无模板插层-剥离勃姆石合成具有优异稳定性的多孔硅掺杂氧化铝二维纳米片

高比表面积和大孔容的多孔氧化铝已被广泛应用在各种领域,但不使用有机模板合成多孔氧化铝仍面临巨大挑战.在此,我们报道了基于插层-剥离策略的多孔氧化铝合成方法,利用硅物种削弱勃姆石(氧化铝前体)的层间作用力,从而在不使用有机模板的情况下将勃姆石剥离成二维纳米片.该合成过程可放大到3 L,并获得厚度为2 nm的二维纳米片.此外,这些二维纳米片可组装成比表面为542 m^(2)g^(-1)和孔容为2.43 cm^(3)g^(-1)的勃姆石.在不同温度下对二维纳米片进行热/水热处理得到的多孔氧化铝其孔结构优于多数有机模板法合成的氧化铝,并表现出优异的吸附性能.本研究为合成二维勃姆石纳米片和多孔氧化铝材料提供了一种新策略.

Study on catalytic mechanisms of Fe_(3)O_(4)-rGO_(x) in three typical advanced oxidation processes for tetracycline hydrochloride degradation

This study explored the catalytic mechanism and performance impacted by the materials ratio of Fe_(3)O_(4)-GO_(x) composites in three typical advanced oxidation processes(AOPs)of O_(3),peroxodisulfate(PDS)and photo-Fenton processes for tetracycline hydrochloride(TCH)degradation.The ratio of GO in the Fe_(3)O_(4)-GO_(x) composites exhibited different trends of degradation capacity in each AOPs based on different mechanisms.Fe_(3)O_(4)-rGO_(20wt%) exhibited the optimum catalytic performance which enhanced the ozone decomposition efficiency from 33.48%(ozone alone)to 51.83%with the major reactive oxygen species(ROS)of O_(2)·-.In PDS and photo-Fenton processes,Fe_(3)O_(4)-rGO_(5wt%) had the highest catalytic performance in PDS and H_(2)O_(2) decomposition for SO_(4)·–,and·OH generation,respectively.Compared with using PDS alone,PDS decomposition rate and TCH degradation rate could be increased by 5.97 and 1.73 times under Fe_(3)O_(4)-rGO_(5wt%) catalysis.In the photo-Fenton system,Fe_(3)O_(4)-rGO_(5wt%) with the best catalyst performance in H_(2)O_(2) decomposition,and TCH degradation rate increased by 2.02 times compared with blank group.Meantime,the catalytic mechanisms in those systems of that the ROS produced by conversion between Fe^(2+)/Fe^(3+)were also analyzed.

Effective electrocatalytic hydrodechlorination of 2,4,6-trichlorophenol by a novel Pd/MnO_(2)/Ni foam cathode

Pd modified electrodes possess problems such as easy agglomeration and low electrolytic ability,and the use of manganese dioxide(MnO_(2)) to facilitate Pd reduction of organic pollutants is just started.However,there is still a limited understanding of how to match the Pd load and MnO_(2) to realize optimal dechlorination efficiency at minimum cost.Here,a Pd/MnO_(2)/Ni foam cathode was successfully fabricated and applied for the efficient electrochemical dechlorination of 2,4,6-trichlorophenol(2,4,6-TCP).The optimal electrocatalytic hydrodechlorination(ECH)performance with 2,4,6-TCP dechlorination efficiency(92.58%in 180 min)was obtained when the concentration of PdCl_(2) precipitation was 1 mmol/L,the deposition time of MnO_(2) was 300 s and cathode potential was-0.8 V.Performance influenced by the exogenous factors(e.g.,initial pH and coexisted ions)were further investigated.It was found that the neutral pH was the most favorable for ECH and a reduction in dechlorination efficiency(6%~47.6%)was observed in presence of 5 mmol/L of NO_(2)^(-),NO_(3)^(-),S^(2-)or SO_(3)^(2-).Cyclic voltammetry(CV)and quenching experiments verified the existence of three hydrogen species on Pd surface,including adsorbed atomic hydrogen(H^(*)_(ads)),absorbed atomic hydrogen(H^(*)_(abs)),and molecular hydrogen(H_(2)).And the introduction of MnO_(2)promoted the generation of atomic H^(*).Only adsorbed atomic hydrogen(H^(*)_(ads)) was confirmed that it truly facilitated the ECH process.Besides H^(*)_(ads) induced reduction,the direct reduction by cathode electrons also participated in the 2,4,6-TCP dechlorination process.Pd/MnO_(2)/Ni foam cathode shows excellent dechlorination performance,fine stability and recyclable potential,which provides strategies for the effective degradation of persistent halogenated organic pollutants in groundwater.

Analysis of floc morphology in a continuous-flow flocculation and sedimentation reactor

The floc morphology was investigated in a continuous-flow reactor, in order to understand the evolution of flocs in practical flocculation and sedimentation processes in water utilities. Kaolin-humic acid suspension was used as the test water, and polyaluminum chloride was chosen as the coagulant. An in-situ recognition system was applied to analyze the floc size, boundary fractal dimension, and eccentricity ratios. Particle numbers and turbidity were also determined in the sedimentation stage. At a coagulant dose of 1 mg/L as Al, the average floc size increased from 62 to 78 μm and the boundary fractal dimension was around 1.14, suggesting that flocs were compact and continuously grew during the entire flocculation process. However, with the dose increased to 5 mg/L, the average floc size decreased and stabilized at around 65 μm, with the fractal dimension of 1.20. It can be concluded that the excess coagulant doses resulted in the formation of chain-shaped, lower density, and more branched structure flocs, thereby restricting flocs’ further growth in the subsequent flocculation. Floc morphology analysis suggested that charge neutralization dominated in the initial flocculation stage, then the bridge and sweep mechanisms were dominant in the subsequent flocculation. In addition, compared with the traditional inclined plate settler, a novel V-shaped plate settler introduced in this study had an advantage in small size floc（less than 5 μm） removal. The V-shaped region could promote aggregate restructuring and re-flocculation; therefore, the V-shaped plate settler provides an alternative method for sedimentation.

Identifying the major fluorescent components responsible for ultrafiltration membrane fouling in different water sources

Three-dimensional fluorescence excitation–emission matrix（EEM） coupled with parallel factor analysis（PARAFAC） was performed for a total of 18 water samples taken from three water sources（two lakes and one wastewater treatment plant（WWTP） secondary effluent）,with the purpose of identifying the major ultrafiltration（UF） membrane foulants in different water sources. Three fluorescent components（C1, C2 and C3） were identified,which represented terrestrially derived humic-like substances（C1）, microbially derived humic-like substances（C2）, and protein-like substances（C3）. The correlations between the different fluorescent components and UF membrane fouling were analyzed. It was shown that for the WWTP secondary effluent, all three components（C1, C2 and C3） made a considerable contribution to the irreversible and total fouling of the UF membrane.However, for the two lakes, only the C3 exhibited a strong correlation with membrane fouling, indicating that the protein-like substances were the major membrane foulants in the lake waters. Significant attachment of C1, C2 and C3 to the UF membrane was also confirmed by mass balance analyses for the WWTP secondary effluent; while the attachment of C1 and C2 was shown to be negligible for the two lakes. The results may provide basic formation for developing suitable fouling control strategies for sustainable UF processes.

Metabolic uncoupler,3,3’,4’,5-tetrachlorosalicylanilide addition for sludge reduction and fouling control in a gravity-driven membrane bioreactor

The gravity-driven membrane bioreactor(MBR)system is promising for decentralized sewage treatment because of its low energy consumption and maintenance requirements.However,the growing sludge not only increases membrane fouling,but also augments operational complexities(sludge discharge).We added the metabolic uncoupler 3,3’,4f,5-tetrachlorosalicylanilide(TC$)to the system to deal with the mentioned issues.Based on the results,TCS addition effectively decreased sludge ATP and sludge yield(reduced by 50%).Extracellular polymeric substances(EPS;proteins and polysaccharides)decreased with the addition of TCS and were transformed into dissolved soluble microbial products(SMPs)in the bulk solution,leading to the break of sludge floes into small fragments.Permeability was increased by more than two times,reaching 60-70 L/m2/h bar when 10-30 mg/L TCS were added,because of the reduced suspended sludge and the formation of a thin cake layer with low EPS levels.Resistance analyses confirmed that appropriate dosages of TCS primarily decreased the cake layer and hydraulically reversible resistances.Permeability decreased at high dosage(50 mg/L)due to the release of excess sludge fragments and SMP into the supernatant,with a thin but more compact fouling layer with low bioactivity developing on the membrane surface,causing higher cake layer and pore blocking resistances.Our study provides a fundamental understanding of how a metabolic uncoupler affects the sludge and bio-fouling layers at different dosages,with practical relevance for in situ sludge reduction and membrane fouling alleviation in MBR systems.

Recent advances in the application of metal organic frameworks using in advanced oxidation progresses for pollutants degradation

Metal-organic frameworks(MOFs)materials with highly ordered and porous crystalline structure,have excellent performance in advanced oxidation progresses(AOPs)for organic contaminants degradation in water treatment.This review intends to summarize the timely references and insights for the recent advances in MOFs that are used in AOPs.Starting with the preparation methodologies,including conventional hydrothermal method,electrochemical method,sol-gel method,and emerging microwave and ultrasound assisted synthesis methods.Application and mechanism for MOFs using in various AOPs of Fenton-like,photocatalysis,catalytic ozonation,persulfate catalysis and other emerging oxidation methods are emphatically discussed.We hope this review can comprehensively summarize the research and application progress of MOFs in AOPs,deepen the understanding of the catalytic mechanisms.

晶面工程优化钴基钙钛矿电子结构及其电解水性能

钴基钙钛矿催化剂的晶面和电子构型与其本征电解水活性密切相关.本文中,我们提出了一种独特的熔盐方法以调控LaCoO_(3)的晶面类型和原子掺杂,进而调制其电子结构.通过引入封端剂(Sr^(2+)),我们制备了具有特定(110)晶面(LCO(110))和(111)晶面(LCO(111))的LaCoO_(3)样品.与LCO(111)相比,CoO_(6)八面体的畸变使LCO(110)和LSCO(111)具有更高的O 2p位置、更强的Co 3d–O 2p共价性以及更高的Co自旋态,从而具有更优的析氧反应(OER)和析氢反应(HER)性能.其中,LCO(110)、LCO(111)和LSCO(111)在10 mA cm^(−2)处的过电位分别为299,322和289 mV.此外,(110)晶面和Sr掺杂使Co–O键能增强,进而提升了LaCoO_(3)的稳定性.本工作通过晶面工程和原子掺杂为电子结构的调控开辟了新的途径,并为阐明OER和HER催化剂的电子结构-电催化活性关系提供了参考.

Ordered mesoporous carbon as an efficient heterogeneous catalyst to activate peroxydisulfate for degradation of sulfadiazine

Catalytic potential of carbon nanomaterials in peroxydisulfate(PDS)advanced oxidation systems for degradation of antibiotics remains poorly understood.This study revealed ordered mesoporous carbon(type CMK)acted as a superior catalyst for heterogeneous degradation of sulfadiazine(SDZ)in PDS sys-tem,with a first-order reaction kinetic constant(k)and total organic carbon(TOC)mineralization efficiency of 0.06 min^(–1) and 59.67%±3.4%within 60min,respectively.CMK catalyzed PDS system exhibited high degradation efficiencies of five other sulfonamides and three other types of antibiotics,verifying the broad-degradation capacity of antibiotics.Under neutral pH conditions,the optimal catalytic parameters were an initial SDZ concentration of 44.0mg/L,CMK dosage of 0.07g/L,and PDS dosage of 5.44mmol/L,respectively.X-ray photoelectron spectroscopy and Raman spectrum analysis confirmed that the defect structure at edge of CMK and oxygen-containing functional groups on surface of CMK were major active sites,contributing to the high catalytic activity.Free radical quenching analysis revealed that both SO_(4)•−and•OH were generated and participated in catalytic reaction.In addition,direct electron transfer by CMK to activate PDS also occurred,further promoting catalytic performance.Configuration of SDZ molecule was optimized using density functional theory,and the possible reaction sites in SDZ molecule were calculated using Fukui function.Combining ultra-high-performance liquid chromatography(UPLC)–mass spectrometry(MS)/MS analysis,three potential degradation pathways were proposed,including the direct removal of SO_(2)molecules,the 14S-17N fracture,and the 19C-20N and 19C-27N cleavage of the SDZ molecule.The study demonstrated that ordered mesoporous carbon could work as a feasible catalytic material for PDS advanced oxidation during removal of antibiotics from wastewater.