自组装超分子前驱体制备管状氮化碳及模拟太阳光光催化降解水中双氯芬酸

石墨相氮化碳(g-C₃N₄,GCN)作为一种新型无金属二维材料,因在可见光驱动下能够降解水中新有机污染物而备受关注. 但传统石墨相氮化碳存在比表面积小与活性位点少的弊端,严重限制了其应用前景. 为改良氮化碳性能,利用超分子自组装前驱体热聚合方法成功制备了微米级管状石墨相氮化碳(TCN),使用扫描电镜(SEM)、傅里叶变换红外光谱(FT-IR)、X射线衍射(XRD)、紫外-可见漫反射光谱(UV-vis DRS)等技术手段,对TCN的形貌、元素组成、晶体结构、电化学性能等进行表征. 研究还选取双氯芬酸(DCF)作为目标污染物,探索其降解行为与机理. 结果表明:①TCN基本结构单元为七嗪环,但比表面积(20.9 m2/g)较GCN增加了1倍以上. ②TCN (100)晶面暴露增强,晶面调控暴露出更多七嗪环边缘氮原子的孤对电子,利于光生电子激发和载流子分离,从而增强光催化活性. ③TCN能带带隙为2.48 eV,小于GCN (2.69 eV),说明TCN对可见光的吸收能力提升. ④莫特-肖特基曲线、光电流、阻抗谱图和扫描伏安谱图等电化学性能测试结果表明,TCN的光生电子转移效率大幅提升,有利于抑制光生空穴-电子对(h+-e-)的复合. ⑤TCN在模拟太阳光驱动下降解双氯芬酸(DCF)的动力学试验中准一级动力学常数(k₁)达6.99×10-2 min-1,是GCN的5.5倍. ⑥电子自旋共振谱(ESR)和自由基淬灭试验证实,体系中超氧根自由基(·O₂-)是最重要的活性氧物种,光生空穴(h+)也对DCF的降解有贡献. 研究显示,以超分子自组装的方式制备石墨相氮化碳的前驱体将有助于促进氮化碳可见光吸收、加速载流子分离,并提升光催化活性.      

熔盐法制备K+-g-C3N4及其光催化降解有机污染物性能

采用熔盐法制备了能级位置可控的钾离子掺杂石墨相氮化碳催化剂（g-C₃N₄）,并考察了其在可见光下降解罗丹明B（RhB）性能.采用XRD、UV-Vis、XPS、N₂吸附、PL、EIS等手段对催化剂进行了表征.结果表明,钾离子的引入降低了催化剂粒径尺寸,提高了比表面积,改善了光生电子-空穴对的分离效率.不仅如此,通过控制钾离子掺杂量可以实现催化剂的能级位置在一定范围内的任意调变,使有机污染物的氧化降解反应从·O₂^-单一氧化剂反应变成·OH和·O₂^-双氧化剂反应,大大提高了降解率.制备的钾离子掺杂g-C₃N₄的RhB降解速率常数达到0.022min^-1,是纯g-C₃N₄的5倍.不仅如此,通过对能级位置的调控,制备的催化剂对其他多种有机污染物如甲基蓝,苯酚等的降解率也有显著提高.     

溴代甲烷在SO42-/TiO2上的光催化降解

采用溶胶-凝胶法制备了SO₄^2-/TiO₂催化剂,运用XRD、BET比表面测定,FTIR等技术对催化剂进行了表征,并在微型常压连续反应装置上进行CH₃Br光催化反应性能考察.结果表明,SO₄^2-引入TiO₂体系使得催化剂的结构和光催化性能得到显著改善.SO₄^2-负载量为9%,烧结温度为450℃时,SO₄^2-/TiO₂催化剂的光催化活性最高;SO₄^2-/TiO₂催化剂对反应物料中的水汽有很好的耐受性;当反应温度低于85℃时,提高反应温度,有利于改善对CH₃Br的光催化反应活性,表观活化能约为19.6kJ·mol^-1,反应温度在85℃～105℃区间时,CH3Br的光催化降解表观活化能为0.     

Effect of wastewater COD/N ratio on aerobic nitrifying sludge granulation and microbial population shift

The effect of COD/N ratio on the granulation process and microbial population succession was investigated. Four identical sequencing batch reactors, R1, R2, R3 and R4, were operated with various initial COD/N ratios ranging from 0/200 to 800/200 (m/m). Ethanol was fed as the source of COD. Aerobic granules were successfully cultivated in R2 and R3, operating with the COD/N ratio of 200/200 and 400/200, respectively. Scanning electron microscope observations indicated that short rod-shaped and spherical bacteria were dominant in R2, while granules produced in R3 were surrounded with a large amount of filamentous bacteria. The average specific nitritation rate in R2 and R3 were 0.019 and 0.008 mg N/(mg MLVSS.hr), respectively. Fluorescence in situ hybridization results demonstrated that nitrifying bacteria population was enriched remarkably in R2. It indicated that nitrification ability and nitrifying bacteria population were enriched remarkably at low COD/N ratio. However, no granules were formed in R1 and R4 which might attribute to either limited or excessive extracellular polymeric substances production. This study contributed to a better understanding of the role of COD/N ratio in nitrifying sludge granulation.     

低温下玉米秸秆与牛粪混合厌氧发酵产气特性研究

通过静态试验,探究在15℃的低温条件下,经过预处理的玉米秸秆和牛粪,在不同混合配比下厌氧发酵的产气特性。试验结果表明:将牛粪与秸秆按1∶1配比的产气效果最好,相对于配比为2∶1、3∶1的累积产气量分别高出52.66%和73.60%。随着发酵过程进行,COD波动很大。发酵过程中碳源主要由玉米秸秆提供,秸秆所占比例越大,COD降解率越高。日产气量达到高峰的时间稍滞后于VFA,秸秆比例越大的组别,VFA整体处于越高水平。而辅酶F420与产气量之间关系不显著。发酵初期CMC酶活力变化显著,且以玉米秸杆与牛粪配比为1∶1为配比的一组CMC酶活力高于其余2组,最高值达到了15.042 U/g。     

水葫芦制备生物气高效工艺中试研究

在5m3发酵规模探索水葫芦中温厌氧制备生物气的高效工艺发酵,试验表明工艺的发酵起动配方为污泥水∶水葫芦∶猪粪便=4∶3∶0.5,C/N 30,TS 8%,酵补料为100%水葫芦,发酵温度35～45℃,间歇搅拌,pH控制7.7±0.1,其中技术要点包括水葫芦应尽量粉碎均匀,接种醋酸杆菌加快酸化速度,添加尿素补充氮素养分等。     

Photo-degradation organic dyes by Sb-based organic-inorganic hybrid ferroelectrics

The organic-inorganic hybrid halide compounds have emerged as one of the most promising photoelectric material for their superior optoelectronic properties and hold great prospects for renewable energy substitutes and environmental protection as photocatalysis. Here, we report the optical properties of the Sb-based organic-inorganic hybrid ferroelectric materials: pyridine-4-aminium tetrachloroantimonate ((C₅H₇N₂)SbCl₄, sample 1), piperidin-1-aminium tetrachloroantimonate ((C₅H₁₃N₂)SbCl₄, sample 2) and tris(trimethylammonium) nonachlorodiantimonate (((CH₃)₃NH)₃Sb₂Cl₉, sample 3), which are a kind of exploited efficient photocatalysts. Samples 2 and 3 exhibit distinct photoelectric respond, which are mainly ascribed to their minor narrow band-gap compared with sample 1. For the ferroelectrics, the intrinsic of spontaneous polarization of sample 3 at room temperature is favourable for the separation of photogenerated electrons and holes within the photorespond process. Moreover, sample 3 shows the highest efficiency of photo-decomposed Rhodamine B (90.2% within 80 min) and Methyl Orange (MO) (97.4% within 50 min), thanks to the photo-excited electrons and holes promoting the formation of oxidative radical species during the photo-redox progress. These findings prove that the development of a novel Sb-based organic-inorganic hybrid halide compounds with good stability in the degradation of organic dyes paves a way to designing new photocatalyst.     

TiO2/PS/Fe3O4 光催化剂的低温制备及其光催化和磁回收性能

以聚苯乙烯(PS)包覆油酸修饰过的纳米Fe3O4为磁核,在低温(90℃)、中性(pH=7左右)条件下,制备了以PS为惰性隔离层的磁载TiO2光催化剂.用X射线衍射仪(XRD)、透射电子显微镜(TEM)、傅里叶红外分光光度计(FT-IR)、振动样品磁强计(VSM)对催化剂的物相组成、形貌、表面性质、磁学性质进行了表征.以苯酚为模拟污染物,考察了其光催化活性,以自制的磁回收装置,考察其回收特性.结果表明,低温制备的TiO2为锐钛矿结构,平均粒径为2～5 nm,催化剂TiO2/PS/Fe3O4[其中物质的量比为n(TiO2)∶n(St)∶n(Fe3O4)=60∶2.5∶1]具有结构完整的壳/壳/核结构,TiO2在PS/Fe3O4表面负载牢固;光催化降解苯酚遵循一级反应动力学方程,TiO2/PS/Fe3O4[n(TiO2)∶n(St)∶n(Fe3O4)=60∶2.5∶1]的反应速率常数K=0.025 8,与纯TiO2的活性接近(K=0.026 2);循环使用5次后,反应速率常数仅降低0.003 4.所制催化剂具有较强的磁感应强度,平均回收率可达到92%以上.该低温水解法制备的磁载TiO2光催化剂具有良好的应用前景.     

TiO2光催化剂的改性研究

采用浸渍法制备了掺杂Fe3+ ,用NH4 Cl提高单分散性并且用稀H2 SO4 表面修饰的TiO2 粉体光催化剂 ,考察了它与TiO2 在紫外光和日光作用下对直接耐晒黑G的降解效果。结果表明 ,以TiO2 干凝胶为母体 ,依次浸渍Fe3+ 、NH+ 4以及SO2 - 4所制备的粉体光催化剂Fe3+ /SO2 - 4/TiO2 在紫外光作用下降解效果比纯TiO2 高 2 .1倍 ,在日光作用下比TiO2 高 1 .9倍。X射线衍射分析表明 ,该法制备的TiO2 粉体中锐钛矿相占 1 0 0 % ,没有金红石相 ,平均晶粒粒径为 4nm ;红外吸收光谱分析表明 ,无论是纯TiO2 还是经过掺杂Fe3+ 、用H2 SO4 进行表面修饰后的TiO2 ,红外吸收光谱图基本相似 ,说明掺杂和表面修饰并没有极大地改变TiO2 的化学结构 ,光催化性能的提高归属于杂质能级的电子捕获陷阱作用、有效光成分增加和光生电子向反应物的迅速转移     

Bi5O7I/g-C3N4Z型异质结的常温沉淀制备及其光催化性能研究

以Bi（NO₃）₃·5H₂O、KI和g-C₃N₄为前驱体,采用常温沉淀法制备Bi₅O₇I/g-C₃N₄Z型异质结复合光催化剂,表征其光吸收性能、微观形貌、光生电子-空穴的分离效率等特性,研究新型光催化剂对RhB的可见光催化降解性能,探讨其可见光催化过程活性基团种类以及作用机理.结果表明：利用沉淀法合成Bi₅O₇I/g-C₃N₄的条件为：Bi（NO₃）₃·5H₂O、KI和g-C₃N₄的投加量分别为4.85g、1.66g和1.61g,乙二醇的用量为50mL,反应液的pH值为12,反应搅拌速度为200r/min,反应温度为25℃.Bi₅O₇I/g-C₃N₄异质结无杂相生成且纯度高,异质结复合发生在g-C₃N₄的（002）晶面和Bi₅O₇I的（203）晶面,但g-C₃N₄和Bi₅O₇I的化学结构未受影响.Bi₅O₇I/g-C₃N₄呈三维纳米花瓣形貌结构,为光生电子-空穴的迁移提供了大量的接触位点.Bi₅O₇I的g-C₃N₄掺杂改性使其光催化活性显著增强,其光吸收边缘由425nm红移至462nm,Bi₅O₇I/g-C₃N₄的能带排列结构与Z型异质结匹配,促进了光生电子-空穴的分离.其光电流密度（11.5mA/cm）约为g-C₃N₄和Bi₅O₇I对应值的2.66倍和1.47倍.Bi₅O₇I/g-C₃N₄对罗丹明B的可见光催化降解率为93.9%,显著高于g-C₃N₄（58%）和Bi₅O₇I（49.7%）的降解效果,其光催化氧化活性主要来自羟基基团、超氧基团和光生空穴等中间态自由基.     

皮革废水对ABR分区进水微生物相的影响研究

在制革废水ρ(COD)=3 000～3 200 mg/L,HRT=24 h时,采用六格室厌氧折流板反应器(ABR),在1、3、5格室以5∶3∶2的比例进水,通过COD、挥发性脂肪酸(VFA)、辅酶F420等指标的变化研究反应器各格室的微生物相分布情况。结果表明:COD和VFA在3,5格室分别出现下降和升高,整体性能稳定,而格室内微生物种群大致相同但优势菌群有所差异,前端格室以产酸菌为主,后端格室以甲烷菌为主。     

微污染原水的生物流化床预处理技术试验研究

以二相颗粒活性炭生物流化床(FBBR)为反应器,对以有机物和NH4+N为主要污染物的某大城市内河原水进行了预处理试验研究,在HRT12～18min,气水比20～25∶1,回流比3～4∶1的条件下FBBR对CODCr、NH4+N、NO2-N、浊度、色度的去除率分别为4132%、100%、97%～100%、6880%、30%～50%,而且对NH4+N和NO2+N有较强的抗冲击负荷能力。     

Ferroelectric polarization effect on the photocatalytic activity of Bi0.9Ca0.1FeO3/CdS S-scheme nanocomposites

BiFeO₃ (BFO), as a kind of narrow band-gap semiconductor material, has gradually emerged advantages in the application of photocatalysis. In this paper, Ca doped BFO nanoparticles Bi_0.9Ca_0.1FeO₃ (BCFO) were prepared by sol-gel method. And BCFO and CdS nanocomposites with two morphologies were obtained by controlling the time of loading CdS under a low temperature liquid phase process. It is found that the band gap becomes narrower after doping Ca into BFO, which is conducive to the absorption of visible light. Among all the samples, the composite of CdS nanowires and BCFO nanoparticles obtained by reaction time of 10 min has the best photocatalytic performance. The degradation rate of Methyl Orange solution was 94% after 90 min under visible light irradiation, which was much higher than that of pure BCFO and CdS. Furthermore, significant enhancement in the degradation rate (100% degradation in 60 min) can be achieved in poled samples after electric polarization process. The highest degradation rate is due to the promoted separation of photogenerated carriers induced by the internal polarization field and the formation of S-scheme heterostructure between BCFO and CdS. Such BCFO-CdS nanocomposites may bring new insights into designing highly efficient photocatalyst.     

黄土丘陵区小流域土壤碳氮比的变化及其影响因素

研究土壤C:N的变化有助于深入理解土壤有机碳氮的积累过程及其土壤质量的变化趋势。以黄土高原丘陵沟壑区砖窑沟小流域为单元,基于地貌类型和土地利用方式两大因素,采集737个土壤样品,研究流域内土壤C:N的变化差异及其影响因素。梁峁坡上,林地和草地0~20 cm土层的土壤C:N分别是农田土壤C:N的1.13和1.03倍;沟坡上,林地、草地和农田土壤的C:N分别为13.88、12.58、9.02。农田条件下,梁峁坡、沟坡和沟谷的土壤C:N分别为10.34、9.02和10.77;林地条件下,沟坡和梁峁坡的土壤C:N分别为13.88、11.67;草地条件下,沟坡土壤C:N是梁峁坡土壤C:N的1.19倍。同一地貌类型或土地利用方式条件下,土壤C:N均呈现表层大于深层的趋势,0~20 cm和20~40 cm土层的土壤C:N分别是40~100 cm土层土壤C:N的1.05~1.17和1.16~1.42倍。     

鸟粪石沉淀法处理鸡粪发酵沼液的试验研究

鉴于北京某养鸡场鸡粪发酵沼液氨氮浓度高的特点,采用了鸟粪石沉淀法对其进行处理。采用单因素和响应面实验的方式优化反应条件。通过单因素实验确定p H=10.0~10.5,n(Mg2+)∶n(NH+4)∶n(PO3-4)=1.3∶1∶1.1,反应时间为20 min,转速为300 r/min时,氨氮去除率最高,达到75.79%,通过响应面实验对所得最佳反应条件进一步优化,得出当p H=10.57,n(Mg2+)∶n(NH+4)∶n(PO3-4)=1.27∶1∶1.12时,氨氮去除率为75.81%。SEM及XRD分析表明沉淀主要成分为磷酸铵镁。     

负载型纳米Pd/Fe对氯代烃脱氯机理研究

采用实验室制备的负载型纳米Pd/Fe对几种常见的挥发性氯代烃:四氯乙烯(ICE)、三氯乙烯(TCE)、1,1-二氯乙烯(1,1-DCE)、氯乙烯(VC)和林丹(γ-HCH)进行了还原脱氯研究.负载型纳米Pd/Fe对PCE、TCE、1,1-DCE、VC和γ-HCH的还原脱氯符合准一级反应动力学方程,其反应速率常数分别为2.79 h-1、2.35 h-1、1.12 h-1、2.14 h-1和4.02 h-1.氯代烃降解过程中几乎没有中间产物生成,终产物主要为C2 H6和C2 H4,如对TCE进行降解时,生成的C2H6和C2 H4分别占总碳质量比的70%和10%.采用暴露在空气中24 h的负载型纳米Pd/Fe对PCE进行脱氯,8次循环后仍能对PCE快速完全降解,表明负载型纳米Pd/Fe的稳定性能良好.以γ-HCH为目标污染物对负载型纳米Pd/Fe的反应持久性进行了研究,200 h后负载型纳米Pd/Fe的反应性没有明显降低,表明负载型纳米Pd/Fe反应持久性能良好.温度对负载型纳米Pd/Fe的脱氯反应影响较大,测得各氯代烃脱氯反应的活化能均高于29 kJ·mol-1.对PCE、TCE进行了脱氯动力学模拟,模拟结果与试验数据基本吻合,表明负载型纳米Pd/Fe对氯代烃的脱氯,是连串、平行及多步骤反应的结合.     

双极液膜法可见光光催化降解染料废水

采用溶胶-凝胶法制备了Bi2O3-TiO2/Ti膜电极,X射线衍射(XRD)、X射线光电子能谱(XPS)、紫外-可见漫反射(DRS)和光电性能测试进行了表征,结果表明,Bi元素掺杂进入了TiO2催化剂,拓展了催化剂的光响应波长,使其在可见光下有较明显的光电响应.将Bi2O3-TiO2/Ti光阳极与Cu阴极组装成双极液膜反应器,在可见光下光催化处理活性艳红X-3B,得出当初始pH值为2.52,废水流量为80mL/min时,处理20mg/L活性艳红X-3B 150min,脱色率可达88%.双极液膜法可见光光催化的初步机理考察表明,光生电子自发由Bi2O3-TiO2表面转移到Cu电极表面,并在Cu电极表面直接还原染料,或与其表面液膜中的溶解氧反应生成H2O2,进而参与染料的氧化,由此可实现Bi2O3-TiO2/Ti的直接氧化和Cu阴极的直接还原和间接氧化的双极双效效果.     

Synthesis and enhanced visible-light responsive of C,N,S-tridoped TiO2 hollow spheres

C,N,S-tridoped TiO2 hollow spheres （labeled as C,N,S-THs） were synthesized using carbon spheres as template and C,N,S-tridoped TiO2 nanoparticles as building blocks. The structure and physicochemical properties of the catalysts were characterized by X- ray diffraction （XRD）, scanning electron microscopy （SEM）, UV-Vis diffuse reflectance spectrum （DRS）, N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy （XPS） and Photoluminescence emission spectroscopy （PL）. The results showed that the hollow spheres had average diameter of about 200 nm and the shell thickness was about 20 nm. The tridoped TiO2 hollow spheres exhibited strong absorption in the visible-light region. C,N,S-tridoped could narrow the band gap of the THs by mixing the orbit O 2p with C 2p, N 2p and S 3p orbits and shift its optical response from ultraviolet （UV） to the visible-light region. PL analysis indicated that the electron-hole recombination rate of TiO2 hollow spheres had been effectively inhibited when doped with C, N and S elements. The photocatalytic activities of the samples were evaluated for the degradation of X-3B （Reactive Brilliant Red dye, C.I. Reactive Red 2） aqueous solution under visible-light （λ 〉 420 nm） irradiation. It was found that the C,N,S-tridoped TiO2 hollow spheres indicated higher photocatalytic activity than commercial P25 and the undoped counterpart photocatalyst.     

Synergetic degradation of Methylene Blue through photocatalysis and Fenton reaction on two-dimensional molybdenite-Fe

The greatest problem in conventional Fenton reaction is the slow production of ROS（reactive oxygen species） because of the inefficient Fe³⁺/Fe²⁺ conversion. Based on the extraordinary photo-response property of two-dimensional molybdenite（2DM）, photogenerated electrons can be easy separated to accelerate the regeneration of Fe²⁺ . In this work, Fe²⁺ -anchored2DM（2DM-Fe） was prepared and used as a heterogeneous Fenton catalyst to investigate the degrada...     

常温高pH条件下与厌氧氨氧化匹配的亚硝化研究

在常温条件下实现了与厌氧氨氧化匹配的亚硝化过程,并考察了高pH对亚硝化的影响效果。试验采用实际生活污水和稳定运行的序批式活性污泥法(SBR)反应器,通过控制温度、p H考察NH+4-N与NO-2-N的对应变化情况。温度为28℃时,亚硝化效果良好,NO-2-N累积率达到93.45%;温度为26℃时,出水NH+4-N/NO-2-N为1∶1.3能够满足后续厌氧氨氧化进水的要求。pH较高时,可以通过中和亚硝化产生的H+以及FA与FNA对硝化细菌的抑制作用实现稳定的亚硝化。