Recent advance on VOCs oxidation over layered double hydroxides derived mixed metal oxides

Catalytic oxidation is regarded as one of the most promising strategies for volatile organic compounds(VOCs)purification.Mixed metal oxides(MMOs),after topological transformation using layered double hydroxides(LDHs)as precursors,are extensively used as catalysts for VOCs oxidation due to their uniformity advantage.This review summarizes the developments in the LDH-derived VOCs heterogeneous catalytic oxidation over the last 10 years.Particularly,it addresses the VOCs abatement performance over MMO,noble metal/MMO,core-shell structured MMO,and integral MMO film catalysts originating from LDHs.Moreover,it highlights the water vapor effect and oxidation mechanism.This review indicates that LDH-based catalysts are a category of important VOCs oxidation materials.

REMOVAL OF ORGANIC POLLUTANTS USING TITANIUM DIOXIDE MEDIATED PHOTOCATALYTIC OXIDATION

A simple and effective method of removing polluted organics in water is reported here.Titanium dioxide is a catalyst in photo-oxidation of monocrotophos.The mechanism of photocatalytic oxidation and the kinetics of the reaction were studied. This same principle also leads to the construction of instrument of PTR-FIA analysis for monitoring organic phosphorus and phosphate in water.

Photoelectrocatalysis for high‐value‐added chemicals production

Photoelectrocatalysis(PEC)is a promising approach that can convert renewable solar energy into chemical energy,while most concern is concentrated on PEC water splitting to obtain high‐value‐added fuel—hydrogen.In practice,more economic benefits can be produced based on PEC technique,such as H_(2)O oxidative H_(2)O_(2) synthesis,organic selective oxidation,organic pollutants degradation and CO_(2) reduction.Although there are plenty of excellent reviews focusing on the PEC water splitting system,the production of various high‐value‐added chemicals in PEC systems has not been discussed synthetically.This Account will focus on the production process of various high‐value‐added chemicals through PEC technology.The photoelectrode design,reaction environment and working mechanisms of PEC systems are also discussed in detail.We believe that this comprehensive Account of the expanded application of photoelectrocatalysis can add an inestimable impetus to the follow‐up development of this technology.

Soil organic carbon pool along different altitudinal level in the Sygera Mountains, Tibetan Plateau

Labile organic carbon（LOC） is one of the most important indicators of soil organic matter quality and dynamics elevation and plays important function in the Tibetan Plateau climate. However, it is unknown what the sources and causes of LOC contamination are. In this study, soil organic carbon（SOC）, total nitrogen（TN）, microbial biomass carbon（MBC）, microbial biomass nitrogen（MBN） and LOC were analyzed based on different soil horizons and elevations using turnover time in an experimental site（3700 m to 4300 m area） in Sygera. SOC and LOC in higher-elevation vegetation types were higher than that of in lower-elevation vegetation types. Our results presented that the soil microbial biomass carbon（SMBC） and soil microbial biomass nitrogen（SMBN）were positively correlated with SOC. The content of easily oxidized carbon（EOC）, particulate organic carbon（POC） and light fraction organic carbon（LFOC） decreased with depth increasing and the content were the lowest in the 60 cm to 100 cm depth.The total SOC, ROC and POC contents decreased with increasing soil horizons. The SOC, TN, MBC and MBN contents increased with increasing altitude in the Sygera Mountains. The MBC and MBN contents weredifferent with the changes of SOC（p＆lt;0.05）,meanwhile, both LFOC and POC were related to total SOC（p＆lt;0.05）. The physical and chemical properties of soil, including temperature, humidity, and altitude,were involved in the regulation of SOC, TN, MBC,MBN and LFOC contents in the Sygera Mountains,Tibetan Plateau.

Effects of Organic Manure Applications on Methane and Nitrous Oxide Emissions in Paddy Fields

This study was carried out in paddy fields to explore how organic manure applications would affect greenhouse emissions in South China. The results showed that the seasonal emission of CH4 under the chemical fertilizer （CF） treatment was 271.47 kg/hm^2. In comparison, the seasonal emissions of CH4 under the treatment of pig manure （PM）, chicken manure （CM） and rice straw （RS） increased by 50.61,260.22 and 602.82 kg/hm^2, respectively. N2O emission under the CF treatment was 1.22 kg/hm^2, while the N20 seasonal emissions under tile PM, CM and RS treatment decreased by 23.6% （P〈0.05）, 31.7% （P〈0.05） and 30.9% （P〈0.05）, respectively. Meanwhile, the readily oxidized organic carbon （which was oxidized by 167 mmol/L potassium permanganate, ROC167） of manure, paddy soil Eh value and temperature could also affect the CH4 emissions. The average yield of the organic fertilizer treatments increased by 6.8% compared with that of the CF treatment. Among all the organic fertilizer treatments, the PM treatment offered the lowest global warming potential and greenhouse gas intensity, in which the PM was of no significant difference from NF （no fertilizing） and CF. Therefore, the pig manure is capable of coordinating the relationship between environment and yield, and it also has a low ROC167 content, so the PM is considered worthy of recommendation.

Biomarker assessments of sources and environmental implications of organic matter in sediments from potential cold seep areas of the northeastern South China Sea

Multi-biomarker indexes were analyzed for two piston cores from potential cold seep areas of the South China Sea off southwestern Taiwan. Total organic carbon（TOC） normalized terrestrial（n-alkanes） and marine（brassicasterol, dinosterol, alkenones and iso-GDGTs） biomarker contents and ratios（TMBR, 1/Pmar-aq, BIT） were used to evaluate the contributions of terrestrial and marine organic matter（TOM and MOM respectively） to the sedimentary organic matter, indicating that MOM dominated the organic sources in Core MD052911 and the sedimentary organic matter in Core ORI-_（86）0-22 was mainly derived from terrestrial inputs, and different morphologies were the likely reason for TOM percentage differences. BIT results suggested that river-transported terrestrial soil organic matter was not a major source of TOM of sedimentary organic matter around these settings.Diagnostic biomarkers for methane-oxidizing archaea（MOA） were only detected in one sample at 172 cm depth of Core ORI-_（86）0-22, with abnormally high iso-GDGTs content and Methane Index（MI） value（0.94）. These results indicated high anaerobic oxidation of methane（AOM） activities at or around 172 cm in Core ORI-_（86）0-22.However in Core MD052911, MOA biomarkers were not detected and MI values were lower（0.19–0.38）, indicated insignificant contributions of iso-GDGTs from methanotrophic archaea and the absence of significant AOM activities. Biomarker results thus indicated that the discontinuous upward methane seepage and insufficient methane flux could not induce high AOM activities in our sampling sites. In addition, the different patterns of TEX_（86） and U_（37）^（K′） temperature in two cores suggested that AOM activities affected TEX_（86）37 temperature estimates with lower values in Core ORI-_（86）0-22, but not significantly on TEX_（86） temperature estimates in Core MD052911.

Ozonation of o-phenylenediamine in the presence of hydrogen peroxide by high-gravity technology

The study herein investigated the effectiveness of simultaneous use of ozone and hydrogen peroxide(O_3/H_2O_2 process) to degrade o-phenylenediamine(o-PDA) in a simulated wastewater. A rotor–stator reactor(RSR) was employed to create a high-gravity environment in order to enhance ozone-liquid mass transfer rate and possibly improve the degradation rate of o-PDA. The degradation efficiency of o-PDA(η) as well as the overall gas-phase volumetric mass transfer coefficient(KGa) were determined under different operating conditions of H_2O_2 concentration, initial o-PDA concentration, temperature of reaction, initial p H and rotation speed of RSR in attempt to establish the optimal conditions. Chemical oxygen demand reduction rate(rCOD) of wastewater treated at a particular set of conditions was also analyzed. Additionally, the intermediate products of degradation were identified using a gas chromatography-mass spectrometer(GC/MS) to further evaluate the extent of o-PDA degradation as well as establish its possible degradation pathway. Results were validated by comparison with those of sole use of ozone(O_3 process), and it was noted that η, KGa and rCODachieved by O_3/H_2O_2 process was 24.4%,31.6% and 25.2% respectively higher than those of O_3 process, indicating that H_2O_2 can greatly enhance ozonation of o-PDA. This work further demonstrates that an RSR can significantly intensify ozone-liquid mass transfer rate and thus provides a feasible intensification means for the ozonation of o-PDA as well as other recalcitrant organics.

Hybrid water electrolysis:Replacing oxygen evolution reaction for energy-efficient hydrogen production and beyond

Renewable energy-driven hydrogen generation from water electrolysis has been widely recognized as a promising approach to utilize sustainable energy resources,reduce our dependence on legacy fossil fuels and alleviate net carbon dioxide emissions.However,conventional water electrolyzers suffer from the high overpotentials,mainly due to the sluggish kinetics of anodic oxygen evolution reaction(OER).This reaction also generates reactive oxygen species that could degrade the proton exchange membrane and oxygen that may mix with the cathodic hydrogen to form explosive gaseous mixtures.To address these issues,an innovative hybrid water electrolysis strategy which involves a certain alternative oxidation reaction to replace OER has been developed,and has led to a burgeoning area that sparks much research interest in finding available alternative reactions and their corresponding electrocatalysts.Herein,we summarize the alternative reactions into three groups:(1)the reagentsacrificing type that can generate H2 with an ultra-low potential while the substrates are oxidized to valueless products;(2)the pollutant-degrading type at which environmental pollutants are used as substrates;(3)the valueadded type that produces valuable products at the anode.Catalyst and electrolyzer designs for hybrid electrolysis are also briefly discussed,with an emphasis on the catalyst reconstruction phenomenon.Finally,the present challenges and perspectives are put forward.

Novel Air Purification System for Installation in Air Handling Units： Development, Assembly and Experimental Analysis

Nowadays, people pass 90% of their time in closed spaces, therefore, an increasing care in the creation and upkeep of healthier environments as a personal and as professional level become a major issue. The present project has as goal the verification and optimization of the implicit need of an OCRAMclima~ AHU （air handling units） in IAQ （indoor air quality） and its effectiveness in treatment and/or air purification, having as basis the legal national and European requirements for IAQ. This work was based on the study of the state of the art of the techniques in air purification and in the evaluation of their performance, culminating in the production of the prototype OCRAMclima~ NPS （nano purifying system）. The purifying phenomena involved are UVGI （ultraviolet germicidal irradiation） and catalytic ionization of air. The performance test was accomplished in a closed loop circuit, which results, obtained by an independent IAQ analyst, were satisfactory, indicating the viability of application of this system to indoor air disinfection. The outcome revealed that the conjugating of both phenomena, the air sterilizing by UV and catalytic ionization, is efficient when used for air purification, mainly for volatile organic compounds and bioaerosols.

Recent Advance in Electrocatalytic Water Splitting for Hydrogen Production by Layered Double Hydroxides

Collecting green hydrogen(H2)from water splitting driven by renewable energy is a new competition to implement the construction of H2 energy industry and promote new economic growth for global governments.The common strategy to enhance the efficiency of H2 production is to reduce the potential of electrolytic cell that is the mainstream way to prepare efficient electrocatalysts.Layered double hydroxides(LDHs)are one of the most active electrocatalysts with adjustable active sites in contemporary research.In this review,we discuss the recent advanced progress of LDHs for hydrogen evolution reaction(HER)on cathode and oxygen evolution reaction(OER)or organic oxidation on anode and emphasize the influence of LDHs structure regulation in water electrolysis process(HER/OER)as well as the current development status of organic oxidation catalyzed by active oxygen species on anode.Finally,we propose the current challenges of LDHs in electrocatalysis and prospect their developing tendency and further application.

Synergistic redox reactions toward co-production of H_(2)O_(2)and value-added chemicals:Dual-functional photocatalysis to achieving sustainability

IntegratingH_(2)O_(2)evolution with oxidative organic synthesis in a semiconductordriven photoredox reaction is highly attractive since H_(2)O_(2)and high-value chemicals can be concurrently produced using solar light as the only energy input.The dual-functional photocatalytic approach,free from sacrificial agents,enables simultaneous production of H_(2)O_(2)and high-value organic chemicals.This strategy promises a green and sustainable organic synthesis with minimal greenhouse gas emissions.In this review,we first elucidate the fundamental principles of cooperative photoredox integration of H_(2)O_(2)synthesis and selective organic oxidation with simultaneous utilization of photoexcited electrons and holes over semiconductor-based photocatalysts.Afterwards,a thorough review on the recent advancements of cooperative photoredox synthesis of H_(2)O_(2)and value-added chemicals is presented.Notably,in-depth discussions and insights into the techniques for unravelling the photoredox reaction mechanisms are elucidated.Finally,critical challenges and prospects in this thriving field are comprehensively discussed.It is envisioned that this review will serve as a pivotal guidance on the rational design of such dual-functional photocatalytic system,thereby further stimulating the development of economical and environmentally benignH_(2)O_(2)and high-value chemicals production.

Alterations of soil aggregates and intra-aggregate organic carbon fractions after soil conversion from paddy soils to upland soils:Distribution,mineralization and driving mechanism

Investigating the impacts of soil conversion on soil organic carbon(OC) content and its fractions within soil aggregates is essential for defining better strategies to improve soil structure and OC sequestration in terrestrial ecosystems. However, the consequences of soil conversion from paddy soil to upland soil for soil aggregates and intra-aggregate OC pools are poorly understood. Therefore, the objective of this study was to quantify the effects of soil conversion on soil aggregate and intra-aggregate OC pool distributions. Four typical rice-producing areas were chosen in North and South China, paired soil samples(upland soil converted from paddy soil more than ten years ago vs. adjacent paddy soil) were collected(0–20 cm) with three replicates in each area. A set of core parameters(OC preservation capacity, aggregate carbon(C) turnover, and biological activity index) were evaluated to assess the responses of intra-aggregate OC turnover to soil conversion. Results showed that soil conversion from paddy soil to upland soil significantly improved the formation of macro-aggregates and increased aggregate stability. It also notably decreased soil intra-aggregate OC pools, including easily oxidized OCa(EOCa), particulate OCa(POCa), and mineral-bound(MOCa) OC, and the sensitivity of aggregate-associated OC pools to soil conversion followed the order: EOCa(average reduction of 21.1%) > MOCa(average reduction of 15.4%) > POCa(average reduction of 14.8%). The potentially mineralizable C(C_(0)) was significantly higher in upland soil than in paddy soil, but the corresponding decay constant(k) was lower in upland soil than in paddy soil. Random forest model and partial correlation analysis showed that EOCa and pH were the important nutrient and physicochemical factors impacting k of C mineralization in paddy soil,while MOCa and C-related enzyme(β-D-cellobiohydrolase) were identified as the key factors in upland soil. In conclusion, this study evidenced that soil conversion from paddy soil to upland soil increased the percentage of macro-aggregates and aggregate stability, while decreased soil aggregate-associated C stock and k of soil C mineralization on a scale of ten years. Our findings provided some new insights into the alterations of soil aggregates and potential C sequestration under soil conversion system in rice-producing areas.

Constructing dual-functional porphyrin-based thorium metal-organic framework toward photocatalytic uranium(Ⅵ)reduction integrated with organic oxidation

The rational fabrication of photocatalysts with dual functions upon visible light, such as photocatalytic radioactive U(Ⅵ)reduction and value-added organic oxidation, is highly desirable but remains huge challenge. Here, we couple the photocatalytic U(Ⅵ) reduction with the oxidative organic synthesis to one system using novel extended π-conjugated framework(Cu@ThTCPP) without the expense of sacrificial reagents. Noticeably, the as-prepared Cu@Th-TCPP linked by tetratopic tetrakis(4-carboxyphenyl)porphyrin(TCPP) ligand and unique Th(μ-O)(HCOO)(HO)secondary building unit(SBU) exhibits significantly enhanced activity when the photocatalytic U(Ⅵ) reduction and thioanisole oxidation were integrated to one system.Further experimental characterizations demonstrate that the highly conjugated framework of Cu@Th-TCPP is good for the charge transfer and separation, while incorporating Cusite further accelerates the charge-carrier dynamics, thus giving rise to the dual-functional property. Apparently, this strategy conforms to atomic economy, opens a new horizon to address radioactive environmental pollution in natural water systems and soils, and simultaneously produces valuable chemicals.

Size distribution and chemical composition of secondary organic aerosol formed from Cl-initiated oxidation of toluene

Secondary organic aerosol （SOA） formed from Cl-initiated oxidation of toluene was investigated in a home-made smog chamber. The size distribution and chemical composition of SOA particles were measured using aerodynamic particle sizer spectrometer and the aerosol laser time-of-flight mass spectrometer （ALTOFMS）, respectively. According to a large number of single aerosol diameter and mass spectra, the size distribution and chemical composition of SOA were obtained statistically. Experimental results showed that SOA particles created by Cl-initiated oxidation of toluene is predominantly in the form of fine particles, which have diameters less than 2.5 μm （i.e., PM2.5）, and glyoxal, benzaldehyde, benzyl alcohol, benzoquinone, benzoic acid, benzyl hydroperoxide and benzyl methyl nitrate are the major products components in the SOA. The possible reaction mechanisms leading to these products are also proposed.

An investigation on catalytic performance and reaction mechanisms of Fe/OMS-2 for the oxidation of carbon monoxide, ethyl acetate, and toluene

The octahedral molecular sieve(OMS-2)-supported Fe( xFe/OMS-2: x = 1, 3, 5, and 10) catalysts were prepared using the pre-incorporation method. Physicochemical properties of the as-synthesized materials were characterized by means of various techniques, and their catalytic activities for CO, ethyl acetate, and toluene oxidation were evaluated. Among all of the samples, performed the best, with the reaction temperature required to achieve 90% conversion( T 90%) being 160 ℃ for CO oxidation, 210 ℃ for ethyl acetate oxidation, and 285 ℃ for toluene oxidation. Such a good catalytic performance of 5Fe/OMS-2 was associated with its high(Mn^(3+) + Mn^(2+)) content and adsorbed oxygen species concentration, and good lowtemperature reducibility and lattice oxygen mobility as well as strong interaction between Fe and OMS-2. In addition, catalytic mechanisms of the oxidation of three pollutants over the 5Fe/OMS-2 catalyst were also studied. It was found that CO, ethyl acetate or toluene was first adsorbed, then the related intermediates were formed, and finally the formed intermediates were completely converted into CO_(2) and H_(2)O.

Enhanced catalytic complete oxidation of 1,2-dichloroethane over mesoporous transition metal-doped γ-Al_2O_3

High-surface-area mesoprous powders of γ-Al2O3 doped with Cu^2＋, Cr^3＋, and V^3＋ ions were prepared uia a modified sol-gel method and were investigated as catalysts for the oxidation of chlorinated organic compounds. The composites retained high surface areas and pore volumes comparable with those of undoped γ-Al2O3 and the presence of the transition metal ions enhanced their surface acidic properties. The catalytic activity of the prepared catalysts in the oxidation of 1,2-dichloroethane （DCE） was studied in the temperature range of 250-400℃. The catalytic activity and product selectivity were strongly dependent on the presence and the type of dopant ion. While Cu^2＋- and Cr^3＋-containing catalysts showed 100% conversion at 300℃ and 350℃, V3＋-containing catalyst showed considerably lower conversion. Furthermore, while the major products of the reactions over γ-alumina were vinyl chloride （C2H3Cl） and hydrogen chloride （HCl） at all temperatures, Cu- and Cr-doped catalysts showed siguiticantly stronger capability for deep oxidation to CO2.

Enhanced Photocatalytic Activity of TiO2 Nanofibers and Their Flexible Composite Films： Decomposition of Organic Dyes and Efficient H2 Generation from Ethanol-Water Mixtures

TiO2 nanofibers decorated with Pt and Pd nanoparticles have been synthesized and studied in various photocatalytic processes. Excellent photocatalytic behavior in the decomposition of organic dyes in water, degradation of organic stains on the surface of flexible freestanding cellulose/catalyst composite films and in generation of hydrogen from ethanol using both suspended and immobilized catalysts are demonstrated. The performance of the nanofiber-based TiO2 materials is competitive with and in some cases outperforms--their conventional nanoparticle-based counterparts. In all cases, Pd-decorated TiO2 nanoparticles and nanofibers proved to be more efficient than their Pt-based counterparts, which could be explained on the basis of the formation of nano-sized Schottky interfaces at the contacts between TiO2 and metal nanoparticles. The feasibility of forming cellulose/catalyst composites provides a novel way of utilizing photocatalyst materials in large-area coatings and freestanding films.

Role of secondary aerosols in haze formation in summer in the Megacity Beijing

A field experiment from 18 August to 8 September 2006 in Beijing, China, was carried out. A hazy day was defined as visibility 〈 10 km and RH（relative humidity） 〈 90%. Four haze episodes, which accounted for ～ 60% of the time during the whole campaign, were characterized by increases of SNA（sulfate, nitrate, and ammonium） and SOA（secondary organic aerosol） concentrations. The average values with standard deviation of SO2-＋4, NO-3, NH4 and SOA were 49.8（± 31.6）, 31.4（±22.3）, 25.8（±16.6） and 8.9（±4.1） μg/m3, respectively, during the haze episodes, which were 4.3, 3.4, 4.1, and 1.7 times those in the non-haze days. The SO2-4,NO-3, NH＋4, and SOA accounted for 15.8%, 8.8%, 7.3%, and 6.0% of the total mass concentration of PM10 during the non-haze days. The respective contributions of SNA species to PM10 rose to about27.2%, 15.9%, and 13.9% during the haze days, while the contributions of SOA maintained the same level with a slight decrease to about 4.9%. The observed mass concentrations of SNA and SOA increased with the increase of PM10 mass concentration, however, the rate of increase of SNA was much faster than that of the SOA. The SOR（sulfur oxidation ratio） and NOR（nitrogen oxidation ratio） increased from non-haze days to hazy days, and increased with the increase of RH. High concentrations of aerosols and water vapor favored the conversion of SO2 to SO2-4and NO2 to NO-3, which accelerated the accumulation of the aerosols and resulted in the formation of haze in Beijing.

Cu–Mn–Ce ternary mixed-oxide catalysts for catalytic combustion of toluene

Cu-Mn, Cu-Mn-Ce, and Cu-Ce mixed-oxide catalysts were prepared by a citric acid sol-gel method and then characterized by XRD, BET, H_2-TPR and XPS analyses. Their catalytic properties were investigated in the toluene combustion reaction. Results showed that the Cu-Mn-Ce ternary mixed-oxide catalyst with 1：2：4 mole ratios had the highest catalytic activity, and 99% toluene conversion was achieved at temperatures below 220°C. In the Cu-Mn-Ce catalyst, a portion of Cu and Mn species entered into the Ce O2 fluorite lattice, which led to the formation of a ceria-based solid solution. Excess Cu and Mn oxides existed on the surface of the ceria-based solid solution. The coexistence of Cu-Mn mixed oxides and the ceria-based solid solution resulted in a better synergetic interaction than the Cu-Mn and Cu-Ce catalysts, which promoted catalyst reducibility, increased oxygen mobility, and enhanced the formation of abundant active oxygen species.

A new green system of HPW@MOFs catalyzed desulfurization using O_2 as oxidant

A series of crystalline compounds were obtained from simple one-step hydrothermal reaction of copper nitrate, benzentricaboxylate and different Keggin polyoxometalates. Phosphotungstic acid immobilized in host matrix was selected for the first time as a recyclable and efficient catalyst in oxidative desulfurization process, under eco-sustainable conditions supported by the green oxidant O2 and the green extracting agent distilled water. The efficiency of desulfurization with air was studied and it is possible to use air as green oxidant in desulfurization. Moreover, the catalyst is effective for the desulfurization of real diesel.