负载型γ-Al2O3三维粒子电极的制备及其对氯霉素的降解

以γ-Al₂O₃为载体,将Ti和Sn两种元素进行负载制备负载型γ-Al₂O₃粒子电极,采用X射线衍射（XRD）、扫描电镜（SEM）、X射线荧光光谱（XRF）、红外光谱（IR）对γ-Al₂O₃和负载型γ-Al₂O₃粒子电极进行表征。研究了电解时间对三维粒子电极法电催化氧化氯霉素的影响。采用初始浓度100 mg/L的CAP模拟废水,持续电解3 h后,制备的粒子电极通过三维电解对CAP去除率为72.8%,对TOC去除率低于3.7%,说明负载型γ-Al₂O₃粒子电极对氯霉素矿化作用较小。三维粒子电极对氯霉素的降解过程近似符合一级动力学方程,CAP初始浓度对去除率影响较小。粒子电极电催化氧化CAP的关键因素之一为·OH,外加叔丁醇对·OH进行清洗,相同条件下,氯霉素去除率降低至30%左右,表明氯霉素的降解是由阳极氧化和·OH间接氧化两种途径协同作用的。     

Fe(Ⅱ)活化亚硫酸盐降解卡马西平的动力学及机制研究

高级氧化技术是去除水中新型有机污染物的重要方法之一。研究Fe （Ⅱ）活化亚硫酸盐（Fe （Ⅱ）/亚硫酸盐）体系降解卡马西平（CBZ）的动力学及体系中活性氧化物种对CBZ降解的贡献。结果表明：当亚硫酸盐浓度由0.20 mmol/L增加至0.50 mmol/L时,反应20 min时Fe （Ⅱ）亚硫酸盐体系对CBZ的去除率不断增加,而进一步增加亚硫酸盐浓度时,卡马西平的去除率不再进一步增加。当反应初始pH值为3.0~7.0时,Fe （Ⅱ）/亚硫酸盐体系均可降解CBZ,在初始pH值为5.0时,此体系对CBZ的去除率最高,反应平衡时CBZ的去除率达87.3%。此外,铁盐中SO₄^2-和Cl^-对Fe （Ⅱ）/亚硫酸盐体系降解CBZ基本无影响。综合电子顺磁共振检测及淬灭剂实验的结果可知,Fe （Ⅱ）/亚硫酸盐体系中所产生的活性氧化物种包括硫酸根自由基（SO₄^-·）、羟基自由基（HO·）和过一硫酸根自由基（SO₅^-·）,它们均对卡马西平的降解起贡献作用,其中SO₄^-·和HO·起主要贡献作用。     

硅基高分散钴氧化物活化亚硫酸盐降解有机污染物的效能

近年来,基于硫酸根自由基（SO₄^·-）的高级氧化技术（SR-AOPs）迅速发展,高效稳定地产生SO₄^·-自由基的催化剂及相关机制成为新的研究重点。采用氨水改性吸附焙烧法制备非均相硅基高分散钴氧化物（CoNSi）催化剂,用于活化工业副产物亚硫酸盐（S（IV））,进而以废治污降解污染物。分别研究了不同pH值、不同CoNSi和亚硫酸钠（Na₂SO₃）投加量、不同橙黄Ⅱ（AO7）浓度以及氧气对底物降解效能的影响,分析了亚硫酸盐浓度和AO7浓度对AO7降解反应初始速率的影响。结果表明：当反应pH值为9.0,CoNSi和Na₂SO₃投加量分别为0.25 g/L和1.0 mM,AO7浓度为7 mg/L,氧气存在的条件下,AO7的降解率可达到79.4%。此外,序批实验证明了CoNSi活化亚硫酸盐的稳定性,自由基抑制实验证明了SO₄^·-自由基是降解AO7的主要活性物种。     

2014—2019年北京和南京地区PM2.5和臭氧质量浓度相关性研究

自2014年以来,中国细颗粒物（PM_2.5）浓度大幅度下降,但臭氧（O₃）浓度逐年缓慢上升,厘清PM_2.5和O₃（P-O）相关性尤为关键.在本研究中,2014—2019年北京和南京PM_2.5年均质量浓度下降幅度分别为-6.86和-6.15 μg·m^-3·a^-1;而日最大8小时平均O₃质量浓度（MDA8 O₃）年均增长幅度为1.50和1.75 μg·m^-3·a^-1.研究期间,北京地区MDA8 O₃质量浓度小于100 μg·m^-3,P-O呈负相关;而当质量浓度大于100 μg·m^-3时,P-O为正相关.通过Pearson相关系数研究P-O两者相关性.在两个城市每月相关性分析中,在每日时间尺度5—9月为强的正相关;而小时时间尺度11月至次年2月趋于负相关.在北京,P-O每月和季节相关性变化大于南京.在日变化中,夏季在16时为强的正相关,春秋两季在13—17时为弱的正相关,而在春、秋和冬季8时,却为强的负相关.     

膜蒸馏用管式疏水陶瓷膜制备与表征

针对膜蒸馏用管式疏水陶瓷膜盐截留率较低的问题进行了实验研究。首先,用自制的氧化物AB与去离子水按一定比例混合,对陶瓷膜管支撑体两端进行均匀涂抹,然后在高温下烧结,对两端进行玻璃化密封,解决了其端面短路流问题。然后,在室温条件下,采用溶液体积为50 mL、浓度为0.01 mol/L的 1H,1H,2H,2H-全氟癸基三乙基氧硅烷（C₁₆H₁₉F₁₇O₃Si,简称FAS）的异丙醇溶液对玻璃化后的陶瓷膜管进行疏水改性,制备疏水性FAS-ZrO₂-Al₂O₃复合膜。通过增加接枝改性次数（每次疏水改性时间为3 d）,以改性后的疏水陶瓷膜管纯水穿透压力为指标,考察膜管的疏水性能。然后对每根膜管进行AGMD实验,疏水膜管内表面的SEM分析、IR分析和水接触角测试。结果表明：在NaCl热溶液温度75 ℃、流量25 L/h、质量浓度为2%,冷却水温度15 ℃以及流量为50 L/h的实验条件下,综合性能最好的是3^#膜管,膜蒸馏通量达到4.29 kg/（m²·h）,截留率达到99.83%;使用FAS改性陶瓷膜管内表面的ZrO₂膜层,氟硅烷中的两个疏水基团C_xF_2x+1和Si-CH₂CH₂·C_xF_2x+1都成功地接枝聚合到了陶瓷膜表面形成很好的疏水表面,水接触角达到142°。因此,经过FAS疏水改性后的FAS-ZrO₂-Al₂O₃复合膜符合膜蒸馏用膜要求,可以通过AGMD淡化高盐度苦咸水,得到高纯度的水。     

平面应变条件下冻融循环对黄土力学性质的影响

以原状黄土为研究对象,通过平面应变试验,研究冻融循环对原状黄土物理力学性质的影响。结果表明：随着冻融循环周期的增大,土样表面损伤越严重;在同含水率、同固结围压的条件下,原状黄土的偏应力-轴向应变（σ₁-σ₃）-ε₁曲线随着冻融循环次数的增大而逐渐减小,并且冻融循环对原状黄土（σ₁-σ₃）-ε₁曲线的劣化作用随着含水率的增大而增大,随着固结围压的增大而减小;根据摩尔-库伦强度准则,得出粘聚力和内摩擦角均随着含水率的增大呈线性减小,黏聚力随着冻融循环周期的增大呈指数减小,内摩擦角随着冻融循环周期的增大而减小,且在3°范围内变化。基于试验数据的合理性,拟合出原状黄土随冻融循环周期的劣化模型,该模型经试验验证可较好地描述原状黄土随冻融循环周期的劣化规律。     

低温等离子体处理甲酰胺溶液过程中活性粒子传质的数值模拟

采用一维漂移-扩散流体模型,对活性粒子在甲酰胺溶液中的传质进行了数值模拟。分析了等离子体处理甲酰胺溶液中5种主要活性氧粒子(OH、OH₂、O₃、O₂^- 、H₂O₂)的浓度和渗透深度。结果表明:在甲酰胺溶液中,O₃和OH的渗透深度可以达到13~14 μm,高于水中的7~9 μm;O₂^-渗透深度为580 μm,约为其在水溶液中的50%;甲酰胺浓度在10^-5~10^-3 mol/L内,对活性氧粒子传质过程的影响较明显;溶液中O₂对活性氧离子多样性有积极作用。这些现象表明,可以通过控制实际环境改变活性氧粒子的渗透深度。     

金华地区夏秋大气中过氧乙酰硝酸酯的污染特征

过氧乙酰硝酸酯（PAN）是由VOCs和NO_x的光化学反应生成的一种典型二次污染物,比O₃更适合作为光化学污染的指示剂.2019年6—10月对浙江中部盆地金华市大气中PAN进行了在线监测,并对影响其体积分数变化的因素进行了分析,同时还分析了一次典型的光化学污染过程.结果表明,观测期间PAN的平均体积分数为0.656×10^-9,最高体积分数为4.348×10^-9,日均体积分数水平在0.130×10^-9~2.203×10^-9之间.PAN日变化特征显著,9月为明显的双峰变化,其他月份均为单峰.受气象条件的影响,夏季的污染程度显著低于秋季.9月27—30日典型污染时段内,PAN的小时均值是整个观测期均值的2.8倍,污染以本地积累为主.前体物浓度水平差异与去除机制的不同是影响PAN和O₃相关性的重要因素,此外NO/NO₂的比值是影响PAN生成速率的重要因素,PAN的峰值基本出现在NO/NO₂比值较低的时段.在生成PAN的VOCs物种中,丙烷、乙烷和间/对二甲苯所占比例较大.     

基于双金属MOFs 制备Co3O4/In2O3 复合物及其气敏性能的研究

以硝酸铟(In(NO₃)₃·xH₂O)、对苯二甲酸(H₂BDC)、六水合硝酸钴(Co(NO₃)· 6H₂O) 为原料, 首先采用一锅油浴法合成了含有Co²⁺ 的铟基金属有机框架材料(MOFs) Co²⁺/CPP-3(In) 材料, 然后在450 ℃ 下焙烧制备Co₃O₄/In₂O₃ 复合物气敏材料, 将Co₃O₄/In₂O₃ 复合物的粉体制作成传感器, 并对其气敏性能进行研究。利用扫描电子显微镜和X 射线衍射仪(XRD) 对双金属MOFs Co²⁺/CPP-3(In) 材料和Co₃O₄/In₂O₃ 复合物进行表征, 采用静态配气法测试其气敏性能。结果表明, Co₃O₄/In₂O₃(n_Co : n_In = 0.4 : 1) 样品的形貌保留了其MOFs 前驱体的棒状结构, 棱柱形框架更为突出, 表面呈凹陷状, 棒体中间粗两边细, 六角截面和棒体均布满了孔洞。结合EDX 和XRD 表征结果, Co²⁺/CPP-3(In) MOFs 前驱体完全转化成Co₃O₄/In₂O₃ 复合物; Co₃O₄/In₂O₃(n_Co : n_In = 0.4 : 1) 复合物在 70 ℃ 下对5×10^-6 H₂S 的气敏性能最优, 响应值达到153, 是同条件下纯备In₂O₃对H₂S 响应值的5 倍, 并且有较好的重复性、选择性和稳定性。     

不同类型稻田亚硝酸型CH4厌氧氧化潜力的比较研究

甲烷(CH₄)厌氧氧化是稻田土壤中消减温室气体排放的重要过程.本试验选择内陆性南京稻田和滨海性上海崇明岛围垦稻田,比较研究稻田耕层(0~10 cm)和深层(50~60 cm)土壤中亚硝酸盐型CH₄厌氧氧化(n-DAMO)潜力的差异及其微生物驱动机制.结果表明,南京稻田耕层土壤的n-DAMO速率为3.51 nmol·g^-1·d^-1(以¹³CO₂计),显著高于围垦稻田耕层土壤(1.43 nmol·g^-1·d^-1).两种类型稻田耕层土壤的n-DAMO速率均显著高于深层土壤.南京稻田和围垦稻田M.oxyfera-like细菌的16S rRNA基因拷贝数分别为(2.31~4.82)×10⁷和(0.89~2.12)×10⁷ copies·g^-1,与亚硝酸盐型CH₄厌氧氧化速率显著正相关.相关性分析发现,土壤有机碳、总氮、无机态氮是稻田n-DAMO速率分异的重要原因.综上所述,内陆性稻田土壤n-DAMO氧化潜力较高,其主要由较高的土壤本底碳、氮水平和功能微生物丰度所致.     

Kinetics of Fe3O4 formation by air oxidation

The kinetics of Fe₃O₄ formation by air oxidation of slightly acidic suspension of Fe(OH)₂ was studied. The effects of initial concentration of Fe(II), temperature, partial pressure of oxygen, air flow rate and stirring rate on the oxidation rate were investigated. The results show that Fe₃O₄ formation is composed of two-step reaction, the first step is the formation of Fe(OH) ₂ ⁺ by oxidation of Fe(OH)⁺ complex ions, the second step is the formation of magnetite by dehydration and deprotonation of Fe(OH)⁺ and Fe(OH) ₂ ⁺ . The oxidation reaction is zero-order with respect to the concentration of Fe(II) and around 0.5-order with respect to partial pressure of oxygen, and oxygen transfer process is rate-limiting step of oxidation reaction with apparent activation energy of 2.74 kJ · mol⁻¹.     

The mechanism of ground granulated blastfurnace slag preventing alkali aggregate reaction

Three different methods were applied to study the alkali content of gelpores in cement. In the closed system, the concentration of K⁺, Na⁺ and OH⁻ have not reduced with the increase of age. In the open system, the diffusion and transferring of K⁺ and Na⁺ towards free space leads to the decrease of total alkali content. In the micro-analysis system, the contents of K⁺ and Na⁺ in the first hydrated layer of ground granulated blastfurnace slag (GBFS) are very low, while the contents of calcium and magnesium are relatively high. This phenomenon shows that the mechanism of GBFS preventing alkali aggregate reaction (AAR) is: when GBFS is dissolved by alkali medium, SiO₂ and Al₂O₃ are dissolved into the cement matrix, then around GBFS particles form reaction rings rich in Ca²⁺ and Mg²⁺, and the C-S-H gel of positive charges formed in the area repulses K⁺ and Na⁺, which are forced to transfer to the mortar’s matrix, pore or mortar sample surface. The transferred K⁺ and Na⁺ form alkali gel products with other dissolved ions, then become evenly distributed in the mortar sample and react with Ca(OH)₂ in pore solutions to form (Na,K) _x−2z ·zCa·(SiO₂)_y·(OH)_x gel products; and thus changes the AAR gel products’ structure. The gel products will not expand, and so they can delay expansion destruction.     

Synthesis and characterization of arsenate antimonic acid AAAc(1 : 1)

The AAAc(1 : 1) was synthesized in water by As₂O₃ and Sb₂O₃ with molar ratio of 1 : 1. AAAc(1 : 1) was characterized by Raman, IR, TG/DTG, DSC, XPS and XRD. The results show that there are four peaks to v _s of As-OH, As-O-Sb, Sb-OH and Sb-O-Sb in Raman spectra of AAAc(1 : 1) at 100 – 1 000 cm⁻¹. The solution of AAAc(1 : 1) was also titrated with KOH solution. The titration results show that AAAc(1 : 1) is a hexabasic acid with dissociation constants of k ₁=3.62 × 10⁻², k ₂=3.05 × 10⁻³, k ₃=6.43 × 10⁻⁶, k ₄ =9.78 × 10⁻⁸, k ₅=1.32 × 10⁻¹¹, k ₆=3.87 × 10⁻¹². AAAc(1 : 1) has a good solubility and stability in water, its solid obtained by free volatilizing water from its solution under air at ambient temperature is amorphous. Chemical and thermal analysis show that the composition of AAAc(1 : 1) is As₂O₅ · Sb₂O₅ · 8H₂O in air at 25 °C. AAAc(1 : 1) has the structure of AsO(OH)₂-OH-Sb(OH)₄-O-Sb(OH)₄-OH-AsO(OH)₂ or As(OH)₃-O-Sb(OH)₄-O-Sb(OH)₄-O-As(OH)₃ (isomerism) through experimental determination and geometry optimization. Foundation item: Project(50274075) supported by the National Natural Science Foundation of China     

Structure and dielectric properties of ZnO and Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> doped BaO-TiO<Subscript>2</Subscript> system microwave ceramics

The microwave dielectric properties and microstructure of BaTi4.3ZnyO9.6＋y ＋0.02 mol% SnO2＋0.01 mol% MnCO3＋x mol% Nb2O5（x=0-0.05, y=0-0.08） system ceramics were studied as a function of the amount of ZnO and Nb2O5 doped. Addition of （y=0-0.05） ZnO and （x=0-0.025） Nb2O5 enhanced the reactivity and decreased the sintering temperature effectively. It also increased the dielectric constant ε r and quality factor Q（=1/tan 8） of the system due to the substitution of Ti^4＋ ions with incorporating Zn^2＋and Nb^5＋ ions, which was analyzed by the reaction ZnO＋Nb2O5＋ 3 TiTxTi →ZnTi＋ 2NbTi＋3TiO2. When the system doped with （y=0.05） ZnO and （x=0.025） Nb205 were sintered at 1 160 ℃ for 6 h, the εr. Qf0 value and rfwere 36.5, 42 000 GHz, and＋1.8 ppm/℃, respectively, at 5 GHz.     

不同污泥龄厌氧氨氧化菌的脱氮效能及其动力学特性

为研究不同污泥龄(SRT)条件下厌氧氨氧化菌的脱氮效能和动力学特性,采用一组SBR反应器研究梯度降低污泥龄过程中系统的NO2--N去除负荷(Nr)和NO2--N污泥负荷(Ns),并对各阶段厌氧氨氧化过程动力学特性进行分析.结果表明,污泥龄由21 d梯度降低到12 d,Nr由0.590 kg/(m3·d)降低到0.493 kg/(m3·d),单位MLVSS Ns由0.178 kg/(kg·d)提升到0.297 kg/(kg·d),系统整体的脱氮性能有所下降,但单位质量的厌氧氨氧化菌脱氮效率显著提升;采用莫诺(Monod)模型可以较好地模拟不同污泥龄运行阶段厌氧氨氧化菌的动力学行为,动力学分析表明,随着污泥龄的降低,NO2--N的最大比降解速率vmax由0.406 d-1提高到0.826 d-1,半饱和常数Ks由23.3 mg/L增加到95.3 mg/L,梯度降低污泥龄能够筛选纯化生长速率较快的厌氧氨氧化菌菌种,提升NO2--N的最大比降解速率,但厌氧氨氧化菌对底物的亲和性会逐渐变差,稳定性降低.     

Effect of additive on synthesis of MnZn ferrite nanocrystal by hydrothermal crystallization

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Biomolecule-assisted solvothermal synthesis and enhanced visible light photocatalytic performance of Bi<Subscript>2</Subscript>S<Subscript>3</Subscript>/BiOCl composites

Novel Bi₂S₃/BiOCl photocatalysts were successfully synthesized via a facile biomolecule-assisted solvothermal method and biomolecule L-cysteine was used as the sulfur source. The structures, morphology, and optical properties of the synthesized samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, transmission electron microscopy (TEM), and UV-vis diffuse reflectance spectroscopy (DRS). The presence of Bi₂S₃ in the Bi₂S₃/BiOCl composites could not only improve the optical properties but also enhance the photocatalytic activities for the degradation of Rhodamine B (RhB) under visible-light irradiation (λ > 420 nm) as compared with single Bi₂S₃ and BiOCl. Especially, the sample displayed the best performance of the photodegradation when the feed molar ratio of BiCl3 and L-cysteine was 2.4:1, which was about 10 times greater than that of pure BiOCl. The enhanced photocatalytic activities could be ascribed to the effective separation of photoinduced electrons and holes and the photosensitization of dye. Moreover, the possible photodegradation mechanism was also proposed, and the results revealed that the active holes (h⁺) and superoxide radicals (?O₂ ^?) were the main reactive species during photocatalytic degradation.     

Photocatalytic H2 evolution activity of CuO/ZrO2 composite catalyst under simulated sunlight irradiation

Zirconia-supported CuO (CuO/ZrO₂) composite photocatalysts were successfully synthesized via citric acid-assisted sol-gel technique. For comparison, CuO/ZrO₂ materials were also prepared by solid state reaction and co-precipitation method. The as-prepared powders were characterized by X-ray diffractometry (XRD), transmission electron microscopy (TEM), and thermogravimetric-differential thermal analysis (TG-DTA). The photocatalytic activity of CuO/ZrO₂ catalyst was investigated based on the H₂ evolution from oxalic acid solution under simulated sunlight irradiation. The effects of molar ratio of CuO to ZrO₂, preparation method, phase change with the calcination temperature and the durability on the photocatalytic activity of the photocatalyst were investigated in detail. It is found that the optimal activity of photocatalytic H₂ evolution (2.41 mmol·h⁻¹μ⁻¹) can be obtained when CuO/ZrO₂ composite photocatalyst is synthesized by sol-gel technique and the mole ratio of CuO to ZrO₂ is 40%. The activity of copper oxide supported on monoclinic ZrO₂ calcined at higher temperature is much higher than that on tetragonal ZrO₂ calcined at lower temperature, and the best calcination temperature is 900 °C.     

人工红树林碳通量变化特征及其影响因素分析

红树林是重要的滨海蓝碳生态系统.人工红树林在恢复过程中碳交换过程受到气候、植被等环境的影响,与成熟红树林呈现较大差异.本研究采用闭路涡动相关系统对珠江河口人工红树林湿地生态系统进行二氧化碳(CO2)通量和甲烷(CH4)通量的观测,并基于通径分析方法探讨了环境要素对总初级生产力(GPP)、生态系统呼吸(Re)、CO2和C...     

Study on the isothermal oxidation behavior in air of Ti3AlC2 sintered by hot pressing

The isothermal oxidation behavior at 900–1300°C for 20 h in air of bulk Ti₃AlC₂ with 2.8 wt% TiC sintered by means of hot pressing was investigated in the work. The isothermal oxidation behavior generally followed a parabolic rate law. The parabolic rate constants increased from 1.39×10⁻¹⁰ kg²·m⁻⁴·s⁻¹ at 900°C to 5.56×10⁻⁹ kg²·m⁻⁴·s⁻¹ at 1300°C. The calculated activation energy was 136.45 kJ/mol. It was demonstrated that Ti₃AlC₂ had excellent oxidation resistance due to the continuous, dense and adhesive protect scales consisted of a mass of α-Al₂O₃ and a little of TiO₂ and/or Al₂TiO₅. In principle, the oxide scale was grown by the inward diffusion of O²⁻ and the outward diffusion of Ti⁴⁺ and Al³⁺. The rapid outward diffusion of cations usually resulted in the formation of cracks, gaps, and holes.