIC) is found only at the peak of the potential cycle, but not at the bottom of the cycle. Stage‐1 GIC is formed in the first half‐cycle from stage‐2 GIC and then transforms into “pristine graphite oxide” (PGO) on the lower side of the potential cycle, after which the cycle restarts with the formation of a new portion of stage‐1 GIC. Water‐washing results in the transformation of PGO into water‐swollen GO with d(001) ~11 Å. These periodic structural changes can be considered a new type of oscillating reaction. The presented results provide broad insights into the oscillating structural changes occurring during the anodic graphite oxidation in aqueous H2SO4 and allow to update of the mechanism of GO electrochemical formation.

Aptamer-Conjugated Covalent-Organic Framework Nanochannels for Selective and Sensitive Detection of Aflatoxin B1.

Sensitive and selective detection of trace aflatoxin B1 (AFB1) in foods is of great importance to guarantee food safety and quality but still challenging because of its trace amount and the interference from the complex food matrix. Here, we report the integration of aptamer (Apt) and an ordered 2D covalent organic framework (COF) to solid-state anodic aluminum oxide (AAO) nanochannels (Apt/COF/AAO) for selective and sensitive detection of trace AFB1. The high specificity of Apt for AFB1 led to a selective change in the surface charge of Apt/COF/AAO and in turn the current change of the nanochannel, permitting the selective and sensitive determination of trace AFB1 in complex food samples. The developed nanofluidic sensor gave a wide linear range (1-500 pg mL-1), low detection limit (0.11 pg mL-1), and good precision (relative standard deviation of 1.5% for 11 replicate determinations of 100 pg mL-1). In addition, the developed sensor was successfully used for the detection of AFB1 in food samples with the recovery of 86.9%-102.5%. The coupling of Apt-conjugated 2D COF with an AAO nanochannel provides a promising way for sensitive and selective determination of food contaminants in complex samples.

Zirconium-doped lead dioxide anodes prepared by sol-gel method for ampicillin removal from simulated pharmaceutical polluted wastewater.

New anodes consisting of zirconium-doped PbO2 coating, growth on titanium dioxide interlayer, were deposited on titanium substrates using spin coating method and have been tested for the removal of ampicillin, a β-lactam antibiotic, from water. Morphological, structural, and electrochemical properties of the prepared coatings were characterized by scanning electron microscopy (SEM), atomic force microscope (AFM), X-ray diffraction (XRD), and electrochemical impendence spectroscopy (EIS). Results showed that the incorporation of zirconium dopant had a noticeable modification in the morphology of anodes. An increase in the surface roughness and the specific active area were observed with Ti/TiO2/PbO2- 10% Zr electrode compared to other anodes. The electrochemical measurements indicated that the anode doped with 10% Zr showed a more protective coating performance than the undoped and 20% Zr-doped PbO2 electrodes. The experiments on ampicillin degradation revealed that doped lead dioxide anodes have excellent electrocatalytic activity. The major byproduct generated during anodic oxidation treatment has been identified as ampicilloic acid by liquid chromatography-mass spectroscopy (LC-MS) analysis. Results demonstrated that Ti/TiO2/PbO2- 10% Zr anode presents the best removal rate of ampicillin with a minimum intermediate amount, which leads to conclude that 10% is the optimum percentage of zirconium dopant for antibiotic wastewater treatment.

Effect of electrochemical anodic oxidation modification on the interfacial properties of carbon fiber reinforced polyimide composites

Effect of electrochemical anodic oxidation modification on the interfacial properties of carbon fiber reinforced polyimide composites

Neutron phase filtering for separating phase- and attenuation signal in aluminium and anodic aluminium oxide

Neutron imaging has gained significant importance as a material characterisation technique and is particularly useful to visualise hydrogenous materials in objects opaque to other radiations. Fields of application include investigations of hydrogen in metals as well as metal corrosion, thanks to the fact that neutrons can penetrate metals better than e.g. X-rays and are highly sensitive to hydrogen. However, at interfaces refraction effects sometimes obscure the attenuation image, which is used for hydrogen quantification. Refraction, a differential phase effect, diverts the neutron beam away from the interface in the image leading to intensity gain and intensity loss regions, which are superimposed to the attenuation image, thus obscuring the interface region and hindering quantitative analyses of e.g. hydrogen content in the vicinity of the interface. For corresponding effects in X-ray imaging, a phase filter approach was developed and is generally based on transport-of-intensity considerations. Here, we compare such an approach, that has been adapted to neutrons, with another simulation-based assessment using the ray-tracing software McStas. The latter appears superior and promising for future extensions which enable fitting forward models via simulations in order to separate phase and attenuation effects and thus pave the way for overcoming quantitative limitations at refracting interfaces.

Empowering Tri-Functional Palladium's Catalytic Activity and Durability in Electrocatalytic Formic Acid Oxidation Reaction via Innovative Self-Caging and Alloying Strategies.

Direct formic acid fuel cells (DFAFCs) stand out for portable electronic devices owing to their ease of handling, abundant fuel availability, and high theoretical open circuit potential. However, the practical application of DFAFCs is hindered by the unsatisfactory performance of electrocatalysts for the sluggish anodic formic acid oxidation reaction (FAOR). Palladium (Pd) based nanomaterials have shown promise for FAOR due to their highly selective reaction mechanism, but maintaining high electrocatalytic durability remains challenging. In this study, a novel Pd-based electrocatalyst (UiO-Pd-E) is reported with exceptional durability and activity for FAOR, which can be attributed to the Pd nanoparticles encapsulated within a carbon framework where concurrent chemical alloying of Pd and Zr occurs. Further, the UiO-Pd-E demonstrates noteworthy multifunctionality in various electrochemical reactions including electrocatalytic ethanol oxidation reaction (EOR) and oxygen reduction reaction (ORR) in addition to the FAOR, highlighting its practical potentials.

Potentiodynamic Polarization Study of PH3 Electrochemical Oxidation

ABSTRACTIn this study, the electrochemical behaviour of phosphine in sulphuric acid solutions on the surface of various electrode materials was conducted by voltammetric investigations. The effects of electrode materials such as lead, copper, and platinum electrodes on the PH3 anodic oxidation were investigated. Polarization curves were recorded by saturating the sulphuric acid solution with phosphine. The results received show that the electrochemical oxidation of phosphine on the lead electrode is accompanied by an oxygen evolution potential and, on the copper electrode, copper (II) ions show catalytic effects. The maximum anodic oxidation of phosphine on a platinum electrode was observed at the potential range of 0.8–1.0 V, and in the presence of copper (II) ions on the polarogram a maximum of phosphine oxidation is recorded at a potential of approximately 0.1–0.2 V.

TiO2 nanotube enhance osteogenesis through Kindlin-2/Integrin β1/YAP pathway-mediated mechanotransduction

Titanium has been widely employed in the fields of orthopaedics and dentistry, attributed to its superior mechanical and biological properties. The mechanical stimulation induced by the titanium dioxide (TiO2) nanotubes (TNTs) morphology resulting from surface modification has been demonstrated to enhance the osteogenic differentiation of bone marrow-derived mesenchymal stem cells (BMSCs). Kindlin-2, a pivotal focal adhesion protein, is involved in mechanical signaling processes through the regulation of stress fibril filament assembly. Additional research is needed to clarify the involvement of Kindlin-2 in the mechanism of TNTs-induced osteogenic differentiation. This study systematically investigated the impact of Kindlin-2 on TNTs-induced osteogenesis and mechanotransduction. TiO2 nanotubes with diameters of approximately 30 nm (TNT-30) and 100 nm (TNT-100) were fabricated and characterized using anodic oxidation. The results showed that TNT-100 significantly increased the expression of Kindlin-2 and enhanced osteogenic differentiation compared to polished titanium (PT) and TNT-30. Additionally, Kindlin-2 promotes cytoskeleton assembly by regulating the integrin β1/FAK/RhoA signaling pathway, impacting osteogenic gene expression and BMSC differentiation in a Yes-Associated Protein (YAP)-dependent manner. Therefore, these findings contribute to a more comprehensive understanding of the fate of BMSCs on TNTs morphologies and provide a novel theoretical foundation for the development of advanced bone repair biomaterials.

Unveiling the Dual Role of Oxophilic Cr4+ in Cr-Cu2O Nanosheet Arrays for Enhanced Nitrate Electroreduction to Ammonia.

Cuprous oxide (Cu2O)-based catalysts present a promising activity for the electrochemical nitrate (NO3-) reduction to ammonia (eNO3RA), but the electrochemical instability of Cu+ species may lead to an unsatisfactory durability, hindering the exploration of the structure-performance relationship. Herein, we propose an efficient strategy to stabilize Cu+ through the incorporation of Cr4+ into the Cu2O matrix to construct a Cr4+-O-Cu+ network structure. In situ and quasi-in situ characterizations reveal that the Cu+ species are well maintained via the strong Cr4+-O-Cu+ interaction that inhibits the leaching of lattice oxygen. Importantly, in situ generated Cr3+-O-Cu+ from Cr4+-O-Cu+ is identified as a dual-active site for eNO3RA, wherein the Cu+ sites are responsible for the activation of N-containing intermediates, while the assisting Cr3+ centers serve as the electron-proton mediators for rapid water dissociation. Theoretical investigations further demonstrated that the metastable state Cr3+-O-Cu+ favors the conversion from the endoergic hydrogenation of the key *ON intermediate to an exoergic reaction in an ONH pathway, and facilitates the subsequent NH3 desorption with a low energy barrier. The superior eNO3RA with a maximum 91.6% Faradaic efficiency could also be coupled with anodic sulfion oxidation to achieve concurrent NH3 production and sulfur recovery with reduced energy input.

Unveiling the Dual Role of Oxophilic Cr4+ in Cr‐Cu2O Nanosheet Arrays for Enhanced Nitrate Electroreduction to Ammonia

Cuprous oxide (Cu2O)‐based catalysts present a promising activity for the electrochemical nitrate (NO3‐) reduction to ammonia (eNO3RA), but the electrochemical instability of Cu+ species may lead to an unsatisfactory durability, hindering the exploration of the structure‐performance relationship. Herein, we propose an efficient strategy to stabilize Cu+ through the incorporation of Cr4+ into the Cu2O matrix to construct a Cr4+‐O‐Cu+ network structure. In situ and quasi‐in situ characterizations reveal that the Cu+ species are well maintained via the strong Cr4+‐O‐Cu+ interaction that inhibits the leaching of lattice oxygen. Importantly, in situ generated Cr3+‐O‐Cu+ from Cr4+‐O‐Cu+ is identified as a dual‐active site for eNO3RA, wherein the Cu+ sites are responsible for the activation of N‐containing intermediates, while the assisting Cr3+ centers serve as the electron‐proton mediators for rapid water dissociation. Theoretical investigations further demonstrated that the metastable state Cr3+‐O‐Cu+ favors the conversion from the endoergic hydrogenation of the key *ON intermediate to an exoergic reaction in an ONH pathway, and facilitates the subsequent NH3 desorption with a low energy barrier. The superior eNO3RA with a maximum 91.6% Faradaic efficiency could also be coupled with anodic sulfion oxidation to achieve concurrent NH3 production and sulfur recovery with reduced energy input.

Influence of micro-arc oxidation on the microstructure and dielectric properties of anodic aluminum oxide

To improve the dielectric performance of the anodic alumina film used in aluminum electrolytic capacitors, this study comparatively investigated the microstructure and dielectric properties of anodic aluminum oxide obtained through micro-arc oxidation (MAO) and conventional anodic oxidation (CAO). It is found that from the perspective of microstructure, the internal structure of the MAO treated oxide film has more and larger pores than that of CAO. This was attributed to the generation and overflow of numerous oxygen bubbles from within the oxide film at the locations where plasma sparks occurred during the process, thus forming larger pores. Regarding dielectric properties, the leakage current of the oxide film after MAO treatment was significantly reduced compared to CAO, with reductions of 58%, 56%, 64%, and 74% for the tested electrolytes Y1–Y4, respectively.

Biogas production from piloted wood-based bioethanol process using high-rate anaerobic treatment – Focusing for inhibition and improving biodegradability

To promote the bioeconomy, biorefineries with novel processes are developed. Biogas technology is commonly applied in biorefineries, and in this study, its feasibility for biogas production from wastewaters generated in a novel piloted wood-based bioethanol process was examined in expanded granular sludge bed reactors (EGSB). The novel wastewater was found to have high organic matter content and contained potentially inhibitory compounds. Wastewater was diluted with reactor effluent or tap water (control), and the proportion of wastewater in the feed was increased gradually to increase the organic loading rate. The wastewater was acidic (pH 4.2–4.6) and contained high concentrations of soluble chemical oxygen demand (sCOD 21–51 g/L) and sulfate (1–2.5 g/L). EGSB reactors had high sCODww (sCOD in the wastewater) removal of 74–77 % with OLRs up to 22 kg-sCODww/m3d and no inhibition either by the sulfide resulting from the high influent sulfate concentration or by the re-use of reactor effluent was seen. Integration of anodic oxidation (AO) to the EGSB reactor was studied in batch experiments increasing the biodegradability and total sCOD removal to 80–83 % and enhancing the methane production by 3 %. The results provide valuable information to support the implementation of anaerobic treatment plants as part of new industrial scale bioproduct production processes and encourages further studies on AO.

Quantitative Analysis of Ferrate(VI) and Its Degradation Products in Electrochemically Produced Potassium Ferrate for Waste Water Treatment

Potassium ferrate(VI) (K2FeO4) as a particularly strong oxidant represents an effective and environmentally friendly waste water treatment material. When produced by anodic oxidation in highly alkaline aqueous solution, the K2FeO4 product is separated and sealed in inert plastic bags with the retention of some liquid phase with high pH. This method proved to be excellent for long-term storage at moderately low temperature (5 °C) for industrial applications. It is still imperative to check the ferrate(VI) content of the product whenever it is to be used. Fe-57 Mössbauer spectroscopy is an excellent tool for checking the ratio of ferrate(VI) to the degradation product iron(III) in a sample. For this purpose, normally the spectral areas of the corresponding subspectra are considered; however, this approximation neglects the possible differences in the corresponding Mössbauer–Lamb factors. In this work, we have successfully determined the Mössbauer–Lamb factors for the ferrate(VI) and for the most common iron(III) degradation products observed. We have found superparamagnetic behavior and low-temperature phase transformation for another iron(III) degradation product that made the determination of the Mössbauer–Lamb factors impossible in that case. The identities of a total of three different iron(III) degradation products have been confirmed.

A review of recent advances in electrochemical and photoelectrochemical late-stage functionalization classified by anodic oxidation, cathodic reduction, and paired electrolysis.

With the resurgence of electrosynthesis in organic chemistry, there is a significant increase in the number of routes available for late-stage functionalization (LSF) of drugs. Electrosynthetic methods, which obviate the need for hazardous chemical oxidants or reductants, offer unprecedented control of reactions through the continuous variation of the applied potential and the possibility of combination with photochemical processes. This capability is a substantial advantage for performing electrochemical or photoelectrochemical LSF. Ultimately, these protocols are poised to become a vital component of the medicinal chemist's toolkit. In this review, we discuss electrochemical protocols that have been demonstrated to be applicable for the LSF of pharmaceutical drugs, their derivatives, and natural substrates. We present and analyze representative examples to illustrate the potential of electrochemistry or photoelectrochemistry for the LSF of valuable molecular scaffolds.

Mechanistic Analysis of Anodic Oxidation of Gold in KOH (0.1 M) Solution Using the Point Defect Model

The potentiostatic, anodic formation of gold oxide at potentials of 0.55 to 0.80 V versus SHE in aqueous KOH (0.1 M) was studied using an impedance-based Point Defect Model (PDM). The film thickness and refractive indices at each formation potential were estimated using spectroscopic ellipsometry. The thickness of the oxide increases linearly with increasing applied voltage within this range. Mott-Schottky (MS) analysis showed that gold oxide formed in KOH (0.1 M) is an n-type semiconductor, and the dominant defect (Aui3+) density is calculated to be in the order of 1021–1022 (1/cm3). The steady-state current density of the oxide formation was independent of voltage, also in agreement with an n-type oxide. Reasonable agreement between PDM predictions and experimental observations of dominant defect density, steady-state current density, and thickness, demonstrates the value of the PDM in this system.

Growth characteristics and physicochemical properties of nanoporous hafnium oxide layers prepared by anodic oxidation of Hf

Well defined nanostructures of doped or undoped HfO2 with unique physicochemical properties are crucial for applications in electronics, optoelectronics, sensors, and biomaterials. In this context, we have studied the fabrication of nanoporous anodic hafnium oxide (AHO) thin layers in ethylene glycol-based electrolytes containing NH4F. Although some earlier works have described the formation of nanoporous/nanotubular AHO layers in F− containing electrolytes, the key factors affecting the porosity, pore diameter, and thickness of synthesized materials have yet to be systematically investigated. We explored the feasibility of tuning unordered nanopores to ordered nanopores by varying the NH4F concentration in the electrolyte. We demonstrated that at constant anodizing voltage and time (30 or 60 V, 30 min), the mean porosity for the ordered porous AHO layer increases with NH4F concentration up to 0.10 M. We investigated the exclusive effects of anodizing time and NH4F concentration on the mean pore diameter, porosity, and thickness of AHO layer. The maximum mean porosity of 24.5 %, pore diameter of 39.8 nm, and the layer thickness of 24.6 μm were observed for AHO layers produced for 60 min at 60 V. Post-treatment thermal studies revealed the nanoporous AHO layer remained structurally stable up to 500 °C. X-ray diffraction studies showed a significant enhancement in crystallinity for thermally treated AHO layers. The composition and chemical environment of core elements at the top and bottom of AHO layer were thoroughly investigated using X-ray photoelectron spectroscopy (XPS). Furthermore, we elucidated the rate limiting step of AHO growth by applying growth models.

Interfacial Acid‐Like Microenvironment and Orbital Modulating Strategy toward Efficient Hydrogen Evolution in Neutral High‐Salinity Wastewater/Seawater

Electrochemical high‐salinity wastewater splitting is a promising technology for green hydrogen (H2) production. However, the kinetics of hydrogen evolution reaction (HER) in neutral media is slow, and the high theoretical potential of oxygen evolution reaction leads to large energy losses. Herein, an iron‐based electrocoagulation‐coupled hydrogen production integrated system (IEHPS) is constructed, which is realized by coupling low‐potential anodic iron oxidation reaction with cathodic HER. The non‐noble metal HxWO3‐Ni catalyst is synthesized by fabricating a proton sponge HxWO3 to achieve an interfacial acid‐like microenvironment and doping it with Ni heteroatom to modulate the 4d orbital of W, thereby weakening the adsorption strength of the W site toward hydrogen. Consequently, the HxWO3 Ni demonstrates remarkable performance characteristics, boasting a mere 131 mV overpotential at 10 mA cm−2 and Tafel slope of 44 mV dec− in neutral media. Operating at an applied voltage of 1.5 V, the IEHPS exhibits a high hydrogen production rate of 235 mL g−1 min−1 in seawater. It achieves nearly complete removal of contaminants like rhodamine B and heavy metal ions within a rapid 8–20 min, with an energy consumption of only 3.7 kWh Nm−3. This study provides a promising pathway for efficient and energy‐saving production of high‐purity hydrogen and effective treatment of high‐salinity wastewater.