Functionalized Modified Ti4O7 Polyaniline Coating for 316SS Bipolar Plate in Proton-Exchange Membrane Fuel Cells.

In this paper, the PANI/PDA-Ti4O7 composite coating was prepared on 316L by constant current deposition with a current density of 2.8 mA·cm-2, in which the Ti4O7 powders were modified by PDA (polydopamine). The open-circuit potential of the obtained PANI/PDA-Ti4O7 composite coating is about 365 mVAg/AgCl, which is more positive than that of the bare 316L. During immersion in 1 M H2SO4 + 2 ppm HF for 200 h, the high stable corrosion potential and the lower Rf indicate that the composite coating has long-term corrosion resistance.

Preparation and Electrochemical Applications of Magnéli Phase Titanium Suboxides: A Review.

Magnéli phase titanium suboxides (M-TSOs) belong to a type of sub-stoichiometric titanium oxides based on the crystal structure of rutile TiO2. They possess a unique shear structure, granting them exceptional electrical conductivity and corrosion resistance. These two advantages are crucial for electrode materials in electrochemistry, hence the significant interest from numerous researchers. However, the preparation of M-TSOs is uneconomic due to high temperature reduction and other complex synthesis process, thus limiting their practical application in electrochemical fields. This review delves into the crystal structure, properties, and synthesis methods of M-TSOs, and touches on their applications as electrocatalysts in wastewater treatment and electrochemical water splitting. Furthermore, it highlights the research challenges and potential future research directions in M-TSOs.

Research on carbon black and cerium co-doped Ti4O7-CB-Ce electrocatalytic oxidation of tetracycline-based antibiotics.

Elemental doping is a promising way for enhancing the electrocatalytic activity of metal oxides. Herein, we fabricate Ti/ Ti4O7-CB-Ce anode materials by the modification means of carbon black and cerium co-doped Ti4O7, and this shift effectively improves the interfacial charge transfer rate of Ti4O7 and •OH yield in the electrocatalytic process. Remarkably, the Ti4O7-CB-Ce anode exhibits excellent efficiency of minocycline (MNC) wastewater treatment (100% removal within 20 min), and the removal rate reduces from 100 to 98.5% after five cycles, which is comparable to BDD electrode. •OH and 1O2 are identified as the active species in the reaction. Meanwhile, it is discovered that Ti/ Ti4O7-CB-Ce anodes can effectively improve the biochemical properties of the non-biodegradable pharmaceutical wastewater (B/C values from 0.25 to 0.44) and significantly reduce the toxicity of the wastewater (luminescent bacteria inhibition rate from 100 to 26.6%). This work paves an effective strategy for designing superior metal oxides electrocatalysts.

Atomically Dispersed Ru-doped Ti4O7 Electrocatalysts for Chlorine Evolution Reaction with a Universal Activity.

Chlorine has been supplied by the chlor-alkali process that deploys dimensionally stable anodes (DSAs) for the electrochemical chlorine evolution reaction (ClER). The paramount bottlenecks have been ascribed to an intensive usage of precious elements and inevitable competition with the oxygen evolution reaction. Herein, a unique case of Ru2+-O4 active motifs anchored on Magnéli Ti4O7 (Ru-Ti4O7) via a straightforward wet impregnation and mild annealing is reported. The Ru-Ti4O7 performs radically active ClER with minimal deployment of Ru (0.13 wt%), both in 5 m NaCl (pH 2.3) and 0.1 m NaCl (pH 6.5) electrolytes. Scanning electrochemical microscopy demonstrates superior ClER selectivity on Ru-Ti4O7 compared to the DSA. Operando X-ray absorption spectroscopy and density functional theory calculations reveal a universally active ClER (over a wide range of pH and [Cl-]), through a direct adsorption of Cl- on Ru2+-O4 sites as the most plausible pathway, together with stabilized ClO* at low [Cl-] and high pH.

Sn Bulk Phase Doping and Surface Modification on Ti4 O7 for Oxygen Reduction to Hydrogen Peroxide.

Developing stable and highly selective two-electron oxygen reduction reaction (2e- ORR) electrocatalysts for producing hydrogen peroxide (H2 O2 ) is considered a major challenge to replace the anthraquinone process and achieve a sustainable green economy. Here, we doped Sn into Ti4 O7 (D-Sn-Ti4 O7 ) by simple polymerization post-calcination method as a high-efficiency 2e- ORR electrocatalyst. In addition, we also applied plain calcination after the grinding method to load Sn on Ti4 O7 (L-Sn-Ti4 O7 ) as a comparison. However, the performance of L-Sn-Ti4 O7 is far inferior to that of the D-Sn-Ti4 O7 . D-Sn-Ti4 O7 exhibits a starting potential of 0.769 V (versus the reversible hydrogen electrode, RHE) and a high H2 O2 selectivity of 95.7 %. Excitingly, the catalyst can maintain a stable current density of 2.43 mA ⋅ cm-2 for 3600 s in our self-made H-type cell, and the cumulative H2 O2 production reaches 359.2 mg ⋅ L-1 within 50,000 s at 0.3 V. The performance of D-Sn-Ti4 O7 is better than that of the non-noble metal 2e- ORR catalysts reported so far. The doping of Sn not only improves the conductivity but also leads to the lattice distortion of Ti4 O7 , further forming more oxygen vacancies and Ti3+ , which greatly improves its 2e- ORR performance compared with the original Ti4 O7 . In contrast, since the Sn on the surface of L-Sn-Ti4 O7 displays a synergistic effect with Tin+ (3≤n≤4) of Ti4 O7 , the active center Tin+ dissociates the O=O bond, making it more inclined to 4e- ORR.

Single-atom Zr embedded Ti4O7 anode coupling with hierarchical CuFe2O4 particle electrodes toward efficient electrooxidation of actual pharmaceutical wastewater.

Electrocatalytic oxidation is commonly restricted by low degradation efficiency, slow mass transfer, and high energy consumption. Herein, a synergetic electrocatalysis system was developed for removal of various drugs, i.e., atenolol, florfenicol, and diclofenac sodium, as well as actual pharmaceutical wastewater, where the newly-designed single-atom Zr embedded Ti4O7 (Zr/Ti4O7) and hierarchical CuFe2O4 (CFO) microspheres were used as anode and microelectrodes, respectively. In the optimal reaction system, the degradation efficiencies of 40 mg L-1 atenolol, florfenicol, and diclofenac sodium could achieve up to 98.8%, 93.4%, and 85.5% in 120 min with 0.1 g L-1 CFO at current density of 25 mA cm-2. More importantly, in the flow-through reactor, the electrooxidation lasting for 150 min could reduce the COD of actual pharmaceutical wastewater from 432 to 88.6 mg L-1, with a lower energy consumption (25.67 kWh/m3). Meanwhile, the electrooxidation system maintained superior stability and environmental adaptability. DFT theory calculations revealed that the excellent performance of this electrooxidation system could be ascribed to the striking features of the reduced reaction energy barrier by single-atom Zr loading and abundant oxygen vacancies on the Zr/Ti4O7 surface. Moreover, the characterization and experimental results demonstrated that the CFO unique hierarchical structure and synergistic effect between electrodes were also the important factors that could improve the system performance. The findings shed light on the single-atom material design for boosting electrochemical oxidation performance.

Insights into antibiotic cefaclor mineralization by electro-Fenton and photoelectro-Fenton processes using a Ti/Ti4O7 anode: Performance, mechanism, and toxic chlorate/perchlorate formation.

A comparative degradation of antibiotic cefaclor (CEC) between Ti/Ti4O7 and Ti/RuO2 anodes, in terms of degradation kinetics, mineralization efficiency, and formation of toxic chlorate (ClO3-) and perchlorate (ClO4-), was performed with electrochemical-oxidation (EO), electro-Fenton (EF), and photoelectro-Fenton (PEF) processes. Besides, CEC degradation by EF with boron-doped diamond (BDD) anode was also tested. Results showed CEC decays always followed pseudo-first-order kinetics, with increasing apparent rate constants in the sequence of EO < EF < PEF. The mineralization efficiency of the processes with Ti/Ti4O7 anode was higher than that of Ti/RuO2 anode, but slightly lower than that of BDD anode. Under the optimal conditions, 94.8% mineralization was obtained in Ti/Ti4O7-PEF, which was much higher than 64.4% in Ti/RuO2-PEF. The use of Ti/RuO2 gave no generation of ClO3- or ClO4-, while the use of Ti/Ti4O7 yielded a small amount of ClO3- and trace amounts of ClO4-. Conversely, the use of BDD led to the highest generation of ClO3- and ClO4-. The reaction mechanism was studied systematically by detecting the generated H2O2 and •OH. The initial N of CEC was released as NH4+ and, in smaller proportion, as NO3-. Four short-chain carboxylic acids and nine aromatic intermediates were also detected, a possible reaction sequence for CEC mineralization was finally proposed.

Fabrication and characterizations of Zn-doped SnO2-Ti4O7 anode for electrochemical degradation of hexafluoropropylene oxide dimer acid and its homologues.

Hexafluoropropylene oxide dimer acid (HFPO-DA) and its homologues, as perfluorinated ether alkyl substances with strong antioxidant properties, have rarely been reported by electrooxidation processes to achieve good results. Herein, we report the use of an oxygen defect stacking strategy to construct Zn-doped SnO2-Ti4O7 for the first time and enhance the electrochemical activity of Ti4O7. Compared with the original Ti4O7, the Zn-doped SnO2-Ti4O7 showed a 64.4% reduction in interfacial charge transfer resistance, a 17.5% increase in the cumulative rate of •OH generation, and an enhanced oxygen vacancy concentration. The Zn-doped SnO2-Ti4O7 anode exhibited high catalytic efficiency of 96.4% for HFPO-DA within 3.5 h at 40 mA/cm2. Hexafluoropropylene oxide trimer and tetramer acid exhibit more difficult degradation due to the protective effect of the -CF3 branched chain and the addition of the ether oxygen atom leading to a significant increase in the C-F bond dissociation energy. The degradation rates of 10 cyclic degradation experiments and the leaching concentrations of Zn and Sn after 22 electrolysis experiments demonstrated the good stability of the electrodes. In addition, the aqueous toxicity of HFPO-DA and its degradation products was evaluated. This study analyzed the electrooxidation process of HFPO-DA and its homologues for the first time, and provided some new insights.

Differentiating the reaction mechanism of three-dimensionally electrocatalytic system packed with different particle electrodes: Electro-oxidation versus electro-fenton.

Recently, there are still some controversial mechanisms of the 3D electrocatalytic oxidation system, which would probably confound its industrial application. From the conventional viewpoint, the Ti4O7 material may be the desired particle electrodes in the 3D system since its high oxygen evolution potential favors the production of •OH via H2O splitting reaction at the anode side of Ti4O7 particle electrodes. In fact, the incorporation of Ti4O7 particles showed phenol degradation of 88% and COD removal of 51% within 120 min, under the optimum conditions at energy consumption of 0.668 kWh g-1 COD, the performance of which was much lower than those in many previous literatures. In contrast, the prepared carbon black-polytetrafluoroethylene composite (CB-PTFE) particles with abundant oxygen-containing functional groups could yield considerable amounts of H2O2 (200 mg L-1) in the 3D reactor and achieved a complete degradation of phenol and COD removal of 80% in the presence of Fe2+, accompanying a low energy consumption of only 0.080 kWh g-1 COD. It was estimated that only 20% of Ti4O7 particles near the anode attained the potential over 2.73 V/SCE at 30 mA cm-2 based on the potential test and simulation, responsible for the low yield of •OH via the H2O splitting on Ti4O7 (1.74 × 10-14 M), and the main role of Ti4O7 particle electrodes in phenol degradation was through direct oxidation. For the CB-PTFE-based 3D system, current density of 10 mA cm-2 was sufficient for all the CB-PTFE particles to attain cathodic potential of -0.67 V/SCE, conducive to the high yield of H2O2 and •OH (9.11 × 10-14 M) in the presence of Fe2+, and the •OH-mediated indirect oxidation was mainly responsible for the phenol degradation. Generally, this study can provide a deep insight into the 3D electrocatalytic oxidation technology and help to develop the high-efficiency and cost-efficient 3D technologies for industrial application.

Electro-enhanced activation of peroxymonosulfate by a novel perovskite-Ti4O7 composite anode with ultra-high efficiency and low energy consumption: The generation and dominant role of singlet oxygen.

Traditional free radicals-dominated electrochemical advanced oxidation processes (EAOPs) and sulfate radical-based advanced oxidation processes (SR-AOPs) are limited by pH dependence and weak reusability, respectively. To overcome these shortcomings, electro-enhanced activation of peroxymonosulfate (PMS) on a novel perovskite-Ti4O7 composite anode (E-PTi-PMS system) was proposed. It achieved an ultra-efficient removal rate (k = 0.467 min-1) of carbamazepine (CBZ), approximately 36 and 8 times of the E-PTi and PTi-PMS systems. Singlet oxygen (1O2) played a dominant role in the E-PTi-PMS system and transformed from SO4•-, O2•-, •OH and oxygen vacancy (Vo••). The electric field expedited the decomposition and utilization of PMS, promoting the generation of radicals and expanding the formation pathway of 1O2. The E-PTi-PMS system presented superiorities over wide pH (3-10) and less dosage of PMS (1 mM), expanding the pH adaptability and reducing the cost of EAOPs. Simultaneously, the excellent reusability (30 cycles) solved the bottleneck of recycling catalysts in SR-AOPs via an ultra-low energy (0.025 kWh/m3-log). This work provides a promising alternative towards high-efficiency and low-cost treatment of polluted waters.

Cobalt-nickel alloys supported on Ti4O7 and embedded in N, S doped carbon nanofibers as an efficient and stable bifunctional catalyst for Zn-air batteries.

Transition metal catalysts for replacing noble metals have been extensively studied, but the deficiencies in intrinsic activity and stability limit their application in electrocatalysis. Here, we present CoNi alloy nanoparticles loaded on Ti4O7 supports and embedded in N, S doped carbon nanofibers by electrospinning method. The prepared CoNi/Ti4O7@NS-CNFs exhibits satisfactory ORR and OER activities with a low potential gap of 0.664 V and shows a high stability over long periods of testing, which are superior to most of the transition metal catalysts reported so far. Accordingly, the Zn-air battery constructed with the prepared catalyst demonstrates a maximum power density of 165.7 mW cm-2 and a specific capacity of 788.4 mA h gZn-1 (1.61 and 1.14 times higher than that of Pt/C + IrO2, respectively). The addition of S element and corrosion-resistant Ti4O7 plays a significant part in the morphology and activity of the prepared catalyst, which optimizes the distribution and electronic structure of active centers, and improves the stability of the catalyst. This effort provides a possible approach to exploring the efficient performance of the other transition metals.

Mesoporous Ti4O7 Spheres with Enhanced Zinc-Anchoring Effect for High-Performance Zinc-Nickel Batteries.

Zinc-nickel batteries are promising competitors for next-generation power supply due to their benefits of high safety, high working voltage, and attractive rate performance. However, their practical applications are plagued by their poor cycling performance, stemming from uneven redistribution of zinc during cycling that results in dendrite formation and shape changes of the electrode. In this work, mesoporous Ti4O7 microspheres are prepared and are employed as additives of a zinc anode. Notably, the presence of mesopores provides abundant chemisorption sites for Zn(OH)42- ions, inhibiting severe zinc redistribution in the electrode. Moreover, due to the good electrical conductivity and mesopores that serve as ion diffusion channels, the reaction reactivity and reversibility of the zinc electrode are greatly facilitated. As a result, the fabricated zinc-nickel battery with mesoporous Ti4O7 additives (ms-Ti4O7) exhibits an enhanced discharge capacity and a significantly prolonged cycling life. Even at a current of 10 A (∼138 mA cm-2), the ms-Ti4O7-modified anode demonstrates stable operation for longer than 718 h (700 cycles) with a discharge voltage of 1.2 V, which is much longer than those of a ZnO anode (192 h, 117 cycles) and a Ti4O7-particle (p-Ti4O7)-modified battery (590 h, 443 cycles). Furthermore, due to the anchoring effect for Zn(OH)42- and the uniform electric field, the effect of mesoporous Ti4O7 on inhibiting dendrite formation and shape change of the zinc electrode is highlighted.

A Case Study of Swine Wastewater Treatment via Electrochemical Oxidation by Ti4O7 Anode.

With the rapid development of breeding industry, the efficient treatment of dramatically increasing swine wastewater is gradually becoming urgent. In particular, the development of application technologies suitable for the relatively small piggeries is critical due to the time cost and space requirements of conventional biological methods. In this study, Electrochemical oxidation (EO) was selected to systematically explore the treatment performance of three different swine wastewaters by Ti4O7 anode. It was observed that the colors changed from dark brown to light yellow after 60 min treatment at 50 mA/cm2, and the removal rates of turbidity and suspended solids ranged from 89.36% to 93.65% and 81.31% to 92.55%, respectively. The chemical oxygen demand (COD), ammonia nitrogen (NH3-N) and total phosphorus (TP) of all the three swine wastewaters were simultaneously removed to a very low concentration in 120 min, especially for sample III, 61 ± 9 mg/L of COD, 6.6 ± 0.4 mg/L of NH3-N and 5.7 ± 1.1 mg/L of TP, which met the Discharge Standard of Pollutants for Livestock and Poultry Breeding (GB 18596-2001). Moreover, 70.93%-85.37% mineralization rates were also achieved in 120 min, confirming that EO treatment by Ti4O7 could efficiently remove the organic matters in wastewater. Excitation-emission matrix (EEM) and UV-vis spectrum characterization results further proved that aromatic compounds and macromolecules in wastewater were rapidly removed, which played important roles in the mineralization processes. The findings here provided an efficient and environment-friendly technology for swine wastewater treatment.

Energy-efficient removal of trace antibiotics from low-conductivity water using a Ti4O7 reactive electrochemical ceramic membrane: Matrix effects and implications for byproduct formation.

The inevitably high energy consumption of traditional electrochemical processes to treat low-conductivity water has limited their wider application. Herein, we present an energy-efficient alternative, i.e., a Ti4O7 reactive electrochemical ceramic membrane (Ti4O7-REM) system with a superior mass transfer ability. For the removal of 10-200 µM norfloxacin (NOR) from low-conductivity (178-832 µS cm-1) water, the Ti4O7-REM system increased the kinetics rate constant by 4.3-34.0 times, thus decreasing the energy cost by 80.5-97.3% compared with a flow-by system. The rapid NOR removal was related to the enhanced direct electron transfer process in the Ti4O7-REM system, which allowed for higher resistance to HCO3- scavenging and a favorable reaction between NOR and the active sites. Meanwhile, this mechanism likely contributed to the less formation of inorganic chlorinated product, ClO3-, in the presence of Cl-. Although organic chlorinated byproducts were not detected during NOR degradation in the Ti4O7-REM system, Cl- influenced the speciation of the intermediates. A single-pass Ti4O7-REM system demonstrated 94-97% removal of trace antibiotics from real water samples in 30 s. The additional energy consumption (<0.02 kWh m-3) using a Ti4O7-REM system only contributed to 5.0-6.4% of the total in a typical tertiary wastewater treatment plant. Based on the above results, we can conclude that the convection-enhanced REM technique is viable for the purification of low-conductivity natural waters.

Mesoporous Ti4 O7 Nanosheets with High Polar Surface Area for Catalyzing Separator to Reduce the Shuttle Effect of Soluble Polysulfides in Lithium-sulfur Batteries.

In the effort to accelerate adsorption and catalytic conversion of lithium polysulfides (Li-PSs) and suppress the shuttle effect of lithium-sulfur batteries (LSBs), the Ti4 O7 nanosheets/carbon material-modified separator is successfully fabricated to reducing soluble Li-PSs' crossover from cathode to anode. The catalyst of mesoporous Ti4 O7 nanosheets with O-Ti-O units synthesized at low temperature shows both excellent conductivity and high surface area. The modified separator can serve as a diffusion barrier of Li-PSs and catalyst for converting soluble low-chain sulfides into insoluble ones and then remarkably enhance the sulfur utilization and electrochemical performance of the LSB. This work provides a feasible avenue in both design and synthesis of mesoporous catalyst materials for suppressing the shuttle effect of lithium-sulfur batteries.

Electrochemical removal of 4-chlorophenol in water using a porous Magnéli-phase (Ti4O7) electrode.

Electro-oxidation is a promising technology for removal of refractory organic pollutants. While the appeal of this technology lies in its chemical-free nature, commercially scale-up application may be limited by the availability of electrode materials and mass transport. Here we report the development of a flow-through electro-oxidation system for removal of chlorophenols in water using Magnéli-phase (Ti4O7) tubular anode and a 304 stainless steel (SS) tubular cathode. The key to this system was the porous and conductive Magnéli-phase Ti4O7 anode, the structure and composition of which was confirmed by scanning electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. System efficacy was evaluated by using 4-chlorophenol (4-CP) as a typical refractory contaminant and model chlorophenol. Under optimized conditions, a complete removal of 4-CP could be obtained within 120 min in 0.04 mol L-1 Na2SO4 solution. Electro-produced HO• and direct electron transfer were both shown to contribute to the 4-CP electro-oxidation process due to the high selectivity and oxygen evolution potential of the Ti4O7 anode. The intermediates of 4-CP degradation were identified and a pathway for its electro-oxidation was proposed. When challenged with industrial wastewater containing 4-CP, chemical oxygen demand (COD) and total organic carbon removal efficiencies of 67.5% and 63.1% respectively could be obtained, accounting for energy consumption of 85.1 kWh·kg COD-1 for degradation of 1 kg of COD in industrial wastewater. This study provides an effective and robust solution for the removal of refractory emerging contaminants from industrial wastewaters using a continuous-flow electro-oxidation system.

Electro-activation of peroxymonosulfate by a graphene oxide/iron oxide nanoparticle-doped Ti4O7 ceramic membrane: mechanism of singlet oxygen generation in the removal of 1,4-dioxane.

Electro-activation of peroxymonosulfate (PMS) has been widely investigated for the degradation of organic pollutants. Herein, we employ graphene oxide (GO)/Fe3O4 nanoparticles (NPs) doped into a Ti4O7 reactive electrochemical membrane through strong chemical bonding as the cathode to activate PMS for the degradation of 1,4-dioxane (1,4-D). The strong chemical interaction between GO, Fe3O4-NPs, and Ti4O7 via Fe-O---GO---O-Ti bonds enhances the electron-transfer efficiency and provides catalytically active sites that boost the electro-activation of PMS. As a result, the 1,4-D oxidation rate of the GO/Fe3O4-NPs@Ti4O7 REM cathode is ~3 times higher (7.21 × 10-3 min-1) than those of other Ti4O7 ceramic membranes, and 1O2 plays a key role (59.9%) in the degradation of 1,4-D. The 1O2 generation mechanism in the electro-activation process of PMS was systematically investigated, and we claimed that 1O2 is mainly generated from the precursors H2O2 and O2•-/HO2• rather than by O2 or •OH, as has been reported in previous studies. A flow-through mode test in the PMS electro-activation system is firstly reported, and the 1,4-D decay efficiency is 7.1 times higher than that obtained by a flow-by mode, showing that an improved PMS mass transfer efficiency enhances the conversion to reactive oxygen species.

Defect Engineering on a Ti4O7 Electrode by Ce3+ Doping for the Efficient Electrooxidation of Perfluorooctanesulfonate.

Defect engineering in an electrocatalyst, such as doping, has the potential to significantly enhance its catalytic activity and stability. Herein, we report the use of a defect engineering strategy to enhance the electrochemical reactivity of Ti4O7 through Ce3+ doping (1-3 at. %), resulting in the significantly accelerated interfacial charge transfer and yielding a 37-129% increase in the anodic production of the hydroxyl radical (OH•). The Ce3+-doped Ti4O7 electrodes, [(Ti1-xCex)4O7], also exhibited a more stable electrocatalytic activity than the pristine Ti4O7 electrode so as to facilitate the long-term operation. Furthermore, (Ti1-xCex)4O7 electrodes were also shown to effectively mineralize perfluorooctanesulfonate (PFOS) in electrooxidation processes in both a trace-concentration river water sample and a simulated preconcentration waste stream sample. A 3 at. % dopant amount of Ce3+ resulted in a PFOS oxidation rate 2.4× greater than that of the pristine Ti4O7 electrode. X-ray photoelectron spectroscopy results suggest that Ce3+ doping created surficial oxygen vacancies that may be responsible for the enhanced electrochemical reactivity and stability of the (Ti1-xCex)4O7 electrodes. Results of this study provide insights into the defect engineering strategy for boosting the electrochemical performance of the Ti4O7 electrode with a robust reactivity and stability.

Fabrication and Characterization of the Porous Ti4O7 Reactive Electrochemical Membrane.

Preparation of the Magnéli Ti4O7 reactive electrochemical membrane (REM) with high purity is of great significance for its application in electrochemical advanced oxidation processes (EAOPs) for wastewater treatment. In this study, the Ti4O7 REM with high purity was synthesized by mechanical pressing of TiO2 powders followed by thermal reduction to Ti4O7 using the Ti powder as the reducing reagent, where the TiO2 monolith and Ti powder were separated from each other with the distance of about 5 cm in the vacuum furnace. When the temperature was elevated to 1333 K, the Magnéli phase Ti4O7 REM with the Ti4O7 content of 98.5% was obtained after thermal reduction for 4 h. Noticeably, the surface and interior of the obtained REM bulk sample has a homogeneous Ti4O7 content. Doping carbon black (0wt%-15wt%) could increase the porosity of the Ti4O7 REM (38-59%). Accordingly, the internal resistance of the electrode and electrolyte and the charge-transfer impedance increased slightly with the increasing carbon black content. The optimum electroactive surface area (1.1 m2) was obtained at a carbon black content of 5wt%, which increased by 1.3-fold in comparison with that without carbon black. The as-prepared Ti4O7 REMs show high oxygen evolution potential, approximately 2.7 V/SHE, indicating their appreciable electrocatalytic activity toward the production of •OH.

Fabrication and characterization of titanium-based lead dioxide electrode by electrochemical deposition with Ti4 O7 particles.

A novelly modified Ti/PbO2 electrode was synthesized with Ti4 O7 particles through electrochemical deposition method (marked as PbO2 -Ti4 O7 ). The properties of the as-prepared electrodes were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS), hydroxyl radical concentration, accelerated life test, etc. Azophloxine was chosen as the model pollutant for electro-catalytic oxidation to evaluate electrochemical activity of the electrode. The experimental results indicated that Ti4 O7 modification could prominently improve the properties of the electrodes, especially, improve the surface morphology, enhance the current response, and reduce the impedance. However, the predominant phases of PbO2 electrodes were unchanged, which were completely pure ß-PbO2 . During the electrochemical oxidation process, the PbO2 -Ti4 O7 (1.0) electrode showed the best performance on degradation of AR1 (i.e., the highest removal efficiency and the lowest energy consumption), which could be attributed to its high oxygen evolution potential (OEP) and strong capability of HO· generation. Moreover, the accelerated service lifetime of PbO2 -Ti4 O7 (1.0) electrode was 175 hr, 1.65 times longer than that of PbO2 electrode (105.5 hr). PRACTITIONER POINTS: PbO2 /Ti4 O7 composite anode was fabricated through electrochemical co-deposition. Four concentration gradients of Ti4 O7 particle were tested. PbO2 -Ti4 O7 (1.0) showed optimal electrocatalytic ability due to its high OEP and HO· productivity.