作者机构：
[Furong Guo; Tingjuan Gao] Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental & Applied Chemistry, College of Chemistry, Central China Normal University, Wuhan 430079, China;School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China;[Jiangshan Li] State Key Laboratory of Geomechanics and Geotechnical Engineering, Institute of Rock and Soil Mechanics, Chinese Academy of Sciences, Wuhan 430071, China;[Shiyu Cao] Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental & Applied Chemistry, College of Chemistry, Central China Normal University, Wuhan 430079, China<&wdkj&>State Key Laboratory of Geomechanics and Geotechnical Engineering, Institute of Rock and Soil Mechanics, Chinese Academy of Sciences, Wuhan 430071, China;[Yanbiao Shi; Lizhi Zhang] Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental & Applied Chemistry, College of Chemistry, Central China Normal University, Wuhan 430079, China<&wdkj&>School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
通讯机构：
[Tingjuan Gao; Lizhi Zhang] K;Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental & Applied Chemistry, College of Chemistry, Central China Normal University, Wuhan 430079, China<&wdkj&>School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China<&wdkj&>Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental & Applied Chemistry, College of Chemistry, Central China Normal University, Wuhan 430079, China
摘要：
Nano zero-valent iron (nZVI) is a promising phosphate adsorbent for advanced phosphate removal. However, the rapid passivation of nZVI and the low activity of adsorption sites seriously limit its phosphate removal performance, accounting for its inapplicability to meet the emission criteria of 0.1 mg P/L phosphate. In this study, we report that the oxalate modification can inhibit the passivation of nZVI and alter the multi-stage phosphate adsorption mechanism by changing the adsorption sites. As expected, the stronger anti-passivation ability of oxalate modified nZVI (OX-nZVI) strongly favored its phosphate adsorption. Interestingly, the oxalate modification endowed the surface Fe(III) sites with the lowest chemisorption energy and the fastest phosphate adsorption ability than the other adsorption sites, by in situ forming a Fe(III)-phosphate-oxalate ternary complex, therefore enabling an advanced phosphate removal process. At an initial phosphate concentration of 1.00 mg P/L, pH of 6.0 and a dosage of 0.3 g/L of adsorbents, OX-nZVI exhibited faster phosphate removal rate (0.11 g/mg/min) and lower residual phosphate level (0.02 mg P/L) than nZVI (0.055 g/mg/min and 0.19 mg P/L). This study sheds light on the importance of site manipulation in the development of high-performance adsorbents, and offers a facile surface modification strategy to prepare superior iron-based materials for advanced phosphate removal.
摘要：
As one of the most widely used disinfectants, active chlorine is synthesized predominantly through electrolysis of saturated sodium chloride solutions, an industrial process known as the chlor-alkali process, with high energy consumption. Seawater is an abundant source of chloride and thus an ideal alternative electrolyte. However, substantial challenges are to be addressed, notably the competing oxygen evolution reaction and progressive anode passivation due to the presence of rich cations in seawater. Here, we show durable and efficient active chlorine electrosynthesis directly from natural seawater with intrinsic turnover frequency and mass activity two orders of magnitude higher than the state of the art. The essential chemistry is an Fe-doped Ti4O7 anode that strengthens the electrophilicity of lattice oxygen to allow for site-selective chloride activation at remarkably lowered kinetic overpotentials relative to the oxygen evolution reaction, while also impeding the precipitation of alkaline earth metal cations on the Ti4O7 surface. A seawater splitting device with an integrated commercial silicon photovoltaic cell delivers an impressive active chlorine production rate of 3.15 mg min-1 for effective simulated ballast water disinfection. This work suggests the possibility to substantially improve the sustainability of the chlor-alkali process without compromising the synthetic performance for the mass production of disinfectants. This work shows a delicate titanium suboxide-based anode design for electrolysis of seawater, delivering selective production of active chlorine for on-site disinfection.
作者机构：
[Liu, Lijuan; Zhang, Lizhi; Gong, JM; Meng, Mingxia; Gong, Jingming; Yao, Qingfeng; Cai, Zheng; Sun, Hongwei; Jiang, Fang] Cent China Normal Univ, Int Joint Res Ctr Intelligent Biosensing Technol &, Key Lab Pesticide & Chem Biol, Coll Chem,Minist Educ, Wuhan 430079, Peoples R China.
通讯机构：
[Gong, JM ] C;Cent China Normal Univ, Int Joint Res Ctr Intelligent Biosensing Technol &, Key Lab Pesticide & Chem Biol, Coll Chem,Minist Educ, Wuhan 430079, Peoples R China.
摘要：
As emerging contaminants in the environment, antibiotic resistance genes (ARGs) have aroused a global health crisis and posed a serious threat to ecological safety and human health. Thus, efficient and accurate onsite detection of ARGs is crucial for environmental surveillance. Here, we presented a colorimetric-photoelectrochemical (PEC) dual-mode bioassay for simultaneous detection of multiple ARGs by smartly incorporating rolling circle amplification (RCA) into a stimuli-responsive DNA nanoassembly, using the tetracycline resistance genes tetA and tetC as models. The tailored DNA nanoassembly containing RCA amplicons hybridized with specific signal probes: CuO nanoflowers-anchored signal DNA1 and HgO nanoparticles-anchored signal DNA2, respectively. Upon exposure to an acidic stimulus, numerous Cu(2+) and Hg(2+) were released, serving as the reporting agent of colorimetric/PEC dual-mode assay. The released Cu(2+) and Hg(2+) induced localized surface plasmon resonance shifts in Au nanorods and triangular Ag nanoplates through an etching process, respectively, enabling visual analysis of ARGs with distinguishing color changes. Meanwhile, numerous Cu(2+) and Hg(2+) triggered the amplified PEC variations via reacting with the photoactive layers of CuS/CdS and ZnS, respectively. Thus, a rapid and ultrasensitive colorimetric/PEC dual-mode detection of multiple ARGs was achieved with the detection limit down to 17.2 aM. Furthermore, such dual-mode bioassay could discriminate single-base mismatch and successfully determine ARGs in E. coli plasmids and sludge samples, holding great promise for point-of-care genetic diagnostics.
作者机构：
[Ling, Cancan; Zhang, Lizhi; Zhan, Guangming] School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China;[Ling, Cancan; Zhan, Guangming] Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental & Applied Chemistry, Central China Normal University, Wuhan 430079, China;[Liang, Chuan; Liu, Xiufan; Sun, Hongwei; Zhao, Jincai; Zhou, Bing; Li, Yaling; Li, Meiqi] Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental & Applied Chemistry, Central China Normal University, Wuhan 430079, China;[Li, Hao] School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China. Electronic address: hao_li@sjtu.edu.cn;[Zhang, Lizhi] Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental & Applied Chemistry, Central China Normal University, Wuhan 430079, China. Electronic address: zhanglizhi@sjtu.edu.cn
通讯机构：
[Hao Li; Lizhi Zhang] S;School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China<&wdkj&>Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental & Applied Chemistry, Central China Normal University, Wuhan 430079, China<&wdkj&>School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
摘要：
Water molecules are actively involved in many catalytic oxidation processes, which require the construction of highly active sites for their activation to accelerate the reaction rate, especially over non-noble metal catalysts. Herein, K species is embeded into the natural 2*2 channel of alpha-MnO2 by a hydrothermal coupled molten salt method, which would make these K species behave in an electron-rich state and provide more electrons for the activation of water molecules. Compared with surface K modification (namely, the electron-deficient K species), channel K confinement can lower the activation energy barrier of H2O dissociation on alpha-MnO2 to generate hydroxyl species with more nucleophilic oxygen atoms, contributing to the superior HCHO catalytic oxidation activity with a fourfold enhancement. The internal relationship among the confined channel, K species, and catalytic performance is systematically elucidated at the molecular level. This work offers a new ion confinement method and opens up new avenues to construct electron-rich metal sites with channel structures for the activation of water molecules.
关键词：
ammonia recovery;atomic hydrogen;electrocatalytic nitrate reduction;fluorine modification;neutral media
摘要：
Electrocatalytic nitrate reduction to ammonia (NITRR) offers an attractive solution for alleviating environmental concerns, yet in neutral media, it is challenging as a result of the reliance on the atomic hydrogen (H*) supply by breaking the stubborn HO-H bond (similar to 492 kJ/mol) of H2O. Herein, we demonstrate that fluorine modification on a Cu electrode (F-NFs/CF) favors the formation of an O-H center dot center dot center dot F hydrogen bond at the Cu-H2O interface, remarkably stretching the O-H bond of H2O from 0.98 to 1.01 & Aring; and lowering the energy barrier of water dissociation into H* from 0.64 to 0.35 eV at neutral pH. As a benefit from these advantages, F-NFs/CF could rapidly reduce NO3- to NH3 with a rate constant of 0.055 min(-1) and a NH3 selectivity of similar to 100%, far higher than those (0.004 min(-1) and 9.2%) of the Cu counterpart. More importantly, we constructed a flow-through coupled device consisting of a NITRR electrolyzer and a NH3 recovery unit, realizing 98.1% of total nitrogen removal with 99.3% of NH3 recovery and reducing the denitrification cost to $5.1/kg of N. This study offers an effective strategy to manipulate the generation of H* from water dissociation for efficient NO3--to-NH3 conversion and sheds light on the importance of surface modification on a Cu electrode toward electrochemical reactions.
期刊：
Journal of Hazardous Materials,2024年465:133009 ISSN：0304-3894
通讯作者：
Jia, FL
作者机构：
[Zhang, Lizhi; Jia, Falong; Guo, Furong; Li, Donglei; Zhang, Yuhang; She, Liang; Ai, Zhihui; Liu, Xiao] Cent China Normal Univ, Coll Chem, Wuhan 430079, Peoples R China.
通讯机构：
[Jia, FL ] C;Cent China Normal Univ, Coll Chem, Wuhan 430079, Peoples R China.
关键词：
Cu(II)-EDTA;Decomplexation;Ferrous formate shell;Oxidative degradation;Zero-valent iron
摘要：
Heavy metal complexes in industrial wastewater are challenging to be removed by conventional methods arising from their stable chelating structure. In this study, zero-valent iron (ZVI) was ball-milled with tiny formic acid (FA), and the as-prepared sample (FA-ZVI(bm)) was attempted to eliminate a model heavy metal complex of Cu(II)-ethylenediaminetetraacetic acid (Cu(II)-EDTA). The addition of FA to ball-milling could dramatically enhance the performance of ball-milled ZVI (ZVI(bm)) towards Cu(II)-EDTA removal and increase the removal rate constant by 80 times. This conspicuous improvement of Cu(II)-EDTA elimination was attributed to the ferrous formate (Fe(HCOO)(2)) shell formed on the surface of FA-ZVI(bm). Results revealed that the Fe(HCOO)(2) shell facilitated the activation of O(2) to reactive oxygen species (ROS) and the leaching of Fe(3+). Cu(II)-EDTA was decomplexed through both oxidative destruction and Fe(3+) replacement, and the released Cu(2+) was reduced by FA-ZVI(bm) and immobilized synchronously. Meanwhile, the ligands underwent oxidative degradation by ROS, thus avoiding the re-chelation ecological risk. Impressively, FA-ZVI(bm) could achieve cyclic treatment of actual copper complex wastewater and possessed promising advantage in treatment cost. This study would offer a promising approach for eliminating Cu(II)-EDTA through EDTA ligands degradation and synchronous Cu(II) removal, moreover to shed light on the decomplexation mechanism.
摘要：
Trichloroethylene (TCE) with trace concentrations is often detected in soils and groundwater, posing potential damages to public health. The elimination of TCE can be achieved through reductive dechlorination using zero-valent iron (ZVI). However, ZVI usually suffers from the presence of passive iron (hydro)oxides layer and low electron transfer rate, thus leading to the unsatisfactory reactivity. Herein, we fabricated oxalated ZVI (Ox-ZVI(bm)) by mechanical ball-milling of micro-scale ZVI and H2C2O4 center dot 2H(2)O to modify the ZVI surface composition. To be specific, the modification of the iron oxide shell by oxalic acid facilitated the generation of unsaturated coordination Fe(II), enhancing TCE adsorption. Furthermore, the formed FeC2O4 on the iron oxide shell improved electron transfer efficiency, contributing to the enhanced TCE reductive dechlorination. Impressively, the rate of TCE degradation by Ox-ZVI(bm) was 10-fold higher than that of ZVI(bm) without oxalate modification. Moreover, Ox-ZVI(bm) samples were filled in a laboratory Permeable Reactive Barriers (PRB) column to treat actual underground wastewater containing TCE pollutants. The effluent concentration of TCE maintained steadily below 0.21 mg/L for over 10 days, complying with the National Groundwater Class IV standard (GBT 14848-2017). This marks a significant step toward practical groundwater treatment.
摘要：
Enrichment of OVs on oxide semiconductors is an effective strategy to promote their photocatalytic performances but limited by the maximum concentration allowed by lattice thermodynamics. Herein, we report that an In(I) doping strategy, realized by an UV light-induced reduction of a sluggish In(III) precursor, can promote OVs-laden BiOCl by up to 6.5 times for the visible-light sodium pentachlorophenate (PCPNa) degradation. The photocatalysis mechanism study highlighted the In(I) site as an electron transfer site could reduce PCPNa directly, related to the In(I) induced more negative conduction band and faster transfer of electron. Moreover, several monocyclic aromatic organic compounds (AOC) exhibited degradation selectivity over In(I) doped OVs-laden BiOCl (BOVs-In) by an electron reduction path, PCPNa with the lowest negative charge density on the benzene ring has been degraded fastest. Differently, the doped In(I) in BOVs-In mainly triggered the multiring Rhodamine B degradation by promoting the O-center dot(2)- generation not the directly electron reduction path. The electron transfer ability, band structure, and the free energy of O-2 activation over BOVs-In were confirmed by TPV spectra, EPR spectra and DFT calculation. This study illustrates an In(I) doping strategy to couple with OVs engineering for champion photoactivity of BiOCl for AOC degradation under visible light irradiation.
摘要：
The comprehensive understanding of contaminant interfacial behavior strongly depends on the in situ characterization technique, which is still a great challenge. In this study, we constructed a device integrated with open-circuit potentialand attenuated total reflectance Fourier transform infrared (OCP-ATR-FTIR) spectroscopy to simultaneously monitor the electrochemical and infrared spectral information on the interfacial reaction for the process analysis, taking the competitive adsorption of hexavalent chromium (Cr(VI)) and oxalate on hematite nanocubes (HNC) as an example. The synchronous OCP and infrared results revealed that Cr(VI) interacted with HNC via bidentate binuclear inner-sphere coordination, accompanied by electron transfer from HNC to Cr(VI), while oxalate was adsorbed on HNC through bidentate mononuclear side-on inner-sphere coordination with electron transfer from HNC to oxalate, and also outer-sphere coordination with negative charge accumulation. When oxalate was added to HNC with preadsorbed Cr(VI), oxalate would occupy the inner-sphere adsorption sites and thus cause the detaching of preadsorbed Cr(VI) from HNC. This study provides a promising in situ characterization technique for real-time interfacial reaction monitoring and also sheds light on the competitive adsorption mechanism of oxalate and Cr(VI) on the mineral surface.
摘要：
Catalytic oxidation technology is currently considered as a feasible approach to degrade and mineralize volatile organic compounds (VOCs). However, it is still challenging to realize efficient removal of VOCs through catalytic oxidation at room temperature. In our study, a novel flow-through electrocatalytic reactor was designed, composed of porous solid-electrolyte, gas-permeable titanium sub-oxides/titanium-foam (TiSO/Ti-foam) as anode and platinum coated titanium foam (Pt/Ti-foam) as cathode. This device could oxidize nearly 100% of benzene (10 ppm) to carbon dioxide at a current density of 1.2 mA/cm2 under room temperature. More importantly, the device maintained excellent stability over 1000 h. Mechanism of benzene mineralization was discussed. Hydroxyl radicals generated on the TiSO/Ti-foam anode played a crucial role in the oxidation of benzene. This study provides a promising prototype of the electrochemical air purifier, and may find its application in domestic and industrial air pollution control.
通讯机构：
[Hongwei Sun; Zhihui Ai] K;Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental Chemistry, Central China Normal University, Wuhan 430079, PR China
关键词：
Heterogeneous fenton reaction;Oxalic acid;Proton transfer;Thiamphenicol;Zero-valent iron
摘要：
Heterogeneous Fenton reactions of zero-valent iron (ZVI) requires the sufficient release of Fe(II) to catalyze the H(2)O(2) decomposition. However, the rate-limiting step of proton transfer through the passivation layer of ZVI restricted the Fe(II) release via Fe(0) core corrosion. Herein we modified the shell of ZVI with highly proton-conductive FeC(2)O(4)·2H(2)O by ball-milling (OA-ZVI(bm)), and demonstrated its high heterogeneous Fenton performance of thiamphenicol (TAP) removal, with 500 times enhancement of the rate constant. More importantly, the OA-ZVI(bm)/H(2)O(2) showed little attenuation of the Fenton activity during 13 successive cycles, and was applicable across a wide pH range of 3.5-9.5. Interestingly, the OA-ZVI(bm)/H(2)O(2) reaction showed pH self-adapting ability, which initially reduced and then sustained the solution pH in the range of 3.5-5.2. The abundant intrinsic surface Fe(II) of OA-ZVI(bm) (45.54% vs. 27.52% in ZVI(bm), according to Fe 2p XPS profiles) was oxidized by H(2)O(2) and hydrolyzed to generate protons, and the FeC(2)O(4)·2H(2)O shell favored the fast transfer of protons to inner Fe(0), therefore, the consumption-regeneration cycle of protons were accelerated to drove the production of Fe(II) for Fenton reactions, demonstrated by the more prominent H(2) evolution and nearly 100% H(2)O(2) decomposition by OA-ZVI(bm). Furthermore, the FeC(2)O(4)·2H(2)O shell was stable and slightly decreased from 1.9% to 1.7% after the Fenton reaction. This study clarified the significance of proton transfer on the reactivity of ZVI, and provided an efficient strategy to achieve the highly efficient and robust heterogeneous Fenton reaction of ZVI for pollution control.
摘要：
Oxygen vacancies (O(V)), as the sites of molecular oxygen adsorption and activation, play an important role in the catalytic combustion process of volatile organic compounds (VOCs). Revealing the relationship between O(V) concentration and molecular oxygen activation behavior is of significance to construct the efficient catalysts. Herein, α-MnO(2) with different O(V) concentrations was prepared to investigate the molecular oxygen activation for C(3)H(8) combustion. It is disclosed that the enhanced O(V) concentration in α-MnO(2) induced the reconfiguration of surface metal atoms, resulting in the transformation of oxygen activation configuration from end-on mode to side-on mode. Oxygen molecules in side-on mode possessed more localized electron density and weaker coordination bond strength with surrounding Mn atoms, which were more favorable to adsorb C(3)H(8) molecules and activate C-H bond for the improved combustion performance. This work provides a new understanding to reveal that the increased O(V) concentration contributes to more efficient VOCs combustion.
通讯机构：
[Gong, JM ] C;Cent China Normal Univ, Inst Environm & Appl Chem, Coll Chem, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Peoples R China.
关键词：
Ammonia nitrogen;6-Trichlorophenol;Peroxymonosulfate;Dechlorination;Active chlorine species
摘要：
Halogenated phenol and ammonia nitrogen (NH4+-N) are typical composite pollutions in wastewater. It is still unclear how the transformation of halogenated phenol affects the fate of co-existing NH4+-N. In this study, the removal performance of the NH4+-N containing the co-existed halogenated organic, using 2, 4, 6-trichlorophenol (TCP) as the model pollutant was firstly investigated in the waste lithium-ion batteries (LIBs) material-derived catalysts activating peroxymonosulfate system (LIBs/PMS). The rapid degradation of TCP and the selective transformation of NH4+-N to N2 were simultaneously achieved. TCP could be degraded rapidly (within 2 min) whether with or without NH4+-N. Interestingly, the NH4+-N removal was initiated by the co-present TCP, strongly dependent on TCP dechlorination. And NH4+-N removal displayed a thermally accelerated process in the temperature range of 25 to 60 degrees C. With the co-present TCP (60 mg/L), 93.7% of NH4+-N could be removed at 50 degrees C. Based on the capture and the electron spin resonance (ESR) experiments, the generated reactive oxygen species (& BULL;OH, SO4 & BULL; and 1O2) participated in the TCP dechlorination, particularly 1O2 with dominant roles, whereas ClO & BULL; played an important role on NH4+-N removal. Theoretical calculations were used not only to predict the possible reactive site of TCP, but also evaluate the difficulty of reaction between NH4+-N and different active species. Moreover, NH4+-N could be removed 80% in outdoor simulated experiment (in Wuhan) and 100% for chlorobenzene and nitrogen-containing wastewater. This study unveiled the influence of the co-existed halogenated phenol toward the fate of NH4+-N in LIBs/PMS system and enriched the treatment of NH4+-N wastewater strategies.
通讯机构：
[Tingjuan Gao; Lizhi Zhang] K;Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, College of Chemistry, Institute of Environmental Chemistry, Central China Normal University, Wuhan 430079, China<&wdkj&>Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, College of Chemistry, Institute of Environmental Chemistry, Central China Normal University, Wuhan 430079, China<&wdkj&>School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
关键词：
In-situ remediation dynamics;Petroleum contaminants;Raman spectroscopy and microscopy;Soil and groundwater
摘要：
The mechanistic study of soil and groundwater remediation in petroleum contaminated lands significantly demands rapid qualitative and quantitative identification of petroleum substances. However, most traditional detection methods cannot provide the on-site or in-situ information of petroleum compositions and contents simultaneously even with multi-spot sampling and complex sample preparation. In this work, we developed a strategy for the on-site detection of petroleum compositions and in-situ monitoring of petroleum contents in soil and groundwater using dual-excitation Raman spectroscopy and microscopy. The detection time was 0.5h for the Extraction-Raman spectroscopy method and one minute for the Fiber-Raman spectroscopy method. The limit of detection was 94ppm for the soil samples and 0.46ppm for the groundwater samples. Meanwhile, the petroleum changes at the soil-groundwater interface were successfully observed by Raman microscopy during the in-situ chemical oxidation remediation processes. The results revealed that hydrogen peroxide oxidation released petroleum from the interior to the surface of soil particles and then to groundwater during the remediation process, while persulfate oxidation only degraded petroleum on the soil surface and in groundwater. This Raman spectroscopic and microscopic method can shed light on the petroleum degradation mechanism in contaminated lands, and facilitate the selection of suitable soil and groundwater remediation plans.
摘要：
Two-dimensional (2D) layered photocatalysts with highly ordered out-of-plane symmetry usually display robust excitonic effects, thus being ineffective in driving catalytic reactions that necessitate unchained charge carriers. Herein, taking 2D BiOBr as a prototype model, we implement a superficial asymmetric [Br-Bi-O-Bi] stacking in the out-of-plane direction by selectively stripping off the top-layer Br of BiOBr. This local asymmetry disrupts the diagnostic confinement configuration of BiOBr to urge energetic exciton dissociation into charge carriers and further contributes to the emergence of a surface dipole field that powers the subsequent separation of transient electron-hole pairs. Distinct from the symmetric BiOBr, which activates O(2) into (1)O(2) via an exciton-mediated energy transfer, surface asymmetric BiOBr favors selective O(2) activation into ·O(2)(-) for a broad range of amine-to-imine conversions. Our work here not only presents a paradigm for asymmetric photocatalyst design but also expands the toolkit available for regulating exciton behaviors in semiconductor photocatalytic systems.
作者机构：
[Zheng, Jiamin; Zhang, Lizhi; Guo, Furong; Liu, Yi; Xie, Fei; Wang, Fanyu; Lan, Jintong; Liu, Xiao] Cent China Normal Univ, Coll Chem, Engn Res Ctr Photoenergy Utilizat Pollut Control &, Minist Educ, Wuhan 430079, Peoples R China.;[Zhang, Lizhi] Shanghai Jiao Tong Univ, Sch Environm Sci & Engn, Shanghai 200240, Peoples R China.;[Sun, Yifei] Beihang Univ, Sch Energy & Power Engn, Beijing 100191, Peoples R China.
通讯机构：
[Sun, YF ] B;[Liu, X ] C;Cent China Normal Univ, Coll Chem, Engn Res Ctr Photoenergy Utilizat Pollut Control &, Minist Educ, Wuhan 430079, Peoples R China.;Beihang Univ, Sch Energy & Power Engn, Beijing 100191, Peoples R China.
摘要：
The degradation of chlorine-containingvolatile organiccompounds(Cl-VOCs) utilizing catalytic combustion technology is subjectto the paradox of toxic byproduct formation and catalyst chlorinepoisoning. Herein, a CaO-assisted strategy is proposed to resolvethe awkward stuff for improving the catalytic combustion performanceof chlorobenzene on SmMn2O5. The CaO-collaboratedSmMn(2)O(5) exhibits a significant decrease in T (90) by 142 and 125 & DEG;C compared with unmodifiedand inert SiO2-composited SmMn2O5, respectively. The integrated characterization results confirm thatCaO collaboration causes electron transfer from CaO to SmMn2O5, resulting in a reduction of the orbital overlap betweenMn and O atoms to activate lattice oxygen (O-latt). Theactivated O-latt enables chlorobenzene to combust completelyat a lower temperature of 275 & DEG;C at which toxic byproducts arenot generated. Furthermore, the switching of the dechlorination sitefrom SmMn2O5 to CaO avoids chlorine poisoningof active sites on SmMn2O5 and thus endows CaO-collaboratedSmMn(2)O(5) with prominent stability.
摘要：
Mineral dust serves as a significant source of sulfate aerosols by mediating heterogeneous sulfur dioxide (SO(2)) oxidation in the atmosphere. Given that a considerable proportion of small organic acids are deposited onto mineral dust via long-range transportation, understanding their impact on atmospheric SO(2) transformation and sulfate formation is of great importance. This study investigates the effect of oxalate on heterogeneous SO(2) uptake and oxidation phenomenon by in situ FTIR, theoretical calculation, and continuous stream experiments, exploiting hematite (Fe(2)O(3)) as an environmental indicator. The results highlight the critical role of naturally deposited oxalate in mononuclear monodentate coordinating surface Fe atoms of Fe(2)O(3) that enhances the activation of O(2) for oxidizing SO(2) into sulfate. Meanwhile, oxalate increases the hygroscopicity of Fe(2)O(3), facilitating H(2)O dissociation into reactive hydroxyl groups and further augmenting the SO(2) uptake capacity of Fe(2)O(3). More importantly, other conventional iron minerals, such as goethite and magnetite, as well as authentic iron-containing mineral dust, exhibit similar oxalate-promoted sulfate accumulation behaviors. Our findings suggest that oxalate-assisted SO(2) oxidation on iron minerals is one of the important contributors to secondary sulfate aerosols, especially during the nighttime with high relative humidity.
通讯机构：
[Yancai Yao] S;School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
关键词：
Cu(II)-EDTA;Heavy metal complexes;Nano zero-valent iron;Decomplexation;Cu capture;Wastewater
摘要：
Heavy metal complexes widely exist in the industrial wastewater, imposing significant threat to public health. Conventional treatment of heavy metal complexes usually requires two-step procedures, including the advanced oxidation process for decomplexation and the subsequent precipitation to remove the released metal ions. Herein, we developed a one-stop technique for simultaneous Cu(II)-EDTA decomplexation and copper capture using nano zero-valent iron (nZVI). The dissolved Fe3+ from nZVI corrosion could rapidly complex with EDTA to destroy the Cu(II)-EDTA, while center dot O-2(-) and center dot OH generated via the reaction of nZVI and molecular oxygen, would degrade the EDTA ligand. The liberated Cu2+ were subsequently reduced to metallic Cu or adsorbed by the iron hydroxides. Impressively, 99 % of Cu(II)-EDTA was removed within 10 min with the rate constant up to 0.49 min(-1) and 70-90 % of Cu captured by nZVI. More importantly, this nZVI based one-stop technique was effective in an extremely broad pH range of 1-12 and could also realize the one-stop removal of Cu complexes from actual wastewater, producing effluent that stably meets the discharge standard of electroplating wastewater. This study provides a facile method to simultaneously destruct Cu(II)-EDTA and capture Cu, and also sheds light on the decomplexation mechanism of heavy metal wastewater.
