Utilizing transparent and conductive SnO2 as electron mediator to enhance the photocatalytic performance of Z-scheme Si-SnO2-TiOx

Z-scheme photocatalysts,with strong redox ability,have a great potential for pollutants degradation.However,it is challenging to construct efficient Z-scheme photocatalysts because of their poor interfacial charge separation.Herein,by employing transparent and conductive SnO2 as electron mediator to pass light through and promote interfacial charge transportation,a novel Z-scheme photocatalyst Si-SnO2-TiOx(i<x<2)was constructed.The Z-scheme photocatalyst displayed an order of magnitude higher photocurrent density and a 4-fold increase in open-circuit potential compared to those of Si.Moreover,the onset potential shifted negatively for approximately 2.2 V.Benefiting from these advantages,this Z-scheme Si-SnO2-TiOx exhibited efficient photocatalytic performance toward phenol degradation and mineralization.15%of the phenol was degraded without bias potential and 70%of the TOC was removed during phenol degradation.Other typical pollutants such as bisphenol A and atrazine could also be degraded without bias potential.Introducing a transparent and conductive electron mediator to construct Z-scheme photocatalyst gives a new sight to the improvement of photocatalytic performance in Z scheme.

Significantly enhanced photocatalytic hydrogen production performance of g-C_(3)N_(4)/CNTs/CdZnS with carbon nanotubes as the electron mediators

The electron mediator can effectively improve the performance of the direct Z-scheme heterojunction photocatalysts. However, it is still a great challenge to select cheap and efficient electron mediators and to design them into the Z-scheme photocatalytic system. In the present paper, the g-C_(3)N_(4)/CNTs/CdZnS Z-scheme photocatalyst was prepared using carbon nanotubes(CNTs) as the electron mediators, and its photocatalytic hydrogen production performance was studied. Compared with single-phase g-C_(3)N_(4),CdZnS and biphasic g-C_(3)N_(4)/CdZnS photocatalysts, the photocatalytic hydrogen production performance of the prepared g-C_(3)N_(4)/CNTs/CdZnS has been significantly enhanced. Meanwhile, g-C_(3)N_(4)/CNTs/CdZnS possesses very good photocatalytic hydrogen production stability. The enhanced photocatalytic hydrogen production performance of g-C_(3)N_(4)/CNTs/CdZnS is attributed to the fact that CNTs, as an electron mediator,can accelerate the recombination of the photogenerated holes in the valence band of g-C_(3)N_(4) and the photogenerated electrons in the conduction band of CdZnS, which makes the g-C_(3)N_(4)/CNTs/CdZnS Zscheme photocatalyst be easier to escape the photogenerated electrons, increases the concentration of the photogenerated carriers and prolongs the lifetime of the photogenerated carriers. This work provides a theoretical basis for the further development and design of CNTs as the intermediate electron mediator of the Z-scheme heterojunction photocatalyst.

Electrochemical Immunoassay of E. coil in Urban Sludge Using Electron Mediator-mediated Enzymatic Catalysis and Gold Nanoparticles for Signal Amplification

An electrochemical immunosensor was developed for sensitive assay ofE. coli in urban sludge, in which electron mediator-mediated enzymatic catalysis and gold nanoparticles（AuNPs） were utilized for signal amplification. The immnuosensing platform chitosan-thionine（chit-thio）/poly（amidoamine） dendrimer-encapsulated AuNPs [PAMAM（Au）] composites were first prepared from chit-thio and PAMAM（Au） using the layer-by-layer method to provide a matrix for high-stability and high-bioactivity bindings of the capture antibody（cAb）. Moreover, the {dAb-AuNPs-HRP} nanoprobes were designed to exploit the amplification effect of the carrier AuNPs due to the loading amounts of horseradish peroxidase（HRP）and the detection antibody（dAb）. The sandwich-type immunoassay was then successfully used to assay E. coli based on the oxidation of thionine as a result of H2O2-induced enzymatic catalytic reaction by HRP. This study presents a powerful tool in electrochemical immunoassay for E. coli detection with rapid response, high-sensitivity and high-specificity, providing a potential new tool for feasibility assessment of sludge recycle.

Polymeric viologen-based electron transfer mediator for improving the photoelectrochemical water splitting on Sb_(2)Se_(3) photocathode

The photogenerated charge carrier separation and transportation of inside photocathodes can greatly influence the performance of photoelectrochemical(PEC)H2 production devices.Coupling TiO_(2) with p-type semiconductors to construct heterojunction structures is one of the most widely used strategies to facilitate charge separation and transportation.However,the band position of TiO_(2) could not perfectly match with all p-type semiconductors.Here,taking antimony selenide(Sb_(2)Se_(3))as an example,a rational strategy was developed by introducing a viologen electron transfer mediator(ETM)containing polymeric film(poly-1,1′-dially-[4,4′-bipyridine]-1,1′-diium,denoted as PV^(2+))at the interface between Sb_(2)Se_(3) and TiO_(2) to regulate the energy band alignment,which could inhibit the recombination of photogenerated charge carriers of interfaces.With Pt as a catalyst,the constructed Sb_(2)Se_(3)/PV^(2+)/TiO_(2)/Pt photocathode showed a superior PEC hydrogen generation activity with a photocurrent density of−18.6 mA cm^(-2) vs.a reversible hydrogen electrode(RHE)and a half-cell solar-to-hydrogen efficiency(HC-STH)of 1.54%at 0.17 V vs.RHE,which was much better than that of the related Sb_(2)Se_(3)/TiO_(2)/Pt photocathode without PV^(2+)(−9.8 mA cm^(-2),0.51%at 0.10 V vs.RHE).

Effect of Fe(Ⅲ) on the bromate reduction by humic substances in aqueous solution

Humic substances are ubiquitous redox-active organic compounds of environment. In this study, experiments were conducted to determine the reduction capacity of humic acid in the man-ix of bromate and Fe（Ⅲ） solutions and the role of Fe（Ⅲ） in this redox process. The results showed that the humic acid regenerated Fe（Ⅱ） and reduced bromate abiotically. The addition of Fe（Ⅲ） could accelerate the bromate reduction rate by forming humic acid-Fe（Ⅲ） complexes. Iron species acts as electron mediator and catalyst for the bromate reduction by humic acid, in which humic acid transfers electrons to the complexed Fe（Ⅲ） to form Fe（Ⅱ）, and the regenerated Fe（Ⅱ） donate the electrons to bromate. The kinetics study on bromate reduction further indicated that bromate reduction by humic acid-Fe（Ⅲ） complexes is pH dependent. The rate decreased by 2-fold with the increase in solution pH by one unit. The reduction capacity of Aldrich humic acid was observed to be lower than that of humic acid or natural organic matter of Suwanne River, indicating that such redox process is expected to occur in the environment.

Green aerobic oxidative desulfurization of diesel by constructing an Fe-Anderson type polyoxometalate and benzene sulfonic acid-based deep eutectic solvent biomimetic cycle

A unique redox-coupled biomimetic system was developed, in which Fe-Anderson type polyoxometalates(POMs) were employed as electron transfer mediators(ETMs) and benzenesulfonic acid(BSA)-based deep eutectic solvents(DESs) were used as electron-donors for aerobic oxidative desulfurization(AODS) of diesel fuel. Different compositions of DESs were used and the polyethylene glycol 2000(PEG2000)/2.5 BSA system showed the highest desulfurization activity, with the removal of dibenzothiophene(DBT) at 60 ℃ reaching 95% in 60 min. The excellent desulfurization activity of the system is due to the in situ formation of peroxysulfonate via a biomimetic process. By constructing a coupled redox system, Fe-Anderson type POMs as ETMs reduce the activation energy of oxygen-activated sulfonate. The physical characteristics of four different DESs were tested. The results show that the conductivity of DESs is correlated with the composition of BSA-based DESs. However, there is no similar trend in viscosity testing at the same temperature, and the maximum viscosity value is obtained for the PEG2000/2.5 BSA system at 60 ℃, which may be associated with the stronger hydrogen bonds. It is worth noting that the PEG2000/2.5 BSA system also possesses the best desulfurization activity, which suggests that the activity of the desulfurization system is related to the strength of the hydrogen bond in DESs. Finally, the biomimetic desulfurization system exhibits excellent performance and good stability under mild reaction conditions(60 ℃, atmospheric pressure, oxygen as the oxidant).

Mediated electron transfer process in α-MnO_(2)catalyzed Fenton-like reaction for oxytetracycline degradation

In Fenton-like oxidation,the catalyst directly influences the reaction mechanism for the degradation of pollutants from water.Here,a α-MnO_(2)catalyst(OAm-1)was synthesized via a self-assembly method with the assistance of a surfactant.OAm-1 possessed a large specific surface area of_(2)21 m2/g,abundant mesoporous structures and a large proportion of Mn(III).Further characterization exhibited that OAm-1 had abundant oxygen vacancies and excellent reducibility and conductivity.The adsorption and catalytic ability of OAm-1 were studied in the degradation of oxytetracycline(OTC)via the activation of hydrogen peroxide(H_(2)O_(2)).Through the radical quenching experiments,electron resonance spectroscopy(EPR),X-ray photoelectron spectroscopy(XPS)and Fourier-transform infrared spectroscopy(FT-IR)analysis,Mn(III)of OAm-1 was proved to be the active sites for the chemisorption of OTC.Systematic electrochemical ex-periments and analysis have shown that a process of electron transfer mediated by OAm-1 occurred be-tween the pollutant and H_(2)O_(2)during a Fenton-like reaction.This work experimentally verifies the elec-tron transfer process dominated nonradical mechanism overα-MnO_(2),which is helpful for understanding the catalytic mechanism of the Fenton-like oxidation.

A tartrate-EDTA-Fe complex mediates electron transfer and enhances ammonia recovery in a bioelectrochemical-stripping system

Traditional bioelectrochemical systems(BESs)coupled with stripping units for ammonia recovery suffer from an insufficient supply of electron acceptors due to the low solubility of oxygen.In this study,we proposed a novel strategy to efficiently transport the oxidizing equivalent provided at the stripping unit to the cathode by introducing a highly soluble electron mediator(EM)into the catholyte.To validate this strategy,we developed a new kind of iron complex system(tartrate-EDTA-Fe)as the EM.EDTA-Fe contributed to the redox property with a midpoint potential of
0.075 V(vs.standard hydrogen electrode,SHE)at pH 10,whereas tartrate acted as a stabilizer to avoid iron precipitation under alkaline conditions.At a ratio of the catholyte recirculation rate to the anolyte flow rate(RC-A)of 12,the NH4 t-N recovery rate in the system with 50mM tartrate-EDTA-Fe complex reached 6.9±0.2 g Nm^(-2) d^(-1),approximately 3.8 times higher than that in the non-EM control.With the help of the complex,our system showed an NH4 t-N recovery performance comparable to that previously reported but with an extremely low RC-A(0.5 vs.288).The strategy proposed here may guide the future of ammonia recovery BES scale-up because the introduction of an EM allows aeration to be performed only at the stripping unit instead of at every cathode,which is beneficial for the system design due to its simplicity and reliability.

Electrocatalytic NAD(P)H regeneration for biosynthesis

The highly efficient chemoselectivity,stereoselectivity,and regioselectivity render enzyme catalysis an ideal pathway for the synthesis of various chemicals in broad applications.While the cofactor of an enzyme is necessary but expensive,the conversed state of the cofactor is not beneficial for the positive direction of the reaction.Cofactor regeneration using electrochemical methods has the advantages of simple operation,low cost,easy process monitoring,and easy product separation,and the electrical energy is green and sustainable.Therefore,bioelectrocatalysis has great potential in synthesis by combining electrochemical cofactor regeneration with enzymatic catalysis.In this review,we detail the mechanism of cofactor regeneration and categorize the common electron mediators and enzymes used in cofactor regeneration.The reaction type and the recent progress are summarized in electrochemically coupled enzymatic catalysis.The main challenges of such electroenzymatic catalysis are pointed out and future developments in this field are foreseen.