基于CO2气体分离的固载离子液体@介孔二氧化硅混合基质膜

为提升混合基质膜对CO₂的气体分离性能,将具有良好CO₂吸附特性能的离子液体首先固载于介孔SiO₂中,而后将该复合材料掺杂到 聚酰亚胺高分子中构建高效分离CO₂的混合基质膜.研究结果表明,固载离子液体主要进入介孔SiO₂的孔道内部,但当绝大部分介孔孔道被离子液体填满后,过多离子液体在SiO₂颗粒外围形成连接.由于离子液体对CO₂优异的吸附性能,其固载后介孔SiO₂对CO₂的吸附性能得到的显著提升,这进一步增强了固载离子液体的介孔SiO₂掺杂混合基质膜对CO₂气体的捕获,随着混合基质膜中离子液体固载量增加其CO₂渗透性能也明显提升.但当固载离子液体加入量达到1.0 g时,固载离子液体的介孔SiO₂在PI高分子中出现了团聚,其CO₂渗透性能反而下降.IL@C-SiO₂-2/PI膜的渗透性能和对CO₂的渗透选择性都达到最佳,其对CO₂/N₂理想选择性可达到30.     

Competitive role of nitrogen functionalities of N doped GO and sensitizing effect of Bi2O3 QDs on TiO2 for water remediation

The promising solar irradiated photocatalyst by pairing of bismuth oxide quantum dots (BQDs) doped TiO₂ with nitrogen doped graphene oxide (NGO) nanocomposite (NGO/BQDs-TiO₂) was fabricated. It was used for degradation of organic pollutants like 2,4-dichlorophenol (2,4-DCP) and stable dyes, i.e. Rhodamine B and Congo Red. X-ray diffraction (XRD) profile of NGO showed reduction in oxygenic functional groups and restoring of graphitic crystal structure. The characteristic diffraction peaks of TiO₂ and its composites showed crystalline anatase TiO₂. Morphological images represent spherical shaped TiO₂ evenly covered with BQDs spread on NGO sheet. The surface linkages of $\text{NO}?\mathrm{O}?\text{Ti}$, $\mathrm{C}?\mathrm{O}?\text{Ti}$, $\mathrm{B}\mathrm{i}?\mathrm{O}?\text{Ti}$ and vibrational modes are observed by Fourier transform infrared spectroscopy (FTIR) and Raman studies. BQDs and NGO modified TiO₂ results into red shifting in visible region as studied in diffused reflectance spectroscopy (DRS). NGO and BQDs in TiO₂ are linked with defect centers which reduced the recombination of free charge carriers by quenching of photoluminescence (PL) intensities. X-ray photoelectron spectroscopy (XPS) shows that no peak related to $\mathrm{C}?\mathrm{O}$ in NGO/BQDs-TiO₂ is observed. This indicated that doping of nitrogen into GO has reduced some oxygen functional groups. Nitrogen functionalities in NGO and photosensitizing effect of BQDs in ternary composite have improved photocatalytic activity against organic pollutants. Intermediate byproducts during photo degradation process of 2,4-DCP were studied through high performance liquid chromatography (HPLC). Study of radical scavengers indicated that ${\mathrm{O}}_2^{·?}$ has significant role for degradation of 2,4-DCP. Our investigations propose that fabricated nanohybrid architecture has potential for degradation of environmental pollutions.     

Effects of humic acid fractions with different polarities on photodegradation of 2, 4-D in aqueous environments

Four fractions (A, B, C, and D) of humic acids (HAs) were separated based on the polarity from weak to strong. UV-vis absorption and Fourier transform infrared spectroscopy (FTIR) analysis show that the fractions C and Dpossessedmore aromatic C=C content. The influences of HAs and their fractions on the photolysis were investigated by the photodegradation of 2,4-D solutions under simulated solar light irradiation. The degradation rate of 2,4-D was found to decrease in the presence of bulk HAs or their fractions especially at high HAs concentration. The fractions of strong polarity C and D retarded the degradation rate more than the fractions of weak polarity A and B. This could be attributed to the different absorption intensity of the four HAs fractions in the order of D ⩾ C > A > B, and the stronger π-π electron donor-acceptor interactions between the strong polar fractions and 2,4-D.     

Green and efficient degradation of cefoperazone sodium by Bi4O5Br2 leading to the production of non-toxic products: Performance and degradation pathway

Photocatalytic process represents a promising approach to overcome the pollution challenge associated with the antibiotics-containing wastewater. This study provides a green, efficient and novel approach to remove cephalosporins, particularly cefoperazone sodium (CFP). Bi₄O₅Br₂ was chosen for the first time to systematically study its degradation for CFP, including the analysis of material structure, degradation performance, the structure and toxicity of the transformation products, etc. The degradation rate results indicated that Bi₄O₅Br₂ had an excellent catalytic activity leading to 78% CFP removal compared with the pure BiOBr (38%) within 120 min of visible light irradiation. In addition, the Bi₄O₅Br₂ presents high stability and good organic carbon removal efficiency. The effects of the solution pH (3.12 - 8.75) on catalytic activity revealed that CFP was mainly photocatalyzed under acidic conditions and hydrolyzed under alkaline conditions. Combined with active species and degradation product identification, the photocatalytic degradation pathways of CFP by Bi₄O₅Br₂ was proposed, including hydrolysis, oxidation, reduction and decarboxylation. Most importantly, the identified products were all hydrolysis rather than oxidation byproducts transformed from the intermediate of β-lactam bond cleavage in CFP molecule, quite different from the mostly previous studies. Furthermore, the final products were demonstrated to be less toxic through the toxicity analysis. Overall, this study illustrates the detailed mechanism of CFP degradation by Bi₄O₅Br₂ and confirms Bi₄O₅Br₂ to be a promising material for the photodegradation of CFP.     

三维有序介孔铈钴铜催化剂的制备及其降解邻二甲苯的机制

以PMMA为模板,通过聚乙二醇(PEG400)和柠檬酸辅助的溶胶凝胶法制备三维有序介孔铈钴铜(3DOM 3C)催化剂,应用BET、SEM、XRD和XPS等对不同煅烧温度的3DOM 3C催化剂进行表征分析,研究了催化剂活性及其影响因素,并利用FT-IR和GC-MS对降解产物进行分析,推测出催化降解邻二甲苯的机理.结果表明,煅烧温度500℃时制备的3DOM 3C催化剂表面具有三维介孔结构,且分散均匀,表面的晶体氧化物最少,存在大量的Cu~(2+)、Ce~(3+)和表面氧,催化剂表面存在更多的固溶体、表面活性位点和氧空位,有利于提高催化活性.在邻二甲苯初始浓度600 ppm、空速16000 h~(-1)、50%O_2条件下,煅烧温度500℃时制备的3DOM 3C催化效果最佳,在260℃时,3DOM 3C催化剂对邻二甲苯的转化率达98%,T_(90)为250℃. 3DOM 3C对邻二甲苯的转化率随着初始浓度、空速和相对湿度的升高而呈下降趋势,随着O_2含量的增加而增加.气流中混入150 ppm的乙酸乙酯能够提高邻二甲苯的转化率,提高其低温催化性能.邻二甲苯催化反应后催化剂表面的O—H、■、C—H和金属—氧键都相应的减少,降解中间产物主要有邻甲基苯甲醛和邻甲基苯甲酸.邻二甲苯降解反应涉及Mars Van Krevelen机理(MVK),先被氧化成邻甲基苯甲醛,再进一步氧化成邻甲基苯甲酸,最终生成CO_2和H_2O.     

介孔氮化碳光催化降解诺氟沙星的动力学机制

采用一种简单高效的制备方法,利用SiO₂为模板制备出具有更高催化活性的介孔氮化碳材料（mpg-C₃N₄）,并通过透视电子显微镜（TEM）、X射线衍射（XRD）、氮气吸脱附测试（BET）、傅里叶变换红外光谱（FT-IR）、光电子能谱（XPS）对mpg-C₃N₄的形貌、组成结构进行表征.结果显示,mpg-C₃N₄表面存在大量直径约12nm的孔状结构,与g-C₃N₄相比,比表面积大幅度增大,并因此提供了更多的活性位点从而提高其光催化活性.使用紫外可见漫反射光谱（UV-vis DRS）和荧光光谱（PL）对其光电化学性能进行测试.结果表明介孔材料的引入使得氮化碳的吸收光谱发生红移,并降低了光生电子-空穴对复合率,从而提高对可见光利用效率.通过对诺氟沙星（NOR）的降解与吸附实验研究表明,NOR的光催化降解过程符合一级动力学和Langmuir-Hinshelwood动力学模型,而mpg-C₃N₄对NOR的吸附符合二级动力学,表明NOR的光催化降解主要发生在催化材料的表面且以化学吸附为主.吸附实验表明mpg-C₃N₄在30min内可以吸附56.78%的NOR,降解实验显示,光解1.5h后,超过90%的NOR可被降解.相比体相g-C₃N₄,mpg-C₃N₄表现出良好的吸附性能和光催化性能.pH值影响实验表明pH值约为7.41时达到最佳降解效果,主要归因于药物形态与材料表面电荷作用.淬灭实验表明O₂^·-和h⁺是降解体系中的主要活性物质.     

硫氮共掺杂碳基材料活化过一硫酸盐降解2,4-二氯苯酚的效能及机理

为了解决外源杂原子掺杂到碳基相催化剂过程中掺杂量低和分布不均的问题,本研究通过直接碳化聚吡咯(PPy)和聚噻吩(PTh)混合物制备得到硫氮共掺杂碳基催化材料(CPPy-PTh),并研究其活化过一硫酸盐(PMS)降解水中的2,4-二氯苯酚(2,4-DCP)的性能.结果表明,CPPy-PTh催化PMS可在30 min内降解...     

Comparing dark- and photo-Fenton-like degradation of emerging pollutant over photo-switchable Bi2WO6/CuFe2O4: Investigation on dominant reactive oxidation species

The extensive use of tetracycline hydrochloride (TCH) poses a threat to human health and the aquatic environment. Here, magnetic p-n Bi₂WO₆/CuFe₂O₄ catalyst was fabricated to efficiently remove TCH. The obtained Bi₂WO₆/CuFe₂O₄ exhibited 92.1% TCH degradation efficiency and 50.7% and 35.1% mineralization performance for TCH and raw secondary effluent from a wastewater treatment plant in a photo-Fenton-like system, respectively. The remarkable performance was attributed to the fact that photogenerated electrons accelerated the Fe(III)/Fe(II) and Cu(II)/Cu(I) conversion for the Fenton-like reaction between Fe(II)/Cu(I) and H₂O₂, thereby generating abundant ?OH for pollutant oxidation. Various environmental factors including H₂O₂ concentration, initial pH, catalyst dosage, TCH concentration and inorganic ions were explored. The reactive oxidation species (ROS) quenching results and electron spin resonance (ESR) spectra confirmed that ?O₂^? and ?OH were responsible for the dark and photo-Fenton-like systems, respectively. The degradation mechanisms and pathways of TCH were proposed, and the toxicity of products was evaluated. This work contributes a highly efficient and environmentally friendly catalyst and provides a clear mechanistic explanation for the removal of antibiotic pollutants in environmental remediation.     

Synthesis, characterization and application of ZnO-Ag as a nanophotocatalyst for organic compounds degradation, mechanism and economic study

The current work deals with ZnO-Ag nanocomposites (in the wide range of x in the Zn_1 − xO-Ag_x chemical composition) synthesized using microwave assisted solution combustion method. The structural, morphological and optical properties of the samples were characterized by XRD (X-ray diffraction), FTIR (Fourier transform infrared spectrometry), SEM (scanning electron microscopy technique), EDX (energy dispersive X-ray spectrum), ICP (inductively coupled plasma technique), TEM (transmission electron microscopy), BET (Brunauer–Emmett–Teller method), UV–Vis (ultraviolet–visible spectrophotometer) and photoluminescence spectrophotometer. The photocatalytic activity of the ZnO-Ag was investigated by photo-degradation of Acid Blue 113 (AB 113) under UV illumination in a semi-batch reactor. This experiment showed that ZnO-Ag has much more excellent photocatalytic properties than ZnO synthesized by the same method. The enhanced photocatalytic activity was due to the decrease in recombination of photogenerated electron-holes. The results showed the improvement of ZnO photocatalytic activity and there is an optimum amount of Ag (3.5 mol%) that needs to be doped with ZnO. The effect of operating parameters such as pH, catalyst dose and dye concentration were investigated. The reaction byproducts were identified by LC/MS (liquid chromatography/mass spectrometry) analysis and a pathway was proposed as well. Kinetic studies indicated that the decolorization process follows the first order kinetics. Also, the degradation percentage of AB 113 was determined using a total organic carbon (TOC) analyzer. Additionally, cost analysis of the process, the mechanism and the role of Ag were discussed.     

Pd/GO/Ni电极的制备及对2,4-二氯酚的降解研究

为去除持久性氯代有机污染物2,4-二氯酚(2,4-DCP),利用电化学沉积法制备了一种新型钯/氧化石墨烯/泡沫镍(Pd/GO/Ni)电极,并通过电化学法降解2,4-二氯酚,取得良好的效果。通过扫描电镜等表征手段观察其表面形貌。结果表明:氧化石墨烯浓度为10 mol/L是制备Pd/GO/Ni电极的最佳浓度,p H为3时,Pd/GO/Ni电极对2,4-二氯酚的去除率达到90.7%。     

EDDS强化Fe0-Al0体系降解废水中4-氯酚的性能和机理

采用乙二胺二琥珀酸（EDDS）强化Fe⁰-Al⁰体系还原水溶液中的O₂产生H₂O₂和·OH等活性氧（ROS）的绿色高级氧化工艺,以4-氯酚（4-CP）模拟废水为研究对象,考察了溶液的初始pH值、铁铝的质量比、EDDS投加量和4-CP的初始浓度等因素对4-CP降解的影响.采用电子自旋共振（ESR）法、苯甲酸捕捉法以及4-CP的降解产物等证实了ROS的产生及4-CP的降解机制.结果表明：EDDS强化Fe⁰-Al⁰/O₂体系对4-CP的去除率随溶液初始pH的升高而降低,但在pH=2.5～9范围内,始终具有较好的4-CP去除率;随Fe⁰：Al⁰质量比增加4-CP的去除率先增大后减小,最佳质量比为4：1;随EDDS投加量和4-CP初始浓度增加,4-CP的去除率增大;EDDS可使体系的高级氧化能力提高9倍,在初始pH=2.5、Fe⁰=8g/L、Al⁰=2g/L、EDDS=1.5mmol/L条件下,反应3h后100mg/L 4-CP的去除率和脱氯率均达到近100%..     

2,4-二硝基酚的超声波及协同降解研究

以 2 ,4 二硝基酚为研究对象 ,探讨了超声功率、氧化剂H2 O2 与Fenton试剂等因素对其超声降解效率的影响 .2 ,4 二硝基酚在超声波 (US)、US H2 O2 和US Fe2 H2 O2 体系中的降解均符合一级反应动力学模式 .超声波和Fe2 H2 O2 体系在 2 ,4 二硝基酚的降解过程中存在着协同效应 ,而在Cu2 H2 O2 和超声波体系中未观察到相似的协同效应 .     

一株耐盐苯酚降解菌的分离、鉴定及耐盐机制研究

从污泥样品中分离得到1株高效的耐盐苯酚降解菌,该菌株能够在温度20～30 ℃、pH5.0～9.0和盐度1％ ～ 10％范围内以苯酚为唯一碳源进行生长.通过形态、生理生化特性分析及16S rDNA序列分析,鉴定该菌株为Rhodococcus sp.,命名为W2.在温度30℃、pH =7.0、NaCl50g·L-1的条件下,菌株可耐受苯酚的最大浓度为700 mg·L-1.粗酶中检测到的邻苯二酚l,2-双加氧酶活性表明,菌株W2通过邻位开环断裂途径代谢苯酚.底物广谱性考察结果表明,菌株W2能够在高盐条件下利用苯甲酸、水杨酸等多种芳香化合物作为碳源生长.对耐盐机理进行的初步分析表明,细胞内甜菜碱和四氢嘧啶的含量随着盐浓度的增加而增大,说明四氢嘧啶和甜菜碱的积累是菌株W2抵抗高盐度的重要机制.     

Photocatalytic parameters and kinetic study for degradation of dichlorophenol-indophenol (DCPIP) dye using highly active mesoporous TiO2 nanoparticles

Highly active mesoporous TiO_2 of about 6 nm crystal size and 280.7 m~2/g specific surface areas has been successfully synthesized via controlled hydrolysis of titanium butoxide at acidic medium. It was characterized by means of XRD(X-ray diffraction), SEM(scanning electron microscopy), TEM(transmission electron microscopy), FT-IR(Fourier transform infrared spectroscopy), TGA(thermogravimetric analysis), DSC(differential scanning calorimetry) and BET(Brunauer–Emmett–Teller) surface area. The degradation of dichlorophenol-indophenol(DCPIP) under ultraviolet(UV) light was studied to evaluate the photocatalytic activity of samples. The effects of different parameters and kinetics were investigated. Accordingly, a complete degradation of DCPIP dye was achieved by applying the optimal operational conditions of 1 g/L of catalyst, 10 mg/L of DCPIP, pH of 3 and the temperature at 25 ± 3°C after 3 min under UV irradiation. Meanwhile, the Langmuir–Hinshelwood kinetic model described the variations in pure photocatalytic branch in consistent with a first order power law model.The results proved that the prepared TiO_2 nanoparticle has a photocatalytic activity significantly better than Degussa P-25.     

氨基乙醇席夫碱Cu2+配合物的合成及其催化染料降解

合成了3个氨基乙醇席夫碱Cu2+配合物并进行了表征.利用分光光度法考查了配合物催化降解酸性蓝9的性能和动力学曲线;利用Graph Pad Prism 5软件进行了米氏常数的测定;利用HPLC法测定了降解产物.发现配合物均为单核五配位配合物.发现配合物能催化废水中酸性蓝9降解,催化活性Cu Cl Lb·H2O最好,Cu Cl La·H2O其次,Cu Cl Lc·H2O最差,说明给电子基团有利于催化活性,位阻基团不利于催化活性.发现Cu Cl La·H2O、Cu Cl Lb·H2O催化酸性蓝9的V-S曲线与米氏方程吻合,米氏常数分别为1.35×10-2mmol·L-1和1.54×10-2mmol·L-1,说明催化过程具有酶促特性,Cu Cl La·H2O与底物的结合能力比Cu Cl Lb·H2O与底物结合能力弱.发现降解产物有顺式丁烯二酸.推测了配合物的催化机理和酸性蓝9的降解机制.得到了两个性能优良的酸性蓝9降解的仿酶催化剂,催化活性可以通过基团进行调控,为开发新的染料废水的有效治理技术提供了理论和实践支持.     

Effect of viscosity, basicity and organic content of composite flocculant on the decolorization performance and mechanism for reactive dyeing wastewater

A coagulation/flocculation process using the composite flocculant polyaluminum chloride-epichlorohydrin dimethylamine (PAC-EPI-DMA) was employed for the treatment of an anionic azo dye (Reactive Brilliant Red K-2BP dye). The effect of viscosity (ηup), basicity (B = [OH]/[Al]) and organic content (W_P) on the flocculation performance as well as the mechanism of PAC-EPI-DMA flocculant were investigated. The ηup was the key factor affecting the dye removal efficiency of PAC-EPI-DMA. PAC-EPI-DMA with an intermediate ηup (2400 mPa.sec) gave higher decolorization efficiency by adsorption bridging and charge neutralization due to the co-effect of PAC and EPI-DMA polymers. The W_P of the composite flocculant was a minor important factor for the flocculation. The adsorption bridging of PAC-EPI-DMA with ηup of 300 or 4300 mPa.sec played an important role with the increase of W_P, whereas the charge neutralization of them was weaker with the increase of W_P. There was interaction between W_P and B on the removal of reactive dye. The composite flocculant with intermediate viscosity and organic content was effective for the treatment of reactive dyeing wastewater, which could achieve high reactive dye removal efficiency with low organic dosage.     

Catalytic performance of Fe3O4-CoO/Al2O3 catalyst in ozonation of 2-(2,4-dichlorophenoxy)propionic acid, nitrobenzene and oxalic acid in water

Fe3O4-CoO/Al2O3 catalyst was prepared by incipient wetness impregnation using Fe(NO3) 3·9H2O and Co(NO3) 2·6H2O as the precursors,and its catalytic performance was investigated in ozonation of 2-(2,4-dichlorophenoxy) propionic acid(2,4-DP) ,nitrobenzene and oxalic acid.The experimental results indicated that Fe3O4-CoO/Al2O3 catalyst enabled an interesting improvement of ozonation eciency during the degradation of each organic pollutant,and the Fe3O4-CoO/Al2O3 catalytic ozonation system followed a radical-type mechanism.The kinetics of ozonation alone and Fe3O4-CoO/Al2O3 catalytic ozonation of three organic pollutants in aqueous solution were discussed under the mere consideration of direct ozone reaction and OH radical reaction to well investigate its performance.In the catalytic ozonation of 2,4-DP,the apparent reaction rate constants(k) were determined to be 1.456×10-2 min-1 for ozonation alone and 4.740×10-2 min-1 for O3/Fe3O4-CoO/Al2O3.And O3/Fe3O4-CoO/Al2O3 had a larger Rct(6.614×10-9) calculated by the relative method than O3 did(1.800×10-9) ,showing O3/Fe3O4-CoO/Al2O3 generated more hydroxyl radical.Similar results were also obtained in the catalytic ozonation of nitrobenzene and oxalic acid.The above results demonstrated that the catalytic performance of Fe3O4-CoO/Al2O3 in ozonation of studied organic substance was universal to a certain degree.     

Photocatalytic degradation of 4-chlorophenol under P-modified TiO2/UV system:Kinetics, intermediates, phytotoxicity and acute toxicity

A series of phosphorus-modified titanium dioxide samples with varying P/Ti atomic ratio were conveniently prepared via a conventional solgel route. The effects of phosphorus content and calcination temperature on the crystalline structure, grain growth, surface area, and the photocatalytic activity of P-modified TiO₂ were investigated. The XRD results showed that P species slow down the particle growth of anatase and increase the anatase-to-rutile phase transformation temperature to more than 900℃. Kinetic studies on the P-modified TiO₂ to degraded 4-chlorophenol had found that the TP5₅₀₀ prepared by adopting a P/Ti atomic ratio equal to 0.05 and calcined at 500℃ had an apparent rate constant equal to 0.0075 min^-1, which is superior to the performance of a commercial photocatalyst Degussa P25 K_app = 0.0045 min^-1 and of unmodified TiO₂ (TP0₅₀₀) K_app = 0.0022 min^-1. From HPLC analyses, various hydroxylated intermediates formed during oxidation had been identified, including hydroquinone (HQ), benzoquinone (BQ) and (4CC) 4-chlorocatechol as main products. Phytotoxicity was assessed before and after irradiation against seed germination of tomato (Lycopersicon esculentum) whereas acute toxicity was assessed by using Folsomia candida as the test organism. Intermediates products were all less toxic than 4-chlorophenol and a significant removal of the overall toxicity was accomplished     

Construction of ternary CuO/CuFe2O4/g-C3N4 composite and its enhanced photocatalytic degradation of tetracycline hydrochloride with persulfate under simulated sunlight

In this study, a graphitic carbon nitride（g-C₃N₄） based ternary catalyst Cu O/Cu Fe₂O₄/gC₃N₄（CCCN） is successfully prepared thorough calcination method. After confirming the structure and composition of CCCN, the as-synthesized composites are utilized to activate persulfate（PS） for the degradation of organic contaminant. While using tetracycline hydrochloride（TC） as pollutant surrogate, the effects of initial p H, PS and catalyst ...     

TiO2/ZSM-5m光催化耦合过硫酸盐降解焦化尾水的研究

以具有介孔结构的沸石分子筛ZSM-5m负载纳米TiO2制备出复合型光催化剂,用扫描电镜、比表面及孔径分析仪和X射线衍射对形貌和结构进行表征,通过序批试验考察了TiO2/ZSM-5m/过硫酸盐体系深度降解焦化生化处理出水中残余有机污染物(ROPs)的效果和机理.结果表明,在COD初始平均浓度为352mg/L,TiO2/ ZSM-5m投加量为1.6g/L,pH值为3.0,C(Na2S2O8)为0.8g/L,常温下反应180min,COD出水平均浓度为76.3mg/L,去除率达到78.2 %,在上述优化条件下可达到现行污染物排放标准.ROPs光催化符合Langmuir-Hinshelwood模型,推测具有微介双孔结构的催化剂表面电子易被S2O82-俘获,降低空穴与电子的复合率,促进了·OH 和SO4-·形成,对ROPs的吸附和光降解有较大的强化作用.用GC-MS对处理前后废水中的污染物进行测定以揭示降解与转化规律,发现苯类特征污染物能有效降解,但产生的中间产物明显增多.