Dual-functional MnS_(2)/MnO_(2) heterostructure catalyst for efficient acidic hydrogen evolution reaction and assisted degradation of organic wastewater

The design and synthesis of non-precious metal dual-functional electrocatalysts through the modulation of electronic structure are important for the development of renewable hydrogen energy.Herein,MnS_(2)/MnO_(2)-CC heterostructure dual-functional catalysts with ultrathin nanosheets were prepared by a twostep electrodeposition method for efficient acidic hydrogen evolution reaction(HER) and degradation of organic wastewater(such as methylene blue(MB)).The electronic structure of Mn atoms at the MnS_(2)/MnO_(2)-CC heterostructure interface is reconfigured under the joint action of S and O atoms.Theoretical calculations show that the Mn d-band electron distribution in MnS_(2)/MnO_(2)-CC catalyst has higher occupied states near the Fermi level compared to the MnO_(2) and MnS_(2) catalysts,which indicates that MnS_(2)/MnO_(2)-CC catalyst has better electron transfer capability and catalytic activity.The MnS_(2)/MnO_(2)-CC catalysts require overpotential of only 66 and 116 mV to reach current density of 10 and 100 mA cm^(-2)in MB/H_(2)SO_(4) media.The MnS_(2)/MnO_(2)-CC catalyst also has a low Tafel slope(26.72 mV dec^(-1)) and excellent stability(the performance does not decay after 20 h of testing).In addition,the MB removal efficiency of the MnS_(2)/MnO_(2)-CC catalyst with a better kinetic rate(0.0226) can reach 97.76%,which is much higher than that of the MnO_(x)-CC catalyst(72.10%).This strategy provides a new way to develop efficient and stable non-precious metal dual-functional electrocatalysts for HER and organic wastewater degradation.

Degradation of Organic Compounds by Active Species Sprayed in a Dielectric Barrier Corona Discharge System

Investigation was made into the degradation of organic compounds by a dielectric barrier corona discharge （DBCD） system. The DBCD, consisting of a quartz tube, a concentric high voltage electrode and a net wrapped to the external wall （used as ground electrode）, was introduced to generate active species which were sprayed into the organic solution through an aerator fixed on the bottom of the tube. The effect of four factors-the discharge voltage, gas flow rate, solution conductivity, and pH of wastewater, on the degradation efficiency of phenol was assessed. The obtained results demonstrated that this process was an effective method for phenol degradation. The degradation rate was enhanced with the increase in power supplied. The degradation efficiency in alkaline conditions was higher than those in acid and neutral conditions. The optimal gas flow rate for phenol degradation in the system was 1.6 L/min, while the solution conductivity had little effect on the degradation.

Role of oxygen vacancies and Sr sites in SrCo_(0.8)Fe_(0.2)O_3 perovskite on efficient activation of peroxymonosulfate towards the degradation of aqueous organic pollutants

Metal-based perovskite oxides have contributed significantly to the advanced oxidation processes(AOPs)due to their diverse active sites and excellent compositional/structural flexibility.In this study,we specially designed a perovskite oxide with abundant oxygen vacancies,SrCo_(0.8)Fe_(0.2)O_(3)(SCF),and firstly applied it as a catalyst in peroxymonosulfate(PMS) activation towards organic pollutants degradation.The result revealed that the prepared SCF catalyst exhibited excellent performance on organic compounds degradation.Besides,SCF showed much better activity than La_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3)(LSCF) in terms of reaction rate and stability for the degradation of the organic compounds.Based on the analysis of scanning electron microscope,transmission electron microscope,X-ray diffraction,N_(2) adsorption-desorption,X-ray photoelectron spectroscopy and electron paramagnetic resonance,it was confirmed that the perovskite catalysts with high content of Sr doping at A-site could effectively create a defect-rich surface and optimize its physicochemical properties,which was responsible for the excellent heterogeneous catalytic activity of SCF.SCF can generate three highly active species:~1 O_(2),SO_(4)^(-)· and ·OH in PMS activation,revealing the degradation process of organic compounds was a coupled multiple active species in both radical and nonradical pathway.Moreover,it was mainly in a radical pathway in the degradation through PMS activation on SCF and SO_(4)^(-)· radicals produced were the dominant species in SCF/PMS system.This study demonstrated that perovskite-type catalysts could enrich OVs efficiently by doping strategy and regulate the PMS activation towards sulfate radical-based AOPs.

Fast inactivation of microbes and degradation of organic compounds dissolved in water by thermal plasma

The multifunctionality and the advantages of thermal plasma for the fast inactivation of viable cells and degradation of organic compounds dissolved in waste water are presented.A complete bacterial inactivation process was observed and studied using a thermal plasma treatment source with very short application times,in particular for Staphylococcus aureus bundle spore survival.The survival curves and analyses of the experimental data of the initial and final densities of S.aureus bacteria show a dramatic inhibitory effect of the plasma discharge on the residual bacteria survival ratio.As the exposure time increased,the inactivation process rate increased for direct exposure more than it did for indirect exposure.The evaluation of direct and indirect exposure was based on the analysis of the ultraviolet spectrum from the absorbance spectra of the organic compound dye called benzene sulfonate（C（16）H（11）N2Na O4S）and of viable cells called S.aureus.Organic compounds were degraded and viable cells were killed in a short time by thermal plasma.Moreover,analyses of total carbon,total organic carbon,and total inorganic carbon showed a fast decrease in organically bound carbon,however,this was not as fast as the absorbance spectra revealed by the exposure time increasing more for direct exposure than indirect exposure.After 100 s of exposure to the organic compound dye the removal had a maximun of 40%for samples with indirect exposure to the plasma and a maximum of 90%for samples with the direct exposure.For both samples,where some organic contaminants still remained in treated water,four electrolytes（KCl,Na Cl,Na2SO4,and CH3COONa）were added to be effective for complete sterilization,reaching a purity of 100%.A proposal is made for an optimized thermal plasma water purification system（TPWPS）to improve fast inactivation of microbes and the degradation of organic compounds dissolved in water（especially for direct exposure rather than indirect exposure）using a hybrid plasma torch with an electrical power of 125 kW（500 V–250 A）producing a high-temperature（10 000 K–19 000 K）plasma jet with a maximum gas consumption of 28 mg s^-1.

Mangrove forest degradation indicated by mangrove-derived organic matter in the Qinzhou Bay,Guangxi,China,and its response to the Asian monsoon during the Holocene climatic optimum

The response of mangrove ecosystems to the Asian monsoon in the future global warming can be understood by reconstructing the development of mangrove forests during the Holocene climatic optimum（HCO）, using proxies preserved in coastal sediments. The total organic matter in sediments of a segmented core, with calibrated age ranges between 5.6 and 7.7 cal. ka BP and corresponding to the HCO, from the Qinzhou Bay in Guangxi, China, is quantitatively partitioned into three end-members according to their sources： mangrove-derived, terrigenous,and marine phytoplanktonic, using a three-end-member model depicted by organic carbon isotope（δ13Corg） and the molar ratio of total organic carbon to total nitrogen（C/N）. The percentage of mangrove-derived organic matter（MOM） contribution is used as a proxy for mangrove development. Three visible drops in MOM contribution occurred at ca. 7.3, ca. 6.9, and ca. 6.2 cal. ka BP, respectively, are recognized against a relatively stable and higher MOM contribution level, indicating that three distinct mangrove forest degradations occurred in the Qinzhou Bay during the HCO. The three mangrove forest degradations approximately correspond to the time of the strengthened/weakened Asian winter/summer monsoon. This indicates that even during a period favorable for the mangrove development, such as the HCO, climatic extremes, such as cold and dry events driven by the strengthened/weakened Asian winter/summer monsoon, can trigger the degradation of mangrove forests.

MESOPOROUS TIO_2 NANO-SPHERES: ELECTROSPRAY COMBINED SOL-GEL FABRICATION AND APPLICATION TO ORGANIC PHOSPHORUS DEGRADATION

In this work, electrospray technique combined sol-gel method was used to prepare porous TiO2 film. X-ray Photoelectron Spectroscopy (XPS), X-Ray Diffraction (XRD), and Scanning Electron Microscope (SEM) analyses were conducted to examine the chemical composition, phase structure, and surface morphology of the sprayed TiO2 film. After calcined at 450℃ in air atmosphere for 2 h, mesoporous TiO2 nano-spheres clusters were formed on the surface of silicon wafer and the average size of nano-spheres was 250 nm. Ti presented as Ti 4+ oxidation state in TiO2 film, and the TiO2 film exhibited the anatase phase. The sprayed porous TiO2 films were employed as photocatalyst to degrade organic phosphorus in water samples. Compared with the TiO2 film prepared by Sol-Gel spin-coating method, the porous TiO2 film deposited by electrospray combined sol-gel method showed higher photocatalytic activity.

Enhanced organic degradation and microbial community cooperation by inoculating Bacillus licheniformis in low temperature composting

Microbial activity and interaction are the important driving factors in the start-up phase of food waste composting at low temperature.The aim of this study was to explore the effect of inoculating Bacillus licheniformis on the degradation of organic components and the potential microbe-driven mechanism from the aspects of organic matter degradation,enzyme activity,microbial community interaction,and microbial metabolic function.The results showed that after inoculating B.licheniformis,temperature increased to 47.8℃ on day2,and the degradation of readily degraded carbohydrates(RDC)increased by 31.2%,and the bioheat production increased by 16.5%.There was an obvious enhancement of extracellular enzymes activities after inoculation,especially amylase activity,which increased by 7.68 times on day 4.The inoculated B.licheniformis colonized in composting as key genus in the start-up phase.Modular network analysis and Mantel test indicated that inoculation drove the cooperation between microbial network modules who were responsible for various organic components(RDC,lipid,protein,and lignocellulose)degradation in the start-up phase.Metabolic function prediction suggested that carbohydrate metabolisms including starch and sucrose metabolism,glycolysis/gluconeogenesis,pyruvate metabolism,etc.,were improved by increasing the abundance of related functional genes after inoculation.In conclusion,inoculating B.licheniformis accelerated organic degradation by driving the cooperation between microbial network modules and enhancing microbial metabolism in the start-up phase of composting.

BiVO_4 Photoanode with Exposed(040) Facets for Enhanced Photoelectrochemical Performance

A BiVO_4 photoanode with exposed(040) facets was prepared to enhance its photoelectrochemical performance.The exposure of the(040) crystal planes of the BiVO_4 film was induced by adding NaCl to the precursor solution. The asprepared BiVO_4 photoanode exhibits higher solar-light absorption and charge-separation efficiency compared to those of an anode prepared without adding Na Cl. To our knowledge,the photocurrent density(1.26 m A cm^(-2) at 1.23 V vs. RHE) of as-prepared BiVO_4 photoanode is the highest according to the reports for bare BiVO_4 films under simulated AM1.5 G solar light, and the incident photon-to-current conversion efficiency is above 35% at 400 nm. The photoelectrochemical(PEC)water-splitting performance was also dramatically improvedwith a hydrogen evolution rate of 9.11 lmol cm^(-2) h^(-1), which is five times compared with the BiVO_4 photoanode prepared without NaCl(1.82 lmol cm^(-2) h^(-1)). Intensity-modulated photocurrent spectroscopy and transient photocurrent measurements show a higher charge-carrier-transfer rate for this photoanode. These results demonstrate a promising approach for the development of high-performance BiVO_4 photoanodes which can be used for efficient PEC water splitting and degradation of organic pollutants.

Investigation of the Photosensitized Mechanisms of PCBs in the Presence of Natural Organic Matter

The structures of 26 different congeners of polychlorinated biphenyls（PCBs, including monothrough deca-chlorinated） were optimized using density functional theory（DFT） calculations with the 6-31＋G（d,p） basis set. The activation energies for the dechlorination of these systems were calculated for direct photodegradation and photosensitized degradation reaction pathways in the presence of natural organic matter（NOM）. The dechlorination mechanism of these PCBs and the ring-opening reaction mechanisms（using QST3 method） of the photosensitive degradation products were analyzed. The results showed that（i） the activation energy for the photosensitized degradation of PCBs was much lower than that of direct photodegradation;（ii） the degradation activities（i.e., C–Cl bond cleavage energies） were the same for both degradation pathways and followed the order ortho 〉 meta 〉 para;（iii） the degradation activities of asymmetric PCBs were higher than those of the corresponding symmetrical PCBs for the direct photodegradation and it was completely opposite in the photosensitive degradation;（iv） there was no correlation between the dissociation energy and the number of C–Cl bonds for the direct photodegradation and dechlorination products were all biphenyl;（v） the degradation activity of PCBs decreased as the number of C–Cl bonds increased in the presence of NOM; and（vi） even when the dechlorination reaction was incomplete, it produced chlorophenol. Furthermore, the free radicals of NOM led to the ring-opening reactions of PCBs via an initial addition step. The main site of these ring-opening reactions was the ortho position. Notably, the likelihood of ring-opening reactions occurring involving the degradation products increased as the degradation degree of PCBs increased.

One-step synthesis of three-dimensional mesoporous Co_(3)O_(4)@Al_(2)O_(3)nanocomposites with deep eutectic solvent:An efficient and stable peroxymonosulfate activator for organic pollutant degradations

The effective,stable,and secure catalysts are essential for sulfate radical(SO_(4)·−)-based advanced oxidation processes(SR-AOPs)to the degradation of organic contaminants in water.Heterogeneous supported cobalt-based catalysts are commonly used to activate peroxymonosulfate(PMS)to achieve the degradation.In this work,we synthesized Co_(3)O_(4)@Al_(2)O_(3)three-dimensional(3D)mesoporous nanocomposite(denoted as Co_(3)O_(4)@Al_(2)O_(33)DPNC)in just one step by calcining cheap and green deep eutectic solvent(DES)solution containing Co salt.Co_(3)O_(4)@Al_(2)O_(33)DPNC with the high specific surface area(93.246 m^(2)/g),uniform pore distribution(3.829 nm)and rich porosity(0.255 cm^(3)/g)were attained in a beautiful hierarchical structure which exhibited the open 3D propeller-like microstructure,two-dimensional lamellar substructure with rich folds,as well as the decoration of highly dispersed Co_(3)O_(4)nanoparticles on mesoporous amorphous Al_(2)O_(3).The excellent chemical and thermal stability of Al_(2)O_(3)ensures the high stability of the catalyst,and the formation of the complex hierarchical structure makes the active Co_(3)O_(4)be homogenously dispersed for effective catalysis.The catalyst demonstrated outstanding performance for catalytic degradations of organic pollutants(acetaminophen,oxytetracycline,5-sulfosalicylic acid,orange G and Rhodamine B)by generated SO_(4)·−,·OH and^(1)O_(2).With a very low cobalt content(equal to 28.2 mg/L of Co),the catalyst exhibited very high stability and excellent reusability in the recycling usages,while the leaching of the cobalt element(<0.145 mg/L)was also at a low level.Our catalyst achieved effective degradations of acetaminophen in cycles without losing its stable hierarchical nanostructure.

Enhanced photocatalytic performance of tungsten-based photocatalysts for degradation of volatile organic compounds: a review

Photocatalytic oxidation process for the degradation of volatile organic compounds(VOCs)contaminants is a promising technology.But until now,the low photocatalytic activity of the conventional TiO_(2) photocatalyst under visible-light irradia-tion hinders the deployment of this technique for VOCs degradation.WO_(3) has been proved to be a suitable photocatalytic material for degradation of various VOCs as its appropriate band-gap,high stability and great capability.Nevertheless,the actual implementation of WO_(3) is still restricted by short lifetime of photoexcited charge carriers and low light energy conver-sion efficiency:its photocatalytic performance is needed to be improved.This review discusses the process of tungsten-based photocatalyst for removal of VOCs and summarizes a variety of strategies to improve the VOCs oxidation performances of WO_(3),such as controlling the morphology structure,engendering chemical defects,coupling heterojunction,doping suitable dopants and loading a co-catalyst.In addition,the practical application of tungsten-based photocatalyst is discussed.

A periodic metallo-supramolecular polymer from a flexible building block: self-assembly and photocatalysis for organic dye degradation

A water-soluble metallo-supramolecular polymer MSP-f-6Np,which possesses a regular pore aperture of 1.4 nm,has been assembled from a structurally flexible naphthalene-appended[Ru(bipy)3]^2+complex and cucurbit[8]uril.As the first periodic metallo-supramolecular polymer formed by a flexible building block,MSP-f-6Np exhibits a hydrodynamic diameter of 122 and 164 nm at 0.1 and 2.0 mM of the monomer concentrations.Synchrotron small angle X-ray scattering experiments confirm that MSP-f-6Np possesses porosity periodicity in both the solution and solid states.Compared with a control,the new highly ordered porous system displays enhanced photocatalytic activity for the degradation of organic dyes.

Bandgap engineering of tetragonal phase CuFeS_(2)quantum dots via mixed-valence single-atomic Ag decoration for synergistic Cr(VI)reduction and RhB degradation

Bandgap engineering through single-atom site binding on semiconducting photocatalyst can boost the intrinsic activity,selectivity,carrier separation,and electron transport.Here,we report a mixed-valence Ag(0)and Ag(I)single atoms co-decorated semiconducting chalcopyrite quantum dots(Ag/CuFeS_(2)QDs)photocatalyst.It demonstrates efficient photocatalytic performances for specific organic dye(rhodamine B,denoted as RhB)as well as inorganic dye(Cr(VI))removal in water under natural sunlight irradiation.The RhB degradation and Cr(VI)removal efficiencies by Ag/CuFeS_(2)QDs were 3.55 and 6.75 times higher than those of the naked CuFeS_(2)QDs at their optimal pH conditions,respectively.Besides,in a mixture of RhB and Cr(VI)solution under neutral condition,the removal ratio has been elevated from 30.2%to 79.4%for Cr(VI),and from 95.2%to 97.3%for RhB degradation by using Ag/CuFeS_(2)QDs after 2 h sunlight illumination.The intrinsic mechanism for the photocatalytic performance improvement is attributed to the narrow bandgap of the single-atomic Ag(I)anchored CuFeS_(2)QDs,which engineers the electronic structure as well as expands the optical light response range.Significantly,the highly active Ag(0)/CuFeS_(2)and Ag(I)/CuFeS_(2)effectively improve the separation efficiency of the carriers,thus enhancing the photocatalytic performances.This work presents a highly efficient single atom/QDs photocatalyst,constructed through bandgap engineering via mixed-valence single noble metal atoms binding on semiconducting QDs.It paves the way for developing high-efficiency single-atom photocatalysts for complex pollutions removal in dyeing wastewater environment.

Photocatalytic parameters and kinetic study for degradation of dichlorophenol-indophenol (DCPIP) dye using highly active mesoporous TiO_2 nanoparticles

Highly active mesoporous TiO_2 of about 6 nm crystal size and 280.7 m^2/g specific surface areas has been successfully synthesized via controlled hydrolysis of titanium butoxide at acidic medium. It was characterized by means of XRD（X-ray diffraction）, SEM（scanning electron microscopy）, TEM（transmission electron microscopy）, FT-IR（Fourier transform infrared spectroscopy）, TGA（thermogravimetric analysis）, DSC（differential scanning calorimetry） and BET（Brunauer–Emmett–Teller） surface area. The degradation of dichlorophenol-indophenol（DCPIP） under ultraviolet（UV） light was studied to evaluate the photocatalytic activity of samples. The effects of different parameters and kinetics were investigated. Accordingly, a complete degradation of DCPIP dye was achieved by applying the optimal operational conditions of 1 g/L of catalyst, 10 mg/L of DCPIP, pH of 3 and the temperature at 25 ± 3°C after 3 min under UV irradiation. Meanwhile, the Langmuir–Hinshelwood kinetic model described the variations in pure photocatalytic branch in consistent with a first order power law model.The results proved that the prepared TiO_2 nanoparticle has a photocatalytic activity significantly better than Degussa P-25.

Coordination polymers： Challenges and future scenarios for capture and degradation of volatile organic compounds

Over the past few decades, coordination polymers/metal organic frameworks （CPs/MOFs） have drawn a great deal of attention for diverse applications due to their advantages of intrinsically ttLnable chemical structure, flexible architecture, high pore volume, high surface area, multifunctional properties, etc. To date, numerous CPs/MOFs have been developed and employed for the treatment and control of gaseous pollutants, such as volatile organic compounds （VOCs）, through capture, sorptive removal, and catalytic degradation. Nevertheless, there are also some key drawbacks and challenges for the practical application of these systems （e.g., poor selectivity, high energy （and fiscal） cost, high synthesis cost, low capacity, and difficulties in regeneration and recycling）. In this review, recent developments in CPs/MOFs research are described with their associated mechanisms for capture, sorptive removal, and catalytic degradation of VOCs. To this end, we discuss the key variables and challenges for afforded abatement of VOCs through CPs/MOFs technologies. Hopefully, this review will help the scientific community set future directions for the advancement of CPs/MOFs techniques for the effective management of diverse environmental issues.

Ni(NH_(3))_(6)^(2+) more efficient than Ni(H_(2)O)_(6)^(2+) and Ni(OH)_(2) for catalyzing water and phenol oxidation on illuminated Bi_(2)MoO_(6) with visible light

Nickel (hydr)oxide (NiOH) is known to be good co-catalyst for the photoelectrochemical oxidation of water,and for the photocatalytic oxidation of organics on different semiconductors.Herein we report a greatly improved activity of Bi_(2)MoO_(6)(BMO) by nickel hexammine perchlorate (NiNH).Under visible light,phenol oxidation on BMO was slow.After NiNH,NiOH,and Ni^(2+)loading,a maximum rate of phenol oxidation increased by factors of approximately 16,8.8,and 4.7,respectively.With a BMO electrode,all catalysts inhibited O_(2)reduction,enhanced water (photo-)oxidation,and facilitated the charge transfer at solidliquid interface,respectively,the degree of which was always NiNH>NiOH>Ni^(2+).Solid emission spectra indicated that all catalysts improved the charge separation of BMO,the degree of which also varied as NiNH>NiOH>Ni^(2+).Furthermore,after a phenol-free aqueous suspension of NiNH/BMO was irradiated,there was a considerable Ni(Ⅲ) species,but a negligible NH_(2)radical.Accordingly,a plausible mechanism is proposed,involving the hole oxidation of Ni(Ⅱ) into Ni(Ⅳ),which is reactive to phenol oxidation,and hence promotes O_(2)reduction.Because NH_(3)is a stronger ligand than H_(2)O,the Ni(Ⅱ) oxidation is easier for Ni(NH_(3))6+than for Ni(H_(2)O)6+.This work shows a simple route how to improve BMO photocatalysis through a co-catalyst.

Topochemical polymerization of hydrogen-bonded organic framework for supporting ultrafine palladium nanoparticles

Topochemical polymerization of molecular crystals into porous materials is of significance due to their promising applications in the field of adsorption and catalysis,yet rarely reported due to the synthesis difficulty.Herein,a hydrogen-bonded organic framework(HOF-45)has been fabricated by the crystallization of a cage-like building block containing three alkynyl groups.It exhibits almost mesoporous structure demonstrated by single crystal X-ray diffraction study.Light-driven topochemical polymerization of HOF-45 with ethanedithiol covalently links alkynyl groups in HOF-45,generating a hydrogen-bond and covalentbond cross-linked material(HOF-45C).In contrast to HOF-45,cross-linked HOF-45C retains the crystalline nature and displays improved solution resistence according to the powder X-ray diffraction data.In particular,HOF-45C is able to support the growth of ultrafine palladium nanoparticles with the average size of ca.1.9 nm for rapidly promoting the degradation of nitrophenol,methyl orange,and congo red with the help of NaBH_(4)as well as Suzuki-Miyaura coupling reaction.This work inputs a new idea on the HOFs application in preparing covalent-linked porous organic materials.

Recent Progress on Visible Light Responsive Heterojunctions for Photocatalytic Applications

Photocatalysis has attracted much attention in recent years due to its potential in solving energy and environmental issues. Even though numerous achievements have been made, the photocatalytic systems developed to date are still far from practical applications due to the low efficiency and poor durability. Efficient light absorption and charge separation are two of the key factors for the exploration of high performance photocatalytic systems, which is generally difficult to be obtained in a single photocata- lyst. The combination of various materials to form heterojunctions provides an effective way to better harvest solar energy and to facilitate charge separation and transfer, thus enhancing the photocatalytic activity and stability. This review concisely summarizes the recent development of visible light respon- sive heterojunctions, including the preparation and performances of semiconductor/semiconductor junctions, semiconductor/cocatalyst junctions, semiconductor/metal junctions, semiconductor/non- metal junctions, and surface heterojunctions, and their mechanism for enhanced light harvesting and charge separation/transfer.

Self-powered electrochemical system by combining Fenton reaction and active chlorine geheration for organic contaminant treatment

Environmental deterioration,especially water pollution,is widely dispersed and could affect the quality of people's life at large.Though the sewage treatment plants are constructed to meet the demands of cities,distributed treatment units are still in request for the supplementary of centralized purification beyond the range of plants.Electrochemical degradation can reduce organic pollution to some degree,but it has to be powered.Triboelectric nanogenerator(TENG)is a newly-invented technology for low-frequency mechanical energy harvesting.Here,by integrating a rotary TENG(R-TENG)as electric power source with an electrochemical cell containing a modified graphite felt cathode for hydrogen peroxide(H2O2)along with hydroxyl radical(·OH)generation by Fenton reaction and a platinum sheet anode for active chlorine generation,a self-powered electrochemical system(SPECS)was constructed.Under the driven of mechanical energy or wind flow,such SPECS can efficiently degrade dyes after power management in neutral condition without any O2 aeration.This work not only provides a guideline for optimizing self-powered electrochemical reaction,but also displays a strategy based on the conversion from distributed mechanical energy to chemical energy for environmental remediation.

Characteristics of ozone and ozone precursors(VOCs and NOx) around a petroleum refinery in Beijing, China

A field measurement campaign for ozone and ozone precursors （VOCs and NOx） was conducted in summer 2011 around a petroleum refinery in the Beijing rural region. Three observation sites were arranged, one at southwest of the refinery as the background, and two at northeast of the refinery as the downwind receptors. Monitoring data revealed the presence of serious surface 03 pollution with the characteristics of high average daily mean and maximum concentrations （64.0 and 145.4 ppbV in no-rain days, respectively） and multi-peak diurnal variation. For NOx, the average hourly concentrations of NO2 and NO were in the range of 20.546.1 and 1.8-6.4 ppbV, respectively. For VOC measurement, a total of 51 compounds were detected. Normally, TVOCs at the background site was only dozens of ppbC, while TVOCs at the downwind sites reached several hundreds of ppbC. By subtracting the VOC concentrations at background, chemical profiles of VOC emission from the refinery were obtained, mainly including alkanes （60.0% ± 4.3%）, alkenes （21.1% ± 5.5%） and aromatics （18.9% ±3.9%）. Moreover, some differences in chemical profiles for the same measurement hours were observed between the downwind sites; the volume ratios of alkanes with low reactivity and those of alkenes with high reactivity respectively showed an increasing trend and a decreasing trend. Finally, based on temporal and spatial variations of VOC mixing ratios, their photochemical degradations and dispersion degradations were estimated to be 0.15-0.27 and 0.42-0.62, respectively, by the photochemical age calculation method, indicating stronger photochemical reactions around the refinery.