水热法制备BiVO4及其可见光催化降解糖蜜酒精废水

以Bi(NO3)3•5H2O为铋源,NH4VO3为钒源,采用简单的水热法制备了BiVO4 光催化剂,并用X-射线衍射(XRD)、扫描电子显微镜(SEM)、红外光谱(IR)和紫外-可见光漫反射光谱(UV-vis)对产品进行了结构表征。同时,在BiVO4光催化降解糖蜜酒精废水反应中考察了催化剂用量、通氧量、溶液pH值、双氧水用量及光照强度对糖蜜酒精废水脱色率的影响。实验结果表明,水热产品属于单斜晶系BiVO4,其带隙能为2.398 eV,并具有良好的可见光催化活性。当降解经30倍稀释的糖蜜酒精废水,BiVO4添加量为3.0 g•L−1 ,通氧量为120 L•h-1,助氧化剂H2O2添加量为9 %,不改变废水pH值,在400W镝灯离液面11cm照射反应180 min的条件下,糖蜜酒精废水的脱色率为88.60 %,COD去除率为25.84%,而添加5g•L−1的FeSO4•7H2O后其脱色率和COD去除率分别提高到90.90 %和91.26%。单斜晶型BiVO4晶体的可见光催化糖蜜酒精废水过程符合一级动力学反应。     

Photocatalytic degradation of Acid Blue 62 over CuO-SnO2 nanocomposite photocatalyst under simulated sunlight

The novel CuO-SnO2 nanocomposite oxide photocatalysts were prepared by simple co-precipitation method, and characterized by X- ray diffraction, transmission electron microscopy, N2 adsorption-desorption measurement and UV-Vis diffuse reflectance spectroscopy. The photocatalytic activities of CuO-SnO2, evaluated using the photodegradation of Acid Blue 62 as a probe reaction under the irradiation of Xenon light, were also found to be related to the calcination temperature and the molar ratio of Cu to Sn. The maximum photocatalytic activity of the CuO-SnO2 photocatalyst was observed to be calcined at 500~C for 3 h （the molar ratio of Cu to Sn was 1：1） due to the sample with good crystallization and high surface area. It also showed much higher photocatalytic activity in treatment dye wastewater under simulated sunlight irradiation compared to Degussa P25 TiO2.     

负载型纳米TiO2/AC对偶氮染料的光催化降解研究

以钛酸四丁酯和粒状活性炭(AC)为主要原料,采用溶胶-凝胶-浸渍法制备出负载型纳米TiO2/AC催化剂.在流化床反应器中分别对2种典型的偶氮类染料橙黄G、活性艳红X-3B模拟废水进行了光催化降解研究,探讨了pH值、外加氧化剂对光催化降解率的影响,并对催化剂进行了回收再生利用试验.结果表明,TiO2/AC催化剂具有良好的光催化活性、吸附特性及可再生性,60 min后对2种染料反应的光催化降解率分别可达到99.71%和97 12%,反应180 min后的TOC去除率分别达到81.54%和81.99%;反应后TiO2/AC催化剂回收率大于95%,经焙烧再生后对橙黄G反应60 min的光催化降解率仍高达95.93%.     

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.     

Photocatalytic degradation of dye effluent by titanium dioxide pillar pellets in aqueous solution

Photocatalytic oxidation (PCO) process is an effective way to deal with organic pollutants in wastewater which could be difficult to be degraded by conventional biological treatment methods. Normally the TiO2 powder in nanometre size range was directly used as photocatalyst for dye degradation in wastewater. However the titanium dioxide powder was arduous to be recovered from the solution after treatment. In this application, a new form of TiO2(i. e. pillar pellets ranging from 2.5 to 5.3 mm long and with a diameter of 3.7 mm) was used and investigated for photocatalytic degradation of textile dye effluent. A test system was built with a flat plate reactor(FPR) and UV light source(blacklight and solar simulator as light source respectively) for investigating the effectiveness of the new form of TiO2. It was found that the photocatalytic process under this configuration could efficiently remove colours from textile dyeing effluent. Comparing with the TiO2 powder, the pellet was very easy to recovered from the treated solution and can be reused in multiple times without the significant change on the photocatalytic property. The results also showed that to achieve the same photocatalytic performance, the FPR area by pellets was about 91% smaller than required by TiO2 powder. At least TiO2 pellet could be used as an alternative form of photocatalyst in applications for textile effluent treatment process, also other wastewater treatment processes.     

H_3PW_(12)O_(40)/TiO_2可见光下光催化降解孔雀石绿的研究

以钛酸四丁酯为原料,采用溶胶-凝胶法制备TiO2光催化剂,然后浸渍法制备出H3PW12O40/TiO2复合型光催化剂,并运用XRD、SEM、FT-IR和DRS对催化剂进行表征和分析.研究了可见光光照下H3PW12O40/TiO2对孔雀石绿降解的光催化活性,考察了浸渍量、催化剂用量、底物浓度、pH值对光催化降解率的影响.实验表明,在pH=5条件下,H3PW12O40/TiO2催化剂用量为0.3g.L-1,浓度为10mg·mL-1的孔雀石绿溶液在2L·min-1曝气、300W可见光下光照4h后光催化降解率为78%,比TiO2光催化活性提高了24%.     

不同pH下糖蜜废水的厌氧产酸发酵类型及微生物群落结构解析

为寻求厌氧产酸发酵反应器的适宜控制参数和微生物学机制,以ACR(厌氧接触式发酵制氢反应器)为试验平台,通过分阶段调控反应器的pH,考察不同pH下ACR系统的产酸发酵类型和产氢性能,并采用聚合酶链式反应-变性梯度凝胶电泳(PCR-DGGE)技术对微生物群落结构进行了解析.以糖蜜废水为基质,以城市污水厂剩余污泥为种泥,在污泥接种量(以MLVSS计)为3.58 g/L、进水ρ(COD_Cr)为5 000 mg/L、HRT为12 h条件下,分别考察了系统在pH为6.0～6.5、5.5～6.0、5.0～5.5、4.5～5.0条件下的运行特性.结果表明,在pH为4.5～5.0时,系统中以Ethanoligenens harbinense YUAN-3为代表的产氢菌群占优,呈现典型的乙醇型发酵特征,活性污泥表现出的产氢性能最佳,其氢气转化率和污泥的比产氢速率分别为1.9 mol/mol和7.8 mmol/(g·d).在pH为5.5～6.5、5.0～5.5的条件下,Clostridium tyrobutyricum strain A1-3、Propionibacterium sp.B2M2分别成为优势菌群,系统分别呈现出丁酸型发酵、混合酸发酵类型.研究显示,随着pH的改变,系统内的产酸发酵菌群随之发生更迭,在不同pH控制水平下形成不同的顶级微生物群落结构,进而使得系统呈现出不同发酵类型和产氢性能.      

Recent advances based on the synergetic effect of adsorption for removal of dyes from waste water using photocatalytic process

The problem of textile dye pollution has been addressed by various methods,mainly physical,chemical,biological,and acoustical.These methods mainly separate and/or remove the dye present in water.Recently,advanced oxidation processes(AOP)have been focused for removal of dye from waste water due to their advantages such as ecofriendly,economic and capable to degrade many dyes or organic pollutant present in water.Photocatalysis is one of the advance oxidation processes,mainly carried out under irradiation of light and suitable photocatalytic materials.The photocatalytic activity of the photocatalytic materials mainly depends on the band gap,surface area,and generation of electron–hole pair for degradation dyes present in water.It has been observed that the surface area plays a major role in photocatalytic degradation of dyes,by providing higher surface area,which leads to the higher adsorption of dye molecule on the surface of photocatalyst and enhances the photocatalytic activity.This present review discusses the synergic effect of adsorption of dyes on the photocatalytic efficiency of various nanostructured high surface area photocatalysts.In addition,it also provides the properties of the water polluting dyes,their mechanism and various photocatalytic materials;and their morphology used for the dye degradation under irradiation of light along with the future prospects of highly adsorptive photocatalytic material and their application in photocatalytic removal of dye from waste water.     

片状Bi2O3的制备及其光催化性能

利用化学沉淀法,分别以Bi（NO₃）₃·5H₂O为铋源、稀HNO₃为溶剂和HTMA为沉淀剂,制备出片状Bi₂O₃光催化剂.利用SEM、XRD和BET分别对制备的Bi₂O₃形貌、厚度、晶型和比表面积进行表征,并借助紫外可见漫反射和光化学反应仪对材料的光催化性能进行测试.结果表明：制备的片状Bi₂O₃光催化剂形貌较好,厚度均一,a-Bi₂O₃晶型,对可见光的吸收较强,表现出较好的光催化性能.在模拟可见光300W下,3.0h后Bi₂O₃光催化剂对四环素溶液的降解率可以达到82.6%,远远高于市售纳米Bi₂O₃颗粒.     

钒酸银改性二氧化钛制备及其可见光光催化性能研究

通过水热法将钒酸银掺杂负载到二氧化钛上,制备了一种新型改性二氧化钛复合光催化剂.利用扫描电镜、透射电镜、X射线衍射、X射线光电子能谱和紫外-可见光漫反射技术对催化剂进行了表征,以亚甲基蓝为目标降解物,考察了该催化剂在可见光下的光催化活性、稳定性等,探讨分析了反应机理.结果表明,可见光下该催化剂降解亚甲基蓝的反应过程符合一级反应动力学,其降解速率常数为0.009min-1,是二氧化钛P25的3倍,且3次回收利用后降解率仅下降4.8%,仍具有较高活性.钒酸银与二氧化钛形成耦合异质结,在可见光照射下,光生电子由钒酸银导带传到二氧化钛导带上,空穴则聚集在钒酸银价带上,产生的h+、·OH等是降解亚甲基蓝的主要物质,电子与受体的结合是反应的限速步骤.     

磁性微球负载光催化剂制备及处理造纸废水研究

采用溶胶-凝胶法,在磁性颗粒表面包覆TiO2,制备了易于固液分离的磁载光催化剂TiO2/SiO2/Fe3O4,通过XRD和TEM对产物的晶体结构、晶粒大小、形貌进行了表征,讨论了焙烧温度、焙烧时间、催化剂用量和光照时间等对TiO2光催化剂处理造纸废水的影响。结果表明:焙烧温度为500℃、焙烧时间3.5h时,光催化活性最高;催化剂用量为2.5g/L,光照时间4h时TiO2降解造纸废水的能力最强。     

流化床光催化氧化处理印染废水中试研究

设计了1种流化床光催化氧化中试处理系统,制备了一种负载型TiO₂光催化剂.以高压汞灯为光源,选用难降解偶氮染料4BS和高分子化学浆料CMC配制的模拟印染废水为处理对象,考察了初始pH值、初始浓度以及光助催化剂H₂O₂浓度、Fe₃₊浓度对光催化降解效果的影响,并对有关的光催化反应动力学规律进行了探讨.结果表明,本工艺系统对配制的印染废水有较好的处理效果,光照74min色度去除率可超过80%,光照150min COD去除率可超过70%,BOD₅/COD可提高至0.4以上.     

磷掺杂的介孔石墨相氮化碳光催化降解染料

将三聚氰胺、三聚氰胺聚磷酸盐和SBA-15热共聚成功制备了磷掺杂的介孔石墨类氮化碳（P-mpg-C₃N₄）,并通过场发射扫描电子显微镜（FESEM）、X射线衍射光谱（XRD）、傅里叶转换红外光谱（FT-IR）、X射线光电子能谱（XPS）、场发射扫描透射电镜能谱（EDS）和紫外可见光漫反射光谱（UV-vis-DRS）等方法对催化剂形貌结构和光学性能进行了表征.结果表明,磷元素成功地掺杂在氮化碳的结构上,呈均匀分布,相对于石墨相氮化碳（g-C₃N₄）,其比表面积可达198.3m²/g,并因此提供大量的活性位点而提高光催化活性.P-mpg-C₃N₄对亮丽春红5R的光催化降解速率是g-C₃N₄的31.3倍,其光催化性能增强的机理是禁带宽度的减小,可见光吸收范围从440nm延伸到了460nm,其次,改性后的光催化剂能显著抑制光生电子空穴对的复合,从而有更多的活性点位以及活性物种能参与光催化反应过程.循环实验表明,经过5个循环降解后光催化性能仍保持在初始状态的91.67%,表明P-mpg-C₃N₄具有很好的光催化稳定性.     

新型纳米材料光催化反应器研究

为了充分发挥纳米材料的光催化性能,研制了一种带有旋转叶片且可负载光催化纳米材料的光催化反应器.并以制备的纳米TiO2/硅藻土复合材料作为光催化剂、TNT生产废水为处理对象,考察了催化材料附载量、废水浓度和多次重复使用对反应器催化降解效率的影响.结果表明:附载有光催化纳米材料的反应器经过6次6h重复使用,对TNT生产废水催化降解效率仍然保持在75%以上,远高于直接分散在废水中纳米材料的处理效率(47.25%),即多次重复使用并保持高降解效率;而且可较好地避免纳米光催化材料的团聚.避免因回收造成的纳米材料光催化效率降低以及回收不完全造成的水体二次污染等现象.     

糖蜜、淀粉与乳品废水厌氧发酵法生物制氢

采用连续流厌氧发酵法研究了糖蜜废水、淀粉废水与牛奶废水生物制氢,讨论了有机物中3大类物质的厌氧发酵产氢的可行性,并对几种底物的产氢稳定性进行了探讨.结果表明,糖蜜废水与淀粉废水都是较好的厌氧发酵法生物产氢底物,在3大类有机物中碳水化合物是目前技术条件下最具有可能性的原材料.在碳水化合物中,溶解性好的糖比溶解性差的淀粉在目前的技术条件下具有生物产氢可行性,而淀粉比溶解性糖更具有产氢前景.不同底物厌氧生物制氢的生态位范围有所不同,对于溶解性好的糖,稳定运行的工程控制参数为pH 4.5±0.3,而溶解性较差的淀粉废水为pH 4.0±0.2;厌氧发酵产氢的ORP值也随底物的不同而不同,但总体必须低于-220mV,在-300mV左右时较好.牛奶废水不适用于作为CSTR反应器中发酵法生物制氢底物.     

Response surface methodology analysis of the photocatalytic removal of Methylene Blue using bismuth vanadate prepared via polyol route

Visible-light driven photocatalyst bismuth vanadate (BiVO₄) photocatalyst was synthesized by the polyol route using ethylene glycol. The precipitate was washed, dried and calcined at 450℃ for 3 hr. The sample was characterized by X-ray diffractometry (XRD), field emission scanning electron microscopy (FE-SEM), zeta potential, surface area (BET method) and band gap energy via diffuse reflectance spectroscopy (DRS). The synthesized BiVO₄ has a monoclinic phase with a surface area of 4.3 m²/g and a band gap energy of 2.46 eV. A majority of the particles were in the range of 90-130 nm as obtained from the particle size distribution histrogram. The efficiency of the sample as a visible-light driven photocatalyst was examined by photodegrading Methylene Blue (MB). The effects of some operational photodegradation parameters such as mass loading, initial dye concentration and pH were also examined. Experimental design methodology was applied by response surface modeling and optimization of the removal of MB. The multivariate experimental design was employed to develop a quadratic model as a functional relationship between the percentage removal of MB and three experimental factors (BiVO₄ loading, MB initial concentration and pH). The percentage removal of MB approached 67.21% under optimized conditions. In addition, a satisfactory goodness-of-fit was achieved between the predictive and the experimental results.     

AgCl/ZnO/GO光催化降解甲基橙的性能研究

为了提高ZnO对偶氮染料污染物的光催化降解效率,以AgCl和GO（氧化石墨烯）作为改性剂,通过水热法和化学沉积法制备了AgCl/ZnO/GO光催化材料,采用XRD、SEM、XPS、UV-Vis方法对材料的物相组成、微观形貌及光学特性进行表征;以MO（甲基橙）为目标污染物,探究其在可见光下的催化降解性能,考察AgCl含量、催化剂投加量、pH对其可见光催化活性的影响.结果表明:①AgCl的沉积和GO的负载增强了ZnO对可见光的响应能力,提高了光生电子-空穴产生、分离效率,同时增加了材料的分散性及其对MO的吸附率,因此AgCl/ZnO/GO光催化材料对MO有良好的可见光催化降解效率.②AgCl/ZnO/GO对MO的催化降解效率随着AgCl含量的增加而增加,随着催化剂投加量的增加呈先增后降的趋势,溶液pH对其降解效果有一定影响,但不显著.③当AgCl/ZnO（二者物质的量的比）为2:1、AgCl/ZnO/GO投加量为70 mg、pH为7、室温下经过可见光照射50 min后,AgCl/ZnO/GO对质量浓度为10 mg/L的MO的降解率可达98.93%;此外,该催化剂重复使用4次对MO仍具有88%的去除率,显示出良好的稳定性.因此,AgCl/ZnO/GO是一种高效、稳定的可见光光催化剂,在废水净化方面具有良好的应用前景.      

Understanding the multifunctionality in Cu-doped BiVO4 semiconductor photocatalyst

A visible light-induced, Cu-doped BiVO_4 photocatalyst was synthesized by a microwave hydrothermal method. The photocatalytic efficiency was investigated in the degradation of model water pollutants like Methylene Blue(dye) and ibuprofen(pharmaceuticals), as well as the inactivation of Escherichia coli(bacteria). The Cu-doped BiVO4 samples showed better efficiency than undoped BiVO_4, and the 1 wt.% Cu-doped BiVO_4 sample showed the best efficiency. The degradation of Methylene Blue reached 95%, while the degradation of ibuprofen reached 75%, and the inactivation of E. coli reached 85% in irradiation with visible light. The appearance of additional absorption band shoulders and widening of the optical absorption in the visible range makes the prepared powder an efficient visible light-driven photocatalyst. Moreover, the formation of an in-gap energy state just above the valance band as determined by density functional theory(DFT) first principle calculation, facilitates the wider optical absorption range of the doped system. Similarly, this in-gap energy state also acts as an electron trap, which is favorable for the efficient separation and photoexcited charge carriers' transfer process. The formation of oxygen vacancies due to doping also improved the separation of the charge carrier, which promoted the trapping of electrons and inhibited electron hole recombination, thus increasing the photocatalytic activity. No decrease in the efficiency of the 1 wt.% Cu-doped BiVO_4 photocatalyst in the degradation of ibuprofen over three consecutive cycles revealed the stability of the photocatalyst towards photocorrosion. These findings highlight the multifunctional applications of Cu-doped BiVO_4 in wastewater containing multiple pollutants.     

Pd/TiO2光催化苯甲酸水溶液产氢性能研究

为了探讨在光催化分解水(下称光解水)制氢反应中含苯有机废水作为牺牲剂的可行性,以光沉积法制备了Pd/TiO₂〔w(Pd)为0.5%〕模型催化剂,并且通过XRD(X射线衍射)、BET(N₂物理吸附)、TEM(透射电镜)、XPS(X射线光电子能谱)和UV-vis DRS(紫外-可见漫反射吸收光谱)等表征手段考察了催化剂的微观结构及性质, 使用泊菲莱Labsolar-Ⅲ AG系统评价了苯甲酸、邻苯二甲酸、间苯三甲酸作为牺牲剂的光催化性能. 结果表明:引入的Pd以Pb0和Pb2+高度分散在TiO₂基底表面,未改变TiO₂的晶体结构;与TiO₂相比,Pd/TiO₂具有更大的比表面积、更小的孔径和更强的光吸收性能. 苯甲酸、邻苯二甲酸、间苯三甲酸光解水产氢速率分别为4.264、6.429和5.400 mmol/(g·h),分别为空白处理〔无牺牲剂,0.733 mmol/(g·h)〕的5.8、8.8、7.4倍. 依据乙酸和三氟乙酸的光解水产氢速率数据及结构特征,初步探讨了苯甲酸参与价带空穴氧化反应的机理,发现光解水产氢速率的大小与苯甲酸牺牲剂的还原性强弱、羧基个数以及空间位阻有关,表现为牺牲剂发生photo-Kolbe脱羧反应越容易、羰基数目越多、空间位阻越小,其光解水产氢速率越高. 未来应进一步探寻高效、稳定的模型牺牲剂,以应用于氢能源生产研究.      

Ag-AgIO3改性BiOI光催化剂湿法脱除气态单质汞

采用沉积沉淀-光还原法制备了不同AgIO₃含量的BiOI光催化剂,利用X射线衍射、N₂吸附-脱附、扫描电子显微镜、X射线光电子能谱、紫外-可见漫反射光谱和电子自旋共振对其物理化学结构进行表征,在光催化反应器上研究了AgIO₃负载量、光照、溶液温度、pH值、SO₂和NO对气态单质汞（Hg⁰）去除性能的影响.结果表明,与BiOI相比,Ag-AgIO₃改性后光催化剂的脱汞性能大幅提高.当AgIO₃负载量为4wt.%时,光催化剂的脱汞效率高达98%.与NO相比,SO₂对脱汞性能的抑制作用更大.由于Ag和AgIO₃在BiOI表面的高度分散性,Ag-AgIO₃（4%） BiOI的可见光吸收性能明显提高.荧光灯辐照与Ag-AgIO₃/BiOI光催化剂协同会产生大量的活性物种.在Ag-AgIO₃/BiOI光催化剂的高效脱汞体系中,超氧阴离子自由基（·O₂^-）为最主要的活性物质,而空穴（h⁺）和羟基自由基（·OH）次之.