TiO2 nanotube enhance osteogenesis through Kindlin-2/Integrin ß1/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 ß1/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.

Homochiral light-sensitive metal-organic framework photoelectrochemical gated transistor for enantioselective discrimination of monosaccharides.

As pure antipodes may differ in biological interactions, pharmacology, and toxicity, discrimination of enantiomers is important in the pharmaceutical and agrochemical industries. Two major challenges in enantiomer determination are transducing and amplifying the distinct chiral-recognition signals. In this study, a light-sensitive organic photoelectrochemical transistor (OPECT) with homochiral character is developed for enantiomer discrimination. Demonstrated with the discrimination of glucose enantiomers, the photoelectrochemically active gate electrode is prepared by integrating Au nanoparticles (AuNPs) and a chiral Cu(II)-metal-organic framework (c-CuMOF) onto TiO2 nanotube arrays (TNT). The captured glucose enantiomers are oxidized to hydrogen peroxide (H2O2) by the oxidase-mimicking AuNPs-loaded c-CuMOF. Based on the confinement effect of the mesopocket structure of the c-CuMOF and the remarkable charge transfer ability of the 1D nanotubular architecture, variations in H2O2 yield are translated into significant changes in OPECT drain currents (ID) by inducing a catalytic precipitation reaction. Variations in ID confer a sensitive discrimination of glucose enantiomers with a limit of detection (LOD) of 0.07 µM for L-Glu and 0.05 µM for D-Glu. This enantiomer-driven gate electrode response strategy not only provides a new route for enantiomer identification, but also helps to understand the origin of the high stereoselectivity in living systems.

Efficient electrochemical degradation of ceftazidime by Ti3+ self-doping TiO2 nanotube-based Sb-SnO2 nanoflowers as an intermediate layer on a modified PbO2 electrode.

Ceftazidime (CAZ) is an emerging organic pollutant with a long-lasting presence in the environment. Although some PbO2 materials exhibit degradation capabilities, inefficient electron transport in the substrate layer and the problem of electrode stability still limit their use. Here, an interfacial design in which TiO2 nanotube arrays generate Ti3+ self-doping oxide substrate layers and highly active 3D Sb-SnO2 nanoflowers-like interlayers was used to prepare PbO2 anodes for efficient degradation of CAZ. Interestingly, after implementing Ti3+ self-doping in the PbO2 anode base layer and introducing 3D nanoflowers-like structures, the capacity for •OH generation increased significantly. The modified electrode exhibited 5-fold greater •OH generation capacity compared to the unmodified electrode, and a 2.7-fold longer accelerated electrode lifetime. The results indicate that interfacial engineering of the base and intermediate layers of the electrodes can improve the electron transfer efficiency, promote the formation of •OH, and extend the anode lifetime of the activated CAZ system.

Enhanced ammonia oxidation by a photoelectrocatalysis­chlorine system: The role of ClO• and free chlorine.

The decomposition of ammonia-N to environmental-friendly N2 remains a fundamental problem for water treatment. We proposed a way to selectively and efficiently oxidize ammonia to N2 through an integrated photoeletrocatalysis­chlorine reactions (PECCl) system based on a bifunctional TiO2 nanotube photoanode. The ·OH and HClO can be simultaneously generated on the TiO2 nanotube photoanode in this system, which can in situ form ClO· for efficient ammonia removal. Compared with electrochemical­chlorine (EC-Cl), photocatalysis­chlorine (PC-Cl) and photoelectrocatalysis (PEC) systems, the PEC-Cl system exhibited much higher electrocatalytic activity due to the synergetic effect of photoelectrocatalyst and electrocatalyst in bifunctional TiO2 nanotube electrode. The removal efficiency of ammonia-N and total-N reached 100.0 % and 93.3 % at 0.3 V (vs Ag/AgCl) in the PEC-Cl system. Moreover, the system was efficient under various pH conditions. The reactions between ClO-/ClO· and the N-containing intermediates contributed to the high performance of the system, which expanded the reactions from the electrode surface to the electrolyte. Furthermore, radical scavenging and free chlorine determination experiments confirmed that ClO· and free chlorine were the main active species that enabled the ammonia oxidation. This study presents new understanding on the role of active species for ammonia removal in wastewater.

Synthesis of P-(NiCo)CO3 /TiO2 /Ti Self-Supported Electrode with High Catalytic Activity and Stability for Hydrogen Evolution.

Hydrogen is considered an ideal clean energy due to its high mass-energy density, and only water is generated after combustion. Water electrolysis is a sustainable method of obtaining a usable amount of pure hydrogen among the various hydrogen production methods. However, its development is still limited by applying expensive noble metal catalysts. Here, the dissolution-recrystallization process of TiO2 nanotube arrays in water with the hydrothermal reaction of a typical nickel-cobalt hydroxide synthesis process followed by phosphating to prepare a self-supported electrode with (NiCo)CO3 /TiO2 heterostructure named P-(NiCo)CO3 /TiO2 /Ti electrode is combined. The electrode exhibits an ultra-low overpotential of 31 mV at 10 mA  cm-2 with a Tafel slope of 46.2 mV dec-1 in 1 m KOH and maintained its stability after running for 500 h in 1 m KOH. The excellent catalytic activity can be attributed to the structure of nanotube arrays with high specific surface area, superhydrophilicity, and super aerophobicity on the electrode surface. In addition, the uniform (NiCo)CO3 /TiO2 heterostructure also accelerates the electron transfer on the electrode surface. Finally, DFT calculations demonstrate that phosphating also improves the ΔGH* and ΔGH2O of the electrode. The synthesis strategy also promotes the exploration of catalysts for other necessary electrocatalytic fields.

Customizing Wettability of Defect-Rich CeO2/TiO2 Nanotube Arrays for Humidity-Resistant, Ultrafast, and Sensitive Ammonia Response.

In all their applications, gas sensors should satisfy several requirements, including low cost, reduced energy consumption, fast response/recovery, high sensitivity, and reliability in a broad humidity range. Unfortunately, the fast response/recovery and sensing reliability under high humidity conditions are often still missing, especially those working at room temperature. In this study, a humidity-resistant gas sensor with an ultrafast response/recovery rate was designed by integrating a defect-rich semiconducting sensing interface and a self-assembled monolayer (SAM) with controllable wettability. As a proof-of-concept application, ammonia (NH3), one of the atmospheric and indoor pollutants, was selected as the target gas. The decoration of interconnected defective CeO2 nanowires on spaced TiO2 nanotube arrays (NTAs) provided superior NH3 sensing performances. Moreover, we showed that manipulating the functional end group of SAMs is an efficient and simple method to adjust the wettability, by which 86% sensitivity retention with an ultrafast response (within 5 s) and a low limit of detection (45 ppb) were achieved even at 75% relative humidity and room temperature. This work provides a new route toward the comprehensive design and application of metal oxide semiconductors for trace gas monitoring under harsh conditions, such as those of agricultural, environmental, and industrial fields.

Micro/nano topological modification of TiO2 nanotubes activates Thy-1 signaling to control osteogenic differentiation of stem cells.

Micro/nano topological modification is critical for improving the in vivo behaviors of bone implants, regulating multiple cellular functions. Titania (TiO2) nanotubes show the capacity of promoting osteoblast-related cell differentiation and induce effective osseointegration, serving as a model material for studying the effects of micro/nano-topological modifications on cells. However, the intracellular signaling pathways by which TiO2 nanotubes regulate the osteogenic differentiation of stem cells are not fully defined. Thy-1 (CD90), a cell surface glycoprotein anchored by glycosylphosphatidylinositol, has been considered a key molecule in osteoblast differentiation in recent years. Nevertheless, whether the micro/nano topology of the implant surface leads to changes in Thy-1 is unknown, as well as whether these changes promote osteogenic differentiation of bone marrow mesenchymal stem cells (BMSCs). Here, TiO2 nanotubes of various diameters were prepared by adjusting the anodizing voltage. qPCR and immunoblot were carried out to assess the mechanism by which TiO2 nanotubes regulate Thy-1. The results revealed Ti plates harboring TiO2 nanotubes ∼100-nm diameter (TNT-100) markedly upregulated Thy-1. Subsequently, upregulated Thy-1 promoted the activation of Fyn/RhoA/MLC Ⅱ/F-actin axis, which enhanced the nuclear translocation of YAP. After Thy-1 knockdown by siRNA, the Fyn/RhoA/MLC Ⅱ/F-actin axis was significantly inhibited and TiO2 nanotubes showed decreased effects on osteogenic differentiation. Therefore, Thy-1 upregulation might be a major mechanism by which micro/nano-topological modification of TiO2 nanotubes promotes osteogenic differentiation in BMSCs. This study provides novel insights into the molecular mechanism of TiO2 nanotubes, which may help design improved bone implants for clinical application.

Ultrathin TiO2 Coatings via Atomic Layer Deposition Strongly Improve Cellular Interactions on Planar and Nanotubular Biomedical Ti Substrates.

This work aims to investigate the chemical and/or structural modification of Ti and Ti-6Al-4V (TiAlV) alloy surfaces to possess even more favorable properties toward cell growth. These modifications were achieved by (i) growing TiO2 nanotube layers on these substrates by anodization, (ii) surface coating by ultrathin TiO2 atomic layer deposition (ALD), or (iii) by the combination of both. In particular, an ultrathin TiO2 coating, achieved by 1 cycle of TiO2 ALD, was intended to shade the impurities of F- and V-based species in tested materials while preserving the original structure and morphology. The cell growth on TiO2-coated and uncoated TiO2 nanotube layers, Ti foils, and TiAlV alloy foils were compared after incubation for up to 72 h. For evaluation of the biocompatibility of tested materials, cell lines of different tissue origin, including predominantly MG-63 osteoblastic cells, were used. For all tested nanomaterials, adding an ultrathin TiO2 coating improved the growth of MG-63 cells and other cell lines compared with the non-TiO2-coated counterparts. Here, the presented approach of ultrathin TiO2 coating could be used potentially for improving implants, especially in terms of shading problematic F- and V-based species in TiO2 nanotube layers.

A novel photoelectrochemical approach with "signal-off" pattern for anodic detection of sunset yellow in food samples based on Bi2WO6/TiO2 NTAs heterostructure nanocomposite.

A new and signal-off photoelectrochemical (PEC) sensing platform utilizing TiO2 nanotube arrays (NTAs) coated with Bi2WO6 nanoparticles (NPs) has been successfully developed for the highly sensitive detection of sunset yellow (SY). The interaction between SY and Bi2WO6 NPs leads to substantial steric hindrance, resulting in a noticeable decrease in the photocurrent signal. The proposed PEC sensor demonstrates quantitative detection capabilities for SY across a wide liner range of 10 fM to 100 µM with an ultralow detection limit (LOD) of 0.78 fM. Furthermore, the designed PEC sensor exhibits several notable advantages, including robust anti-interference properties, desirable repeatability, good reproducibility, and excellent stability. Finally, the designed PEC sensor was applied to determine SY in diverse real samples without any remarkable difference compared to the UV-Vis reference method.

Porous-Wall Titania Nanotube Array Layers: Preparation and Photocatalytic Response.

Electrochemical anodization is already a well-established process, owing to its multiple benefits for creating high-grade titanium dioxide nanotubes with suitable characteristics and tunable shapes. Nevertheless, more research is necessary to fully comprehend the basic phenomena at the anode-electrolyte interface during anodization. In a recent paper, we proposed the use of sawtooth-shaped voltage pulses for Ti anodization, which controls the pivoting point of the balance between the two processes that compete to create nanotubes during a self-organization process: oxide etching and oxidation. Under these conditions, pulsed anodization clearly reveals the history of nanotube growth as recorded in the nanotube morphology. We show that by selecting the suitable electrolyte and electrical discharge settings, a nanoporous structure may be generated as a repeating pattern along the nanotube wall axis. We report the findings in terms of nanotube morphology, crystallinity, surface chemistry, photocatalytic activity, and surface hydrophilicity as they relate to the electrical parameters of electrochemical anodization. Aside from their fundamental relevance, our findings could lead to the development of a novel form of TiO2 nanotube array layer.

Multivariate optimization of methylene blue dye degradation using electro-Fenton process with self-doped TiO2 nanotube anode.

This paper reports the optimization of the electro-Fenton (EF) process using different anode materials for the degradation of Methylene Blue (MB) dye as a model compound. The cathode used was an air-diffusion PTFE, while three different anode materials (Pt, DSA, and self-doped TiO2 nanotubes - SD-TNT) were tested individually. A full factorial design (FFD) with a central point combined with response surface methodology (RSM) was employed to optimize the experimental variables, including solution pH, applied current, and anode material. The optimized EF conditions involved a pH of 4.0, a current of 100 mA, and an SD-TNT anode for 120 min of electrolysis. Under these conditions, the MB solution achieved complete decolorization and 45% of total organic carbon (TOC) removal after 120 min of EF treatment. The findings indicate that the hydroxyl radical (•OH) plays a crucial role as the primary oxidizing agent in the EF process. The decay of MB followed pseudo-first-order kinetics, reflecting a consistent formation of •OH radicals that effectively attacked the MB dye and its subproducts during mineralization. Moreover, the EF process exhibited superior performance in terms of energy consumption (EC) and mineralization current efficiency (ECM) in the initial treatment stages, while the presence of recalcitrant by-products and loss of anode self-doping impacted performance in the later stages. The optimized EF conditions and the understanding gained from this study contribute to the advancement of sustainable wastewater treatment strategies for the removal of organic dyes.

Development of SDS-Modified PbO2 Anode Material Based on Ti3+ Self-Doping Black TiO2NTs Substrate as a Conductive Interlayer for Enhanced Electrocatalytic Oxidation of Methylene Blue.

Efficient and stable electrode materials are urgently required for wastewater treatment in the electrocatalytic degradation of toxic and refractory organic pollutants. Ti3+ self-doping black TiO2 nanotube arrays (Ti/B-TiO2-NTs) as an interlayer were used for preparing a novel PbO2 electrode via an electrochemical reduction technology, and a sodium dodecyl sulfate (SDS)-modified PbO2 catalytic layer was successfully achieved via an electrochemical deposition technology. The physicochemical characterization tests showed that the Ti/B-TiO2-NTs/PbO2-SDS electrodes have a denser surface and finer grain size with the introduction of Ti3+ in the interlayer of Ti/TiO2-NTs and the addition of SDS in the active layer of PbO2. The electrochemical characterization results showed that the Ti3+ self-doping black Ti/TiO2-NTs/PbO2-SDS electrode had higher oxygen evolution potential (2.11 V vs. SCE), higher electrode stability, smaller charge-transfer resistance (6.74 Ω cm-2), and higher hydroxyl radical production activity, leading to it possessing better electrocatalytic properties. The above results indicated that the physicochemical and electrochemical characterization of the PbO2 electrode were all enhanced significantly with the introduction of Ti3+ and SDS. Furthermore, the Ti/B-TiO2-NTs/PbO2-SDS electrodes displayed the best performance on the degradation of methylene blue (MB) in simulated wastewater via bulk electrolysis. The removal efficiency of MB and the chemical oxygen demand (COD) could reach about 99.7% and 80.6% under the optimal conditions after 120 min, respectively. The pseudo-first-order kinetic constant of the Ti/B-TiO2-NTs/PbO2-SDS electrode was 0.03956 min-1, which was approximately 3.18 times faster than that of the Ti/TiO2-NTs/PbO2 electrode (0.01254 min-1). In addition, the Ti/B-TiO2-NTs/PbO2-SDS electrodes showed excellent stability and reusability. The degradation mechanism of MB was explored via the experimental identification of intermediates. In summary, the Ti3+ self-doping black Ti/TiO2-NTs/PbO2-SDS electrode is a promising electrode in treating wastewater.

Nano selenium-doped TiO2 nanotube arrays on orthopedic implants for suppressing osteosarcoma growth.

Osteosarcoma, the most common primary malignant bone tumor, is characterized by malignant cells producing osteoid or immature bone tissue. Most osteosarcoma patients require reconstructive surgery to restore the functional and structural integrity of the injured bone. Metal orthopedic implants are commonly used to restore the limb integrity in postoperative patients. However, conventional metal implants with a bioinert surface cannot inhibit the growth of any remaining cancer cells, resulting in a higher risk of cancer recurrence. Herein, we fabricate a selenium-doped TiO2 nanotube array (Se-doped TNA) film to modify the surface of medical pure titanium substrate, and evaluate the anti-tumor effect and biocompatibility of Se-doped TNA film. Moreover, we further explore the anti-tumor potential mechanism of Se-doped TNA film by studying the behaviors of human osteosarcoma cells in vitro. We provide a new pathway for achieving the anti-tumor function of orthopedic implants while keeping the biocompatibility, aiming to suppress the recurrence of osteosarcoma.

Ultrasound-Driven Defect Engineering in TiO2-x Nanotubes─Toward Highly Efficient Platinum Single Atom-Enhanced Photocatalytic Water Splitting.

Single-atom catalysts (SACs) have demonstrated superior catalytic activity and selectivity compared to nanoparticle catalysts due to their high reactivity and atom efficiency. However, stabilizing SACs within hosting substrates and their controllable loading preventing single atom clustering remain the key challenges in this field. Moreover, the direct comparison of (co-) catalytic effect of single atoms vs nanoparticles is still highly challenging. Here, we present a novel ultrasound-driven strategy for stabilizing Pt single-atomic sites over highly ordered TiO2 nanotubes. This controllable low-temperature defect engineering enables entrapment of platinum single atoms and controlling their content through the reaction time of consequent chemical impregnation. The novel methodology enables achieving nearly 50 times higher normalized hydrogen evolution compared to pristine titania nanotubes. Moreover, the developed procedure allows the decoration of titania also with ultrasmall nanoparticles through a longer impregnation time of the substrate in a very dilute hexachloroplatinic acid solution. The comparison shows a 10 times higher normalized hydrogen production of platinum single atoms compared to nanoparticles. The mechanistic study shows that the novel approach creates homogeneously distributed defects, such as oxygen vacancies and Ti3+ species, which effectively trap and stabilize Pt2+ and Pt4+ single atoms. The optimized platinum single-atom photocatalyst shows excellent performance of photocatalytic water splitting and hydrogen evolution under one sun solar-simulated light, with TOF values being one order of magnitude higher compared to those of traditional thermal reduction-based methods. The single-atom engineering based on the creation of ultrasound-triggered chemical traps provides a pathway for controllable assembling stable and highly active single-atomic site catalysts on metal oxide support layers.

Flow-through Gas Phase Photocatalysis Using TiO2 Nanotubes on Wirelessly Anodized 3D-Printed TiNb Meshes.

In this work, for the first time 3D Ti-Nb meshes of different composition, i.e., Ti, Ti-1Nb, Ti-5Nb, and Ti-10 Nb, were produced by direct ink writing. This additive manufacturing method allows tuning of the mesh composition by simple blending of pure Ti and Nb powders. The 3D meshes are extremely robust with a high compressive strength, giving potential use in photocatalytic flow-through systems. After successful wireless anodization of the 3D meshes toward Nb-doped TiO2 nanotube (TNT) layers using bipolar electrochemistry, they were employed for the first time for photocatalytic degradation of acetaldehyde in a flow-through reactor built based on ISO standards. Nb-doped TNT layers with low concentrations of Nb show superior photocatalytic performance compared with nondoped TNT layers due to the lower amount of recombination surface centers. High concentrations of Nb lead to an increased number of recombination centers within the TNT layers and reduce the photocatalytic degradation rates.

Antibacterial and anti-inflammatory effects of PGLa-loaded TiO2 nanotube arrays.

Objectives: This study investigated the antimicrobial effect and anti-inflammatory activities of PGLa-loaded TiO2 nanotube arrays (TiO2 NTs) in osteoblast-like MG-63 cells. Methods: The surface morphology and roughness of three titanium (Ti) substrates (Ti, TiO2 NTs, PGLa-loaded TiO2 NTs) were evaluated by scanning electron microscopy (SEM) and atomic force microscope (AFM). The wettability of three titanium substrates was evaluated by contact angle. Biocompatibility of PGLa-loaded TiO2 NTs were evaluated in MG-63 cells (cell adhesion, proliferation, cytoskeletal evaluation and alkaline phosphatase activity). Spread plate counting method was used to evaluate antibacterial abilities of the titanium substrates. The calcein AM/PI staining evaluated cell viability of MG-63 cells on the substrates with or without proinflammatory factors (TNF-α). Results: The average surface roughness of untreated Ti, TiO2 NTs, PGLa-loaded TiO2 NTs were found to be 135.8 ± 6.4 nm, 300.5 ± 10.5 nm, 348.9 ± 16.9 nm, respectively. The contact angle of the untreated Ti was 77.4° ± 6.6°. TiO2 NTs displayed excellent wettability which of contact angle was 12.1° ± 2.9°. The contact angle of the PGLa-loaded TiO2 NTs was 34.6° ± 4.9°. MG-63 cells on surface of PGLa-loaded TiO2 NTs showed better cell adhesion, proliferation and osteogenic activity. The antibacterial rate of PGLa-loaded TiO2 NTs group significantly increased (84.6% ± 5.5%, p < 0.05). The rate of dead cells on the surfaces of the PGLa-loaded TiO2 NTs with TNF-α decreased significantly (4.49% ± 0.02, p < 0.01). Conclusion: PGLa-loaded TiO2 NTs have multi-biofunctions including biocompatibility, antibacterial and anti-inflammatory properties.

Photoelectrochemical performance of BiOI/TiO2 nanotube arrays (TNAs) p-n heterojunction synthesized by SILAR-ultrasonication-assisted methods.

In order to extend the visible region activity of titania nanotube array (TNAs) films, the successive ionic layer adsorption and reaction (SILAR)-ultrasonication-assisted method has been used to prepare BiOI-modified TiO2 nanotube arrays (BiOI/TNAs). The band gap of BiOI/TNAs for all the variations reveals absorption in the visible absorption. The surface morphology of BiOI/TNAs is shown in the nanoplate, nanoflake and nanosheet forms with a vertical orientation perpendicular to TiO2. The crystalline structure of BiOI did not change the structure of the anatase TNAs, with the band gap energy of the BiOI/TNAs semiconductor in the visible region. The photocurrent density of the BiOI/TNAs extends to the visible-light range. BiOI/TNAs prepared with 1 mM Bi and 1 mM KI on TNAs 40 V 1 h, 50 V 30 min show the optimum photocurrent density. A tandem dye-sensitized solar cell (DSSC)-photoelectrochemical (PEC) was used for hydrogen production in salty water. BiOI/TNAs optimum was used as the photoanode of the PEC cell. The solar to hydrogen conversion efficiency (STH) of tandem DSSC-PEC reaches 1.34% in salty water.

Efficient Electrochemical Oxidation of Chloramphenicol by Novel Reduced TiO2 Nanotube Array Anodes: Kinetics, Reaction Parameters, Degradation Pathway and Biotoxicity Forecast.

The key component of electrochemical advanced oxidation technology are high-efficiency anodes, and highly efficient and simple-to-prepare materials have generated a lot of interest. In this study, novel self-supported Ti3+-doped titanium dioxide nanotube arrays (R-TNTs) anodes were successfully prepared by a two-step anodic oxidation and straightforward electrochemical reduction technique. The electrochemical reduction self-doping treatment produced more Ti3+ sites with stronger absorption in the UV-vis region, a band gap reduction from 2.86 to 2.48 ev, and a significant increase in electron transport rate. The electrochemical degradation effect of R-TNTs electrode on chloramphenicol (CAP) simulated wastewater was investigated. At pH = 5, current density of 8 mA cm-2, electrolyte concentration of 0.1 M sodium sulfate (Na2SO4), initial CAP concentration of 10 mg L-1, CAP degradation efficiency exceeded 95% after 40 min. In addition, molecular probe experiments and electron paramagnetic resonance (EPR) tests revealed that the active species were mainly •OH and SO4-, among which •OH played a major role. The CAP degradation intermediates were discovered using high-performance liquid chromatography-mass spectrometry (HPLC-MS), and three possible degradation mechanisms were postulated. In cycling experiments, the R-TNTs anode demonstrated good stability. The R-TNTs prepared in this paper were an anode electrocatalytic material with high catalytic activity and stability, which could provide a new approach for the preparation of electrochemical anode materials for difficult-to-degrade organic compounds.

Electrochemical treatment of electroplating wastewater using synthesized GO/TiO2 nanotube electrode.

The graphene oxide (GO) deposited TiO2 nanotube (GO/TiO2) electrode on a titania plate was prepared using a simple anodization method. The morphological and structural properties of TiO2 and GO/TiO2 electrodes have been studied using field emission scanning electron microscopy energy dispersive spectroscopy (FESEM-EDS), X-ray diffraction (XRD), UV-vis diffuse reflectance spectroscopy (UV-vis DRS), Raman spectroscopy, Fourier transform infrared spectra (FT-IR), and X-ray photoelectron spectroscopy (XPS). FESEM-EDS analysis confirmed that the 13.56% wt of GO nanoparticles was formed over the TiO2 substrate, with the thickness of the wall to be ∼300 nm. The crystallite size of GO/TiO2, i.e., 19.53 nm, was confirmed by XRD analysis. Analysis of the UV-DRS spectrum showed the bandgap of the synthesized GO/TIO2 nanotube electrode to be 3.052 eV. Box-Behnken design (BBD) under response surface methodology (RSM) was used to design the experiments. The effect of operating input parameters like pH, current (i), and degradation time (t) on % COD degradation (X1) and energy consumed (X2) were also examined. At optimum process parameters, the value of X1 and X2 were 57.61% and 15.00 kWh/m3, respectively. Possible intermediates were identified based on the GC-MS data analysis. Scavenger tests showed that •OH radical plays a major role in electroplating effluents degradation. Based on the results, the EO process using GO/TiO2 electrodes could be considered a promising technique for electroplating effluent degradation due to high degradation efficiency.

Nano-Polycrystalline Cu Layer Interlaced with Ti3+-Self-Doped TiO2 Nanotube Arrays as an Electrocatalyst for Reduction of Nitrate to Ammonia.

The electrochemical nitrate reduction reaction (NO3RR) is considered as a promising strategy to degrade nitrate-containing wastewater and synthesize recyclable ammonia at atmospheric pressure and room temperature. In this work, the copper oxides-derived nano-polycrystalline Cu (NPC Cu) was integrated with Ti3+-self-doped TiO2 nanotube arrays (NTA) to fabricate the NPC Cu/H-TiO2 NTA. Ti3+-self-doped TiO2 NTAs and the NPC Cu facilitate electron transfer and mass transportation and create abundant active sites. The unique nanostructure in which Cu nano-polycrystals interlace with the TiO2 nanotube accelerates the electron transfer from the substrate to surface NPC Cu. The density functional theory calculations confirm that the built-in electric field between Cu and TiO2 improves the adsorption characteristic of the NPC Cu/H-TiO2 NTA, thereby converting the endothermic NO3- adsorption step into an exothermic process. Therefore, the high NO3- conversion of 98.97%, the Faradic efficiency of 95.59%, and the ammonia production yield of 0.81 mg cm-2 h-1 are achieved at -0.45 V vs reversible hydrogen electrode in 10 mM NaNO3 (140 mg L-1)-0.1 M Na2SO4. This well-designed NPC Cu/H-TiO2 NTA as an effective electrocatalyst for the 8e- NO3RR possesses promising potential in the applications of ammonia production.