Fe~(3+)及Ce~(3+)掺杂对TiO_2纳米粒子性能的影响

以溶胶-凝胶法制备纯的和分别掺杂Fe3+、Ce3+的TiO2纳米粒子,以橙黄IV的光催化氧化评价纳米粒子的紫外光与可见光活性,利用TG-DSC、XRD、BET及UV-Vis吸收光谱考察掺杂对TiO2的相变、粒径、比表面积及光吸收性能的影响,在归一化条件下探讨Fe3+及Ce3+掺杂对TiO2活性和表面性质产生影响的机制。结果表明:Fe3+及Ce3+的最佳掺杂量分别为0.2%和0.04%;Ce3+抑制TiO2由锐钛矿向金红石转变以及改善TiO2高温组织稳定性的能力均明显大于Fe3+;Fe3+和Ce3+掺杂均能提高TiO2的紫外光活性并扩展TiO2的光响应范围,但光生电子与空穴复合以及光腐蚀使它们对TiO2可见光活性的提高并不显著。Fe3+和Ce3+的半径及其相应氧化物的性质决定了两者对TiO2性能的不同影响。     

Zn2+及Fe3+对嗜淀粉乳杆菌开放式发酵产乳酸的影响

研究了在餐厨垃圾中接种嗜淀粉乳杆菌进行开放式乳酸发酵(即发酵原料不灭菌)的可行性,探讨了添加Fe3+、Zn2+的发酵体系中相关酶活与代谢产物的关系.结果表明,开放式发酵体系的乳酸产量高于非开放式发酵体系.加Fe3+体系的乳酸脱氢酶活性较高,导致乳酸产量增加(最高达29.5g/L),比未添加微量元素的对照体系增加了24.2%;而加Zn2+体系的乙醇脱氢酶(ADH)活性较高,导致副产物乙醇产量的增加,从而使乳酸产量低于对照体系;添加不同微量元素时嗜淀粉乳杆菌对底物中淀粉的利用率由高到低的顺序为:加Fe3+体系(65.7%) > 对照体系 (38.5%)>Zn2+体系(28.1%).此外,在嗜淀粉乳酸菌的发酵体系中,蔗糖和麦芽糖比乳糖容易降解成葡萄糖,果糖,最终被乳酸菌利用.     

Effect of Mn2+ on the phosphorus removal and bioflocculation under anoxic condition

Manganese ion (Mn²⁺) generated from metallurgical, steel making and chemical industries enters sewage treatment plants and affects the sludge activity and flocculation. The effect of Mn²⁺ on the removal of chemical oxygen demand (COD) and total phosphorus (TP) and sludge activity were investigated in anoxic zone of an anaerobic/anoxic/oxic (A²O) process. The compositions and structures of extracellular polymeric substances (EPS) were characterized using three-dimensional excitation emission matrix fluorescence spectroscopy (3D-EEM), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) to reveal the relationship among Mn²⁺, EPS and sludge flocculation.The results showed that low concentration of Mn²⁺ (<5 mg/L) improved removal efficiencies of COD and TP and increased the activity of alkaline phosphatase, acid phosphatase and dehydrogenase. Meanwhile, the addition of Mn²⁺ increased total EPS, sludge contact angle, Zeta potential and sludge particle size, and thus enhanced sludge flocculation. However, high concentration of Mn²⁺ (>10 mg/L) hindered microbial flocculation and reduced removal efficiencies of the pollutants. When Mn²⁺was 5 mg/L, removal efficiencies of COD and TP reached 65% and 90%, respectively. Sludge flocculation was the best and SVI was 70.56 mL/g. The changes of Mn²⁺ concentration caused deviation of groups’ compositions in LB-EPS and TB-EPS, where the main components were always protein (PN) and polysaccharide (PS). The addition of Mn²⁺ resulted in the degradation of humic acids. However, it did not give rise to significant morphology changes of EPS.     

Efficient removal of Cr(VI) by a 3D Z-scheme TiO2-ZnxCd1-xS graphene aerogel via synergy of adsorption and photocatalysis under visible light

Efficient and robust photocatalysts for environmental pollutants removal with outstanding stability have great significance. Herein, we report a kind of three dimensional (3D) photocatalyst presented as Z-scheme heterojunction, which combining TiO 2 and Zn x Cd 1- x S with graphene aerogel to contrast TiO 2 -Zn x Cd 1- x S graphene aerogel (TSGA, x = 0.5) through a moderate hydrothermal process. The as-prepared Z-scheme TSGA was used to remove aqueous Cr(VI) via a synergistic effect of adsorption and visible light photocatalysis. The adsorption equilibrium can be reached about 40 min, then after about 30 min irradiation under visiblelight (wavelength ( λ) > 420 nm) the removal rate of Cr(VI) almost reached 100%, which is much better than the performance of pristine TiO 2 and Zn 0.5 Cd 0.5 S, as well as TiO 2 graphene aerogel (TGA) and Zn 0.5 Cd 0.5 S graphene aerogel (SGA). The virulent Cr(VI) was reduced to Cr(III) with hypotoxicity after photocatalysis on TSGA, meanwhile the as-synthesized TSGA presented a good stability and reusability. The reduced graphene oxide (rGO) sheets between TiO 2 and Zn 0.5 Cd 0.5 S played a role as charge transfer mediator, promoting the photoinduced electrons transfer and photocatalysis ability of TSGA was enhanced significantly. Hence,such photocatalyst exhibits a potential application on removing heavy metals with high efficiency and stability from polluted aqueous environment.     

Role of NO and SO2 in mercury oxidation over a La2O3/Fe2O3 catalyst with high thermal stability

In this study, the thermal stability of a ferric oxide catalyst for mercury oxidation was found to be considerably promoted by doping with La₂O₃. The catalysts doped with La₂O₃ maintained a higher surface area when subjected to high-temperature calcination, with lower average pore size and a narrower pore size distribution. X-ray diffraction (XRD) results revealed that La₂O₃ doping hinders the growth of catalyst particles and crystallization of the material at high temperatures. Both NO and SO₂ inhibited Hg⁰ oxidation over the La₂O₃/Fe₂O₃ catalyst. Fourier transform infrared (FTIR) spectra revealed that SO₂ reacts with O₂ over the catalysts to form several species that are inert for mercury oxidation, such as SO₄^2?, HSO₄^?, or other related species; these inert species cover the catalyst surface and consequently decrease Hg⁰ oxidation capacity. In addition, NO or SO₂ competed with Hg⁰ for active sites on the La₂O₃/Fe₂O₃ catalyst and hindered the adsorption of mercury, thereby inhibiting subsequent Hg⁰ oxidation. Hg⁰ oxidation on the La₂O₃/Fe₂O₃ catalyst mainly followed the Eley–Rideal mechanism. Moreover, the inhibition effects of NO and SO₂ were at least partially reversible, and the catalytic activity was temporarily restored after eliminating NO or SO₂.     

新型MIL-100(Fe)基MOFs材料的制备及其对Sr2+的吸附

采用水热法和溶剂热法制备了金属有机骨架材料——MIL-100(Fe)和MIL-100(Fe)-DMA.利用FTIR、XRD、SEM、XPS和N₂吸附/脱附对材料结构进行了表征.通过静态吸附实验,探究了初始Sr²⁺浓度、吸附时间、溶液pH值和不同共存阳离子对材料吸附性能的影响,研究了两种材料对Sr²⁺吸附过程的吸附动力学和吸附等温线模型.表征结果表明:两种材料基本骨架一致,吸附Sr²⁺对材料骨架影响均可忽略;虽然MIL-100(Fe)-DMA比表面积小于MIL-100(Fe),但由于晶粒尺寸小,堆积形成的介孔结构更有利于Sr²⁺的扩散.吸附实验结果表明:随着反应时间和初始Sr²⁺浓度的增加,两种材料对Sr²⁺的吸附量先迅速增大再逐渐达到平衡;随着pH值的增大,两种材料对Sr²⁺的吸附量增大,且碱性条件下吸附效果好;两种材料吸附过程均符合准二级动力学模型、颗粒内扩散模型和Langmuir吸附等温模型;采用三价铁盐作为铁源以及DMA作为有机溶剂可提高MIL-100(Fe)材料对Sr²⁺的吸附效果.     

Biofilm response and removal via the coupling of visible-light-driven photocatalysis and biodegradation in an environment of sulfamethoxazole and Cr(VI)

The widespread contamination of water systems with antibiotics and heavy metals has gained much attention. Intimately coupled visible -light-responsive photocatalysis and biodegradation (ICPB) provides a novel approach for removing such mixed pollutants. In ICPB, the photocatalysis products are biodegraded by a protected biofilm, leading to the mineralization of refractory organics. In the present study, the ICPB approach exhibited excellent photocatalytic activity and biodegradation, providing up to ∼1.27 times the degradation rate of sulfamethoxazole (SMX) and 1.16 times the Cr(VI) reduction rate of visible-light-induced photocatalysis . Three-dimensional fluorescence analysis demonstrated the synergistic ICPB effects of photocatalysis and biodegradation for removing SMX and reducing Cr(VI). In addition, the toxicity of the SMX intermediates and Cr(VI) in the ICPB process significantly decreased. The use of MoS₂/CoS₂ photocatalyst accelerated the separation of electrons and holes, with•O₂^– and h⁺ attacking SMX and e^– reducing Cr(VI), providing an effective means for enhancing the removal and mineralization of these mixed pollutants via the ICPB technique. The microbial community results demonstrate that bacteria that are conducive to pollutant removal are were enriched by the acclimation and ICPB operation processes, thus significantly improving the performance of the ICPB system.     

Efficient degradation of Rhodamine B by magnetically recoverable Fe3O4-modified ternary CoFeCu-layered double hydroxides via activating peroxymonosulfate

Environment-friendly nano-catalysts capable of activating peroxymonosulfate (PMS) have received increasing attention recently. Nevertheless, traditional nano-catalysts are generally well dispersed and difficult to be separated from reaction system, so it is particularly important to develop nano-catalysts with both good catalytic activity and excellent recycling efficiency. In this work, magnetically recoverable Fe₃O₄-modified ternary CoFeCu-layered double hydroxides (Fe₃O₄/CoFeCu-LDHs) was prepared by a simple co-precipitation method and initially applied to activate PMS for the degradation of Rhodamine B (RhB). X-ray diffraction (XRD), fourier transform infrared spectrometer (FT-IR), scanning electron microscope (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller method (BET), and vibrating sample magnetometer (VSM) were applied to characterize morphology, structure, specific surface area and magnetism. In addition, the effects of several key parameters were evaluated. The Fe₃O₄/CoFeCu-LDHs exhibited high catalytic activity, and RhB degradation efficiency could reach 100% within 20 min by adding 0.2 g/L of catalyst and 1 mmol/L of PMS into 50 mg/L of RhB solution under a wide pH condition (3.0-7.0). Notably, the Fe₃O₄/CoFeCu-LDHs showed good super-paramagnetism and excellent stability, which could be effectively and quickly recovered under magnetic condition, and the degradation efficiency after ten cycles could still maintain 98.95%. Both radicals quenching tests and electron spin resonance (ESR) identified both HO? and SO₄^?? were involved and SO₄^?? played a dominant role on the RhB degradation. Finally, the chemical states of the sample's surface elements were measured by X-ray photoelectron spectroscopy (XPS), and the possible activation mechanism in Fe₃O₄/CoFeCu-LDHs/PMS system was proposed according to comprehensive analysis.     

Enhanced photoelectrocatalytic decomplexation of Ni-EDTA and simultaneous recovery of metallic nickel via TiO2/Ni-Sb-SnO2 bifunctional photoanode and activated carbon fiber cathode

In order to enhance Ni-EDTA decomplexation and Ni recovery via photoelectrocatalytic (PEC) process, TiO₂/Ni-Sb-SnO₂ bifunctional electrode was fabricated as the photoanode and activated carbon fiber (ACF) was introduced as the cathode. At a cell voltage of 3.5 V and initial solution pH of 6.3, the TiO₂/Ni-Sb-SnO₂ bifunctional photoanode exhibited a synergetic effect on the decomplexation of Ni-EDTA with the pseudo-first-order rate constant of 0.01068 min⁻¹ with 180 min by using stainless steel (SS) cathode, which was 1.5 and 2.4 times higher than that of TiO₂ photoanode and Ni-Sb-SnO₂ anode, respectively. Moreover, both the efficiencies of Ni-EDTA decomplexation and Ni recovery were improved to 98% from 86% and 73% from 41% after replacing SS cathode with ACF cathode, respectively. Influencing factors on Ni-EDTA decomplexation and Ni recovery were investigated and the efficiencies were favored at acidic condition, higher cell voltage and lower initial Ni-EDTA concentration. Ni-EDTA was mainly decomposed via ·OH radicals which generated via the interaction of O₃, H₂O₂, and UV irradiation in the contrasted PEC system. Then, the liberated Ni²⁺ ions which liberated from Ni-EDTA decomplexation were eventually reduced to metallic Ni on the ACF cathode surface. Finally, the stability of the constructed PEC system on Ni-EDTA decomplexation and Ni recovery was exhibited.     

Environmental factors affecting degradation of perfluorooctanoic acid (PFOA) by In2O3 nanoparticles

Nanophotocatalysts have shown great potential for degrading poly-and perfluorinated substances (PFAS).In light of the fact that most of these catalysts were studied in pure water,this study was designed to elucidate effects from common environmental factors on decomposing and defluorinating perfluorooctanoic acid (PFOA) by In₂O₃ nanoparticles.Results from this work demonstrated that among the seven parameters,pH,sulfate,chloride,H₂O₂,In₂O     

Influence of drying and calcination temperatures for Ce-Cu-Al trimetallic composite catalyst on simultaneous removal H2S and PH3: Experimental and DFT studies

This work explored the influences of the drying and calcination temperatures on a Ce-Cu-Al trimetallic composite catalyst for the simultaneous removal of H₂S and PH₃. The effects of both temperatures on the structural features and activity were examined. The density functional theory method was used to calculate adsorption energies and further analyze their adsorption behavior on different slabs. Experiments revealed suitable drying and calcination temperatures to be 60 and 500°C, respectively. The capacity reached 323.8 and 288.1 mg/g. Adjusting drying temperature to 60°C is more inclined to form larger and structured grains of CuO. Rising calcinating temperature to 500°C could increase the grain size and redox capacity of CuO to promote performance. Higher temperatures would destroy the surface structure and lead to a crystal phase transformation, which was that the CuO and Al₂O₃ were gradually recombined into CuAl₂O₄ with a spinel structure. The exposed crystal planes of surficial CuO and CuAl₂O₄ were determined according to characterization results. Calculation results showed that, compared with CuO (111), H₂S and PH₃ have weaker adsorption strength on CuAl₂O₄ (100) which is not conducive to their adsorption and removal.     

The transport and retention of CQDs-doped TiO2 in packed columns and 3D printed micromodels

CQDs-doped TiO₂（C-TiO₂） has drawn increased attention in recent because of its excellent catalytic performance.Understanding the transport of C-TiO₂ in porous media is necessary for evaluating the environmental process of this new nanomaterial.Column experiments were used in this study to investigate ionic strength（IS）,dissolved organic matter（DOM）and sand grain size on the transport of C-TiO₂.The mobility of C-TiO₂ was inhibited by the incr...     

Zn2+络合促进土霉素在粘土矿物表面的吸附

土霉素(OTC)和Zn2+作为饲料添加剂大量应用于畜禽养殖中,会通过畜禽粪便施用等方式进入土壤环境.研究了它们在粘土矿物上的吸附行为及其相互影响.结果发现,阳离子交换量大的蒙脱石对OTC的吸附系数(Kd)明显高于高岭石;而电荷属性的不同,导致2种粘土的Kd随pH呈现不同的趋势.Zn2+可对OTC吸附产生影响,在4相似文献   

基于吡啶甲基萘酰亚胺的水中痕量铁检测方法研究

合成了一种新型的荧光分子探针N-(2-吡啶甲基)-1,8-萘酰亚胺(PMN),研究了其在环境水样中痕量铁离子的检测应用.结果表明,该方法选择性好,灵敏度高,操作简便,且常见金属离子不干扰测定.Fe3+浓度在1×10-7~8×10-5mol/L范围内,荧光强度与其浓度呈良好的线性关系.方法用于自来水、井水、生活污水中痕量铁的测定,回收率在95.78%~104.02 %之间.     

水葫芦对Zn2+、Cd2+和Fe3+的去除速率

通过静态水培实验和原子吸收分光光度法的测定,发现水葫芦对个别重金属离子累积去除率头两天为Zn≈Cd>Fe,以后为Fe>Zn>Cd;5天中,Cd2 在水葫芦老黄茎叶中的积累量增长了130 0倍;在混合离子培养液中,Zn2 的去除速率明显下降,而Cd2 和Fe3 变化不明显。表明水葫芦在治理含镉废水方面有良好的应用前景。     

UV/H2O2 oxidation of tri(2-chloroethyl) phosphate: Intermediate products, degradation pathway and toxicity evaluation

Tri(2-chloroethyl) phosphate(TCEP) with the initial concentration of 5 mg/L was degraded by UV/H₂O₂ oxidation process. The removal rate of TCEP in the UV/H₂O₂ system was 89.1% with the production of Cl-and PO₄^3- of 0.23 and 0.64 mg/L. The removal rate of total organic carbon of the reaction was 48.8% and the pH reached 3.3 after the reaction. The oxidative degradation process of TCEP in the UV/H₂O₂ system ...     

Effect of reduction pretreatments on PdAg/Al2O3 for HCHO and CO oxidation

PdAg/Al₂O₃ were pretreated by CO and H₂ reduction pretreatments, respectively. The reduced catalysts were tested for HCHO and CO oxidation and characterized by Brunner Emmet Teller (BET), X-ray diffraction (XRD), transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS) and oxygen temperature programmed desorption (O₂-TPD). These results indicate that the pretreatments have effect on PdAg reconstruction, PdAg particle size and active oxygen species, which are responsible for the catalytic performance. Compared with H₂ reduction method, CO reduction is more suitable for PdAg/Al₂O₃ pretreatment. PdAg/Al₂O₃-CO exhibited better catalytic performance.     

Kinetic and product studies of the reactions of NO3 with a series of unsaturated organic compounds

Rate coefficients for the reaction of NO₃ radicals with 6 unsaturated volatile organic compounds (VOCs) in a 7300 L simulation chamber at ambient temperature and pressure have been determined by the relative rate method. The resulting rate coefficients were determined for isoprene, 2-carene, 3-carene, methyl vinyl ketone (MVK), methacrolein (MACR) and crotonaldehyde (CA), as (6.6 ± 0.8) × 10^?13, (1.8 ± 0.6) × 10^?11, (8.7 ± 0.5) × 10^?12, (1.24 ± 1.04) × 10^?16, (3.3 ± 0.9) × 10^?15 and (5.7 ± 1.2) × 10^?15 cm³/(molecule?sec), respectively. The experiments indicate that NO₃ radical reactions with all the studied unsaturated VOCs proceed through addition to the olefinic bond, however, it indicates that the introduction of a carbonyl group into unsaturated VOCs can deactivate the neighboring olefinic bond towards reaction with the NO₃ radical, which is to be expected since the presence of these electron-withdrawing substituents will reduce the electron density in the π orbitals of the alkenes, and will therefore reduce the rate coefficient of these electrophilic addition reactions. In addition, we investigated the product formation from the reactions of 2-carene and 3-carene with the NO₃ radical. Qualitative identification of an epoxide (C₁₀H₁₆OH⁺), caronaldehyde (C₁₀H₁₆O₂H⁺) and nitrooxy-ketone (C₁₀H₁₆O₄NH⁺) was achieved using a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) and a reaction mechanism is proposed.     

Modeling of spatial and temporal variations of ozone-NOx-VOC sensitivity based on photochemical indicators in China

Comprehensive air quality model with extensions (CAMx)-decoupled direct method (DDM) was used to simulate ozone-NO_x-VOCs sensitivity of for May–November in 2016–2018 in China. Based on the relationship between the simulated ozone (O₃) sensitivity values and the ratio of formaldehyde (HCHO) to NO₂ (FNR) and the ratio of production rate of hydrogen peroxide (H₂O₂) to production rate of nitric acid (HNO₃) ($P_{{\mathrm{H}}_2{\mathrm{O}}_2}/P_{\text{HN}{\mathrm{O}}_3}$), the localized range of FNR and $P_{{\mathrm{H}}_2{\mathrm{O}}_2}/P_{\text{HN}{\mathrm{O}}_3}$ thresholds in different regions in China were obtained. The overall simulated FNR values are about 1.640–2.520, and $P_{{\mathrm{H}}_2{\mathrm{O}}_2}/P_{\text{HN}{\mathrm{O}}_3}$ values are about 0.540–0.830 for the transition regime. Model simulated O₃ sensitivities or region specific FNR or $P_{{\mathrm{H}}_2{\mathrm{O}}_2}/P_{\text{HN}{\mathrm{O}}_3}$ thresholds should be applied to ensure the accurate local O₃ sensitivity regimes. Using the tropospheric column FNR values from ozone monitoring instrument (OMI) satellite data as an indicator with the simulated threshold values, the spatial distributions of O₃ formation regimes in China are determined. The O₃ sensitivity regimes from eastern to central China are gradually from VOC-limited, transition to NO_x-limited spatially, and moving toward to transition or NO_x-limited regime from 2005 to 2019 temporally.     

Relationships between chemical elements of PM2.5 and O3 in Shanghai atmosphere based on the 1-year monitoring observation

Mass level of fine particles(PM_2.5) in main cities in China has decreased significantly in recent years due to implementation of Chinese Clean Air Action Plan since 2013,however,03 pollution is getting worse than before,especially in megacities such as in Shanghai.In this work,O₃ and PM_2.5 were continuously monitored from May 27,2018 to March 31,2019.Our data showed that the annual average concentration of PM_2.5 and O₃(O₃-8 hr,max...