In situ electrogenerated Cu(III) triggers hydroxyl radical production on the Cu-Sb-SnO2 electrode for highly efficient water decontamination.

The electrochemical oxidation process has the unique advantage of in-situ •OH generation for deep mineralization of organic pollutants, which is expected to provide a solution for the globally decentralized wastewater treatment and reuse. However, it is still a great challenge to develop low-cost anodes with ultrahigh •OH yield and low energy consumption. Here, a low-cost and stable mixed metal oxide (MMO) anode (Cu-Sb-SnO2) developed by a simple and scalable preparation process presents extremely high organic pollutants degradation efficiency and low energy consumption. The tetracycline degradation kinetics constant of the Cu-Sb-SnO2 system (0.362 min-1) was 9 to 45 times higher than that of other prepared anodes, which is superior to the existing anodes reported so far. The experimental results and theoretical calculations indicate that the Cu-Sb-SnO2 has moderate oxygen evolution potential, larger water adsorption energy, and lower reaction energy barrier, which is conducive to selective water oxidation to generate •OH. Notably, it is systematically and comprehensively confirmed that the generation of •OH triggered by in situ electrogenerated Cu(III) increased •OH steady-state concentration by over four times. Furthermore, the doped Cu species can play a key role in promoting charge transfer as an "electronic porter" between Sn and Sb in the electrocatalytic process by adjusting the electronic structure of the Sb-SnO2 electrode. This work paves the way for the development of MMO anodes utilizing the advantage of the Cu redox shuttle.

Microscopic-Level Insights into P-O-Induced Strong Electronic Coupling Over Nickel Phosphide with Efficient Benzyl Alcohol Electrooxidation.

Electrooxidation of biomass into fine chemicals coupled with energy-saving hydrogen production for a zero-carbon economy holds great promise. Advanced anode catalysts determine the cell voltage and electrocatalytic efficiency greatly, further the rational design and optimization of their active site coordination remains a challenge. Herein, a phosphorus-oxygen terminals-rich species (Ni2P-O-300) via an anion-assisted pyrolysis strategy is reported to induce strong electronic coupling and high valence state of active nickel sites over nickel phosphide. This ultimately facilitates the rapid yet in-situ formation of high-valence nickel with a high reaction activity under electrochemical conditions, and exhibits a low potential of 1.33 V vs. RHE at 10 mA cm-2, exceeding most of reported transition metal-based catalysts. Advanced spectroscopy, theoretical calculations, and experiments reveal that the functional P-O species can induce the favorable local bonding configurations for electronic coupling, promoting the electron transfer from Ni to P and the adsorption of benzyl alcohol (BA). Finally, the hydrogen production efficiency and kinetic constant of BA electrooxidation by Ni2P-O-300 are increased by 9- and 2.8- fold compared with the phosphorus-oxygen terminals-deficient catalysts (Ni2P-O-500). This provides an anion-assisted pyrolysis strategy to modulate the electronic environment of the Ni site, enabling a guideline for Ni-based energy/catalysis systems.

Tandem Electrochemical Oxidation of Polycyclic Aromatic Amines Towards Carbazoles and Phenazine-based Aza-helicenes.

Experimental and theoretical study of the regioselectivity and mechanism of polycyclic aromatic amine (PAA) electrochemical oxidation is important for designing nitrogen doped large π-conjugated functional molecules. Herein, we used binary-, ternary-, and quaternary-fused PAAs as electro-oxidative reaction substrates to investigate the yield changes of carbazole and phenazine based aza-helicene other than oligomers, which were obtained through pyrrole and pyrazine annulation pathways. Combined with the restrained electrostatic potential (RESP) and steric hindrance factor analysis of the substrate, the electron spin density distribution of free radical resonance hybrid and the spin population analysis of the atoms in the structure of each free radical tautomer indicate that the degree of delocalized dispersion of N free radical and the resulting change in the spin density distribution of C free radical tautomers determine the reaction regioselectivity. The potential charge of the K-region, Bay-region, and L-region adjacent to the C(α)-C(ß1) bond is higher than that of other regions within the molecule, and the charge in these high RESP regions tends to delocalize more strongly toward electron-deficient N free radicals. Thus, the activity of N-C(α)-C(ß1) region is increased, which supports the proposed free radical addition and free radical coupling mechanism for the electro-oxidative reaction of PAA.

Tuning the Locally Enhanced Electric Field Treatment (LEEFT) between Electrophysical and Electrochemical Mechanisms for Bacteria Inactivation.

Efficient drinking water disinfection methods are critical for public health. Locally enhanced electric field treatment (LEEFT) is an antimicrobial method that uses sharp structures, like metallic nanowires, to enhance the electric field at tips and cause bacteria inactivation. Electroporation is the originally designed mechanism of LEEFT. Although oxidation is typically undesired due to byproduct generation and electrode corrosion, it can enhance the overall disinfection efficiency. In this work, we conduct an operando investigation of LEEFT, in which we change the electrical parameters to tune the mechanisms between electrophysical electroporation and electrochemical oxidation. Pure electroporation (i.e., without detectable oxidation) could be achieved under a duty cycle of ≤0.1% and a pulse width of ≤2 µs. Applying 2 µs pulses at 7-8 kV/cm and 0.1% duty cycle results in 80-100% bacteria inactivation with pure electroporation. A higher chance of oxidation is found with a higher duty cycle and a longer pulse width, where the antimicrobial efficiency could also be enhanced. For water with a higher conductivity, a higher antimicrobial efficiency can be achieved under the same treatment conditions, and electrochemical reactions could be induced more easily. The findings shown in this work improve the fundamental understanding of LEEFT and help optimize the performance of LEEFT in real applications.

Electrochemistry promotion of Fe(â ¢)/Fe(â ¡) cycle for continuous activation of PAA for sludge disintegration: Performance and mechanism.

In this study, electrochemistry was used to enhance the advanced oxidation of Fe(Ⅱ)/PAA (EC/Fe(Ⅱ)/PAA) to disintegrate waste activated sludge, and its performance and mechanism was compared with those of EC, PAA, EC/PAA and Fe(Ⅱ)/PAA. Results showed that the EC/Fe(Ⅱ)/PAA process effectively improved sludge disintegration and the concentrations of soluble chemical oxygen demand, polysaccharides and nucleic acids increased by 62.85%, 41.15% and 12.21%, respectively, compared to the Fe(Ⅱ)/PAA process. Mechanism analysis showed that the main active species produced in the EC/Fe(Ⅱ)/PAA process were •OH, R-O• and FeIVO2+. During the reaction process, sludge flocs were disrupted and particle size was reduced by the combined effects of active species oxidation, electrochemical oxidation and PAA oxidation. Furthermore, extracellular polymeric substances (EPS) was degraded, the conversion of TB-EPS to LB-EPS and S-EPS was promoted and the total protein and polysaccharide contents of EPS were increased. After sludge cells were disrupted, intracellular substances were released, causing an increase in nucleic acids, humic acids and fulvic acids in the supernatant, and resulting in sludge reduction. EC effectively accelerated the conversion of Fe(Ⅲ) to Fe(Ⅱ), which was conducive to the activation of PAA, while also enhancing the disintegration of EPS and sludge cells. This study provided an effective approach for the release of organic matter, offering significant benefits in sludge resource utilization.

An insight on the plausible biological and non-biological detoxification of heavy metals in tannery waste: A comprehensive review.

A key challenge for the tannery industries is the volume of tannery waste water (TWW) generated during the processing of leather, releasing various forms of toxic heavy metals resulting in uncontrolled discharge of tannery waste (TW) into the environment leading to pollution. The pollutants in TW includes heavy metals such as chromium (Cr), cadmium (Cd), lead (Pb) etc, when discharged above the permissible limit causes ill effects on humans. Therefore, several researchers have reported the application of biological and non-biological methods for the removal of pollutants in TW. This review provides insights on the global scenario of tannery industries and the harmful effects of heavy metal generated by tannery industry on micro and macroorganisms of the various ecological niches. It also provides information on the process, advantages and disadvantages of non-biological methods such as electrochemical oxidation, advanced oxidation processes, photon assisted catalytic remediation, adsorption and membrane technology. The various biological methods emphasised includes strategies such as constructed wetland, vermitechnology, phytoremediation, bioaugmentation, quorum sensing and biofilm in the remediation of heavy metals from tannery wastewater (TWW) with special emphasize on chromium.

Efficient electrochemical oxidation of antibiotic wastewater using a graphene-loaded PbO2 membrane anode: Mechanisms and applications.

This paper aims to develop a flow-through electrochemical system with a series of graphene nanoparticles loaded PbO2 reactive electrochemical membrane electrodes (GNPs-PbO2 REMs) on porous Ti substrates with pore sizes of 100, 150, 300 and 600 µm, and apply them to treat antibiotic wastewater. Among them, the GNPs-PbO2 with Ti substrate of 150 µm (Ti-150/GNPs-PbO2) had superior electrochemical degradation performance over the REMs with other pore sizes due to its smaller crystal size, larger electrochemical active specific area, lower charge-transfer impedance and larger oxygen evolution potential. Under the relatively optimized conditions of initial pH of 5, current density of 15 mA cm-2, and membrane flux of 4.20 m3 (m2·h)-1, the Ti-150/GNPs-PbO2 REM realized 99.34% of benzylpenicillin sodium (PNG) removal with an EE/O of 6.52 kWh m-3. Its excellent performance could be explained as the increased mass transfer. Then three plausible PNG degradation pathways in the flow-through electrochemical system were proposed, and great stability and safety of Ti-150/GNPs-PbO2 REM were demonstrated. Moreover, a single-pass Ti-150/GNPs-PbO2 REM system with five-modules in series was designed, which could consistently treat real antibiotic wastewater in compliance with disposal requirements of China. Thus, this study evidenced that the flow-through electrochemical system with the Ti-150/GNPs-PbO2 REM is an efficient alternative for treating antibiotic wastewater.

Mn-Co-Ce/biochar based particles electrodes for removal of COD from coking wastewater by 3D/HEFL system: Characteristics, optimization, and mechanism.

In this work, the Mn, Co, Ce co-doped corn cob biochar (MCCBC) as catalytic particle electrodes in a three-dimensional heterogeneous electro-Fenton-like (3D-HEFL) system for the efficient degradation of coking wastewater was investigated. Various characterization methods such as SEM, EDS, XRD, XPS and electrochemical analysis were employed for the prepared materials. The results showed that the MCCBC particle electrodes had excellent electrochemical degradation performances of COD in coking wastewater, and the COD removal and degradation rates of the 3D/HEFL system were 85.35% and 0.0563 min-1 respectively. RSM optimized conditions revealed higher COD removal rate at 89.23% after 31.6 min of electrolysis. The efficient degradability and wide adaptability of the 3D/HEFL system were due to its beneficial coupling mechanism, including the synergistic effect between the system factors (3D and HEFL) as well as the synergistic interactions between the ROS (dominated by •OH and supplemented by O2•-) in the system. Moreover, the COD removal rate of MCCBC could still remain at 81.41% after 5 cycles with a lower ion leaching and a specific energy consumption of 11.28 kWh kg-1 COD. The superior performance of MCCBC, as catalytic particle electrodes showed a great potential for engineering applications for the advanced treatment of coking wastewater.

Fundamental insight into electrochemical oxidation of methane towards methanol on transition metal oxides.

Electrochemical oxidation of CH4 is known to be inefficient in aqueous electrolytes. The lower activity of methane oxidation reaction (MOR) is primarily attributed to the dominant oxygen evolution reaction (OER) and the higher barrier for CH4 activation on transition metal oxides (TMOs). However, a satisfactory explanation for the origins of such lower activity of MOR on TMOs, along with the enabling strategies to partially oxidize CH4 to CH3OH, have not been developed yet. We report here the activation of CH4 is governed by a previously unrecognized consequence of electrostatic (or Madelung) potential of metal atom in TMOs. The measured binding energies of CH4 on 12 different TMOs scale linearly with the Madelung potentials of the metal in the TMOs. The MOR active TMOs are the ones with higher CH4 binding energy and lower Madelung potential. Out of 12 TMOs studied here, only TiO2, IrO2, PbO2, and PtO2 are active for MOR, where the stable active site is the O on top of the metal in TMOs. The reaction pathway for MOR proceeds primarily through *CH x intermediates at lower potentials and through *CH3OH intermediates at higher potentials. The key MOR intermediate *CH3OH is identified on TiO2 under operando conditions at higher potential using transient open-circuit potential measurement. To minimize the overoxidation of *CH3OH, a bimetallic Cu2O3 on TiO2 catalysts is developed, in which Cu reduces the barrier for the reaction of *CH3 and *OH and facilitates the desorption of *CH3OH. The highest faradaic efficiency of 6% is obtained using Cu-Ti bimetallic TMO.

Zirconium-based hydrophobic-MOFs as innovative electrode modifiers for flibanserin determination: Exploring the electrooxidation mechanism using a comprehensive spectroelectrochemical study.

Three different types of Zr-based MOFs derived from benzene dicarboxylic acid (BDC) and naphthalene dicarboxylic acid as organic linkers (ZrBDC, 2,6-ZrNDC, and 1,4-ZrNDC) were synthesized. They were characterized using X-ray diffraction analysis (XRD), X-ray photoelectron spectroscopy (XPS), Fourier-transform IR spectroscopy (FT-IR), and Transmission electron microscopy (TEM). Their hydrophilic/hydrophobic nature was investigated via contact angle measurements; ZrBDC MOF was hydrophilic and the other two (ZrNDC) MOFs were hydrophobic. The three MOFs were combined with MWCNTs as electrode modifiers for the determination of a hydrophobic analyte, flibanserin (FLB), as a proof-of-concept analyte. Under the optimized experimental conditions, a significant enhancement in the oxidation peak current of FLB was observed when utilizing 2,6-ZrNDC and 1,4-ZrNDC, being the highest when using 1,4-ZrNDC. Furthermore, a thorough investigation of the complex oxidation pathway of FLB was performed by carrying out simultaneous spectroelectrochemical measurements. Based on the obtained results, it was verified that the piperazine moiety of FLB is the primary site for electrochemical oxidation. The fabricated sensor based on 1,4-ZrNDC/MW/CPE showed an oxidation peak of FLB at 0.8 V vs Ag/AgCl. Moreover, it showed excellent linearity for the determination of FLB in the range 0.05 to 0.80 µmol L-1 with a correlation coefficient (r) = 0.9973 and limit of detection of 3.0 nmol L-1. The applicability of the developed approach was demonstrated by determination of FLB in pharmaceutical tablets and human urine samples with acceptable repeatability (% RSD values were below 1.9% and 2.1%, respectively) and reasonable recovery values (ranged between 97 and 103% for pharmaceutical tablets and between 96 and 102% for human urine samples). The outcomes of the suggested methodology can be utilized for the determination of other hydrophobic compounds of pharmaceutical or biological interest with the aim of achieving low detection limits of these compounds in various matrices.