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水热法生长二氧化钛纳晶及在染料敏化太阳能电池板的应用1 引言1991 年瑞士学者Gratzel 等在Nature 上发表文章,提出了一种新型的以染料敏化二氧化钛纳晶薄膜为光阳极的太阳能电池,其具有制作简单、成本低廉、效率高和寿命长等优点,光电转换效率目前可以达到11%以上,因此成为新一代太阳能电池的主要研究发展方向[1-4]。染料敏化太阳能电池的光电转换效率的提高要归功于其独特的纳晶多孔薄膜电极,其可以使电子在薄膜中有较快的传输速度,且具有足够大的比表面积,能够吸附大量的染料,并且与染料的能级相匹配。所以因对染料敏化太阳能电池的复杂的作用,许多科学工作者致力于制备功能和性能良好的TiO2 纳晶多孔薄膜电极[5, 6]。在纳晶TiO2 的三种晶型中,锐钛矿相的光电活性最好,最实用于染料敏化太阳能电池中,所以在制备纳晶TiO2 时,金红石相和板钛矿相纳晶应该尽量避免。对TiO2 纳晶的生长,许多研究者开始在水热法中采用有机碱做胶溶剂来制备TiO2 纳晶[7-9]。Yang 用三种有机碱做胶溶剂制备了粒经和形貌不相同的TiO2 纳晶,其结果证明了有机碱的加入对纳晶粒子大小、形貌及表面积等有一定影响[10]。但是,如何制备晶型和形貌都能满足于染料敏化太阳能电池的要求却很少讨论。在本章中,采用水热法基础上,分别使用三种有机碱四甲基氢氧化铵(TMAOH)、四乙基氢氧化铵(TEAOH)、四丁基氢氧化铵(TBAOH)做胶溶剂来制TiO2 备纳晶并应用于染料敏化太阳能电池中并研究了制备条件的不同对纳晶形貌、粒径大小及电池光电性能的影响。2 实验主要药品和仪器钛酸四正丁酯、异丙醇、聚乙二醇20,000、碘、碘化锂、4-叔丁基吡啶(TBP)、OP乳化剂(Triton X-100)(AR,均购于中国医药集团上海化学试剂公司);敏化染料(cis-[(dcbH2)2Ru(SCN)2],SOLARONIX SA.);四甲基氢氧化铵(TMAOH)(25 %)、四乙基氢氧化铵(TEAOH)(20 %)、四丁基氢氧化铵(TBAOH)(10 %) (均购于中国医药集团上海化学试剂公司);可控温磁力搅拌器(C-MAG HS4,德国IKA);马弗炉(上海实验电炉厂);100 W 氙灯(XQ-100 W,上海电光器件有限公司);导电玻璃基片(FTO,15 Ω/cm2,北京建筑材料研究院);X 射线粉末衍射仪(XRD) D8-advance(Bruker 公司);扫描电子显微镜(SEM)S-3500N(日本日立公司);透射电镜(TEM)JEM-2010(日本);红外光谱分析仪Nicolet Impact 410 spectrometer;紫外–可见分光光度计UV-Vis 3100 (Shimadzu corporation, Japan)。3 实验部分 纳晶TiO2 的制备根据文献的制备方法[6-11],把钛酸四正丁酯与等体积的异丙醇混合均匀并逐滴加入到蒸馏水中并不断的搅拌30分钟([H2O]/[Ti(OBu)4] = 150),过滤并用水和乙醇溶液洗剂2-3次。在强烈搅拌下,把所得到的沉淀加入到pH=的含有有机碱的溶液中,在100 °C搅拌24小时,得到半透明的胶体。将得到胶体装入高压釜(填充度小于80%)。在200 oC水热处理12小时。水热处理后,得乳白色混合物并伴有鱼腥味,这表明有机碱分解为了胺类化合物。将高压釜处理后的TiO2胶体连同沉淀一起倒入烧杯,经50 oC浓缩至原来的1/5,加入相当于TiO2量20%-30%的聚乙二醇20,000及几滴Triton X-100,搅拌至均匀,得稳定的TiO2纳晶浆体。 纳晶薄膜电极的制备将洗净的导电玻璃四边用透明胶带覆盖,通过控制胶带的厚度和胶体的浓度来控制膜的厚度[12],中间留出约1×1 cm2空隙,将在酸性条件下制备的小粒径的纳晶TiO2胶体用玻片均匀的平铺在空隙中。空气中自然晾干后,在马弗炉中升温至450 ?C热处理30分钟,使TiO2固化并烧去聚乙二醇等有机物,冷却至80 ?C,经过仪器测量,薄膜的平均厚度在6微米左右。将获得的纳晶多孔薄膜浸泡于N3染料溶液中24小时,使染料充分地吸附在TiO2上,取出后用乙醇浸泡3-5分钟,洗去吸附在表面的染料,在暗处自然晾干,即得到染料敏化的纳晶多孔TiO2薄膜电极。首先按上文所述制备纳晶多孔薄膜,制备的薄膜平均厚度在微米左右,将其重新用透明胶带覆盖,把用TMAOH做胶溶剂的条件下制备的大粒径的纳晶TiO2浆体用玻片均匀的平铺在空隙中。空气中自然晾干后,重新在马弗炉中升温至450 ?C热处理30分钟,反射层的纳晶薄膜的平均厚度控制在微米左右,热处理后即得双层纳晶薄膜。浸泡染料后即得双层纳晶薄膜电极。 DSSC 的组装以染料敏化纳晶多孔TiO2薄膜电极为工作电极,以镀铂电极为对阴极[13],将染料敏化电极与对阴极用夹子固定,在其间隙中滴入以乙腈为溶剂、以 mol/L LiI+ mol/L I2+ TBP为溶质的液态电解质,封装后即得到染料敏化太阳能电池。 光电性能测量采用100 W氙灯作为太阳光模拟器,其入射光强Pin为100 mW/cm2。在室温下进行测量,记录其短路电流ISC和开路电压VOC,并应用公式计算其填充因子ff和光电转换效率η。 表征与分析采用 D8-advance 型X 射线粉末衍射仪测定TiO2 的晶体结构,测试条件为:Cu Kα(λ= ?),电压:40 KV,电流:40 mA。扫描速度:6?/min,扫描范围:10?-80?。采用KBr 压片法测量样品的红外光谱,测试条件:400-4000 cm-1,软件:OMNIC ,扫描次数30 次。采用JEM-2010(日本)型透射电子显微镜(TEM)观察TiO2 纳晶的表面形貌及粒径大小。用紫外-可见分光光度计(UV-3100)测试不同粒径TiO2 纳晶多孔薄膜电极吸附染料的吸光度。TG 的升温速度:10 ℃/min,范围:室温至1000 ℃,测试仪器:SDT 2960 同步DSC-TGA 装置 (USA TA 设备)。4 结果与讨论 有机碱对TiO2 纳晶的形貌和粒径的影响Sugimoto 和他的合作者们研究了影响TiO2 纳晶生长的一些因素,其中pH 的值、有机碱的烷基链的长短、水热的温度以及水热的时间等因素都对TiO2 纳晶颗粒的大小和形貌有很大的影响[14-17]。通过研究发现,四烷基有机碱作为模板来控制TiO2 纳晶的形貌和大小。所以可以使用不同的有机碱来制备适合于染料敏化太阳能电池光电传输的晶型完整并具有较大的比表面积的TiO2 纳晶。是在不同的有机碱做胶溶剂时制备的TiO2 纳晶的TEM 图,a 图是采用TMAOH 做胶溶剂,b 图是采用TEAOH 做胶溶剂,c 图是采用TBAOH 做胶溶剂。从图中可以看出,在相同pH 值下,不同的有机碱做胶溶剂时,制备的纳晶明显不同,这说明胶溶剂对TiO2纳晶的粒径大小和形貌有很大的影响,而且随着有机碱胶溶剂烷基链的加长,TiO2 纳晶的粒径减小,并且粒子为多面体。当用TMAOH 做胶溶剂时,制备的TiO2 纳晶的粒子多为四方体,颗粒宽12-20 nm,粒子长20-40 nm,如图1a 所示。当用TEAOH 做胶溶剂时制备的TiO2 纳晶的粒子颗粒不均匀,而且形貌也不规则有多面体形的也有四面体形的,粒子宽度8-10 nm,长度10-25 nm,如图1b 所示。而当有机碱的烷基链长从两个碳原子增加到四个碳原子时,即用TBAOH 用作胶溶剂时制备的纳晶颗粒粒子大小较均匀而且形貌也较规则,多为正方体,粒子大小一般在5nm 左右,如图1c 所示。在TiO2 纳晶的水热生长过程中,有机碱首先是吸附在TiO2 的晶核上,而烷基链的长短不同吸附的能力不同,吸附能力越大则就会阻碍纳晶的生长。研究发现[6],烷基链越长则有机碱吸附在晶核上的吸附力越大,则会阻碍晶体的生长,所以随着有机碱烷基链的长度的增加,纳晶颗粒在不断的减小;并且研究发现,胶溶剂的浓度不能太大,太大时制备的TiO2 纳晶就会出现严重的团聚现象[10]。 有机碱对TiO2 纳晶晶型的影响是用三种有机碱做胶溶剂时制备的TiO2 纳晶的XRD 图,a 是制备的TiO2 纳晶经过自然风干后的XRD,b 是制备的三种TiO2 纳晶经过50 °C 热处理30 分钟中后的XRD 图。从图2a 中可以看出,2θ = °是TiO2 纳晶锐钛矿的特征峰,但是还有一些其它的杂峰,这些杂峰证明是有机胺类化合物的峰。当把制备的纳晶经过450 °C 热处理30 分钟中后,a 图中的杂峰就消失,TiO2 在2q =°,°,°,°,°和°的衍射峰的d 值均与标准PDF 卡片锐钛矿型TiO2 衍射峰相符,说明所制备的TiO2 的晶型为锐钛矿,没有金红石相和板钛矿相出现,制备的为纯的锐钛矿相TiO2 纳晶。在传统水热方法中,采用硝酸做胶溶剂,制备的纳晶TiO2 中,含有少量的金红石相和板钛矿相,而这两种的光电性能较差,影响染料敏化太阳能电池的光电转换效率。而用有机碱做胶溶剂制备的TiO2 纳晶可满足染料敏化太阳能电池中对锐钛矿相的要求。随着有机碱烷基链的增加,样品的特征衍射峰宽逐渐变大,并且衍射峰值逐渐减小,这表明制备纳晶颗粒不断减小,这与TEM 的结果一致。 TiO2 纳晶的热稳定性分析是用三种有机碱制备的TiO2 纳晶的红外光谱图,(a) 是制备的纳晶粉末在80 °C 烘干24 小时,(b)是制备的纳晶粉末在450 °C 热处理1 小时,光谱范围是400-4000 cm-1。从红外光谱图可知,三种纳晶红外图谱相近。图3(a)中出现了有机化合物的一些键如C-H, N-H,和O-H 等键,但随着在450 °C 热处理1 小时后,这些化合键就消失了,而TiO2 薄膜的红外谱图中主要有Ti-O-Ti 键伸缩振动峰在500cm-1 附近,没有出现宽的吸收带,如图3(b)所示,这一结果与文献中的结果相一致[7]。这说明在有机碱条件下制备的TiO2 纳晶在经过450 °C后为稳定的锐钛矿相,吸附在其表面的有机物分解完全。从XRD 的结果也可以得出(图 3b),所有有机化合物在经过450 °C 热处理后都消失完全了,这说明二氧化钛化合物在高于450 °C热处理后,可以晶化为稳定的锐钛矿相TiO2 纳晶。是用有机碱做胶溶剂时制备的TiO2 纳晶粉末热稳定性的TG 分析。这些纳晶粉末是在105 °C 下烘干24 小时,而没有进行任何热处理的。从图中可以看出,有两个失重过程。第一个过程是100~250 °C 之间的明显失重,可以认为是失去了吸附在纳晶粉末表面的水分子和一些醇。第二个过程是250~400 °C 之间的失重,是因为粉体中吸附的有机物成份的失去。有机物与制备的氧化物之间有很强的键和作用,这些有机物包裹着氧化物,当温度达到400 °C 时,这些键和作用才会消失,有机物完全分解,这说明有机物与纳晶颗粒之间的力结合不是太大不影响纳晶的晶化。另外发现,在不同有机碱胶溶剂下制备的纳晶粉末的失重情况明显不同,在采用TBAOH 做胶溶剂时的失重明显要高于使用TMAOH 做胶溶剂时的,这说明前者表面吸附了更多的有机物。吸附有机物的量不同,表明制备的纳晶粉末的形貌和粒径大小也明显不同[14],这与TEM 的结果一致,在采用TBAOH 做胶溶剂时制备的TiO2纳晶颗粒较小表面积较大,这就使吸附在纳晶表面的有机物就增多,所以在进行热分解时失重较多;而采用TMAOH 做胶溶剂时制备的TiO2 纳晶颗粒明显大许多,表面积又小所以吸附的有机物就会减小,所以在热分解时失重较少。从失重量的多少也可以简单分析出制备的纳晶颗粒和形貌的异同。用有机碱做胶溶剂来制备TiO2 纳晶,会对其晶型及其晶型的稳定性有一定的影响。图5 为有机碱TEAOH 做胶溶剂的条件下制备的TiO2 纳晶及其分别在300 °C,500 °C,700 °C,800 °C,900 °C 烧结1 小时样品的XRD 谱图。在TiO2 纳晶的晶型中,峰位于2θ=°是锐钛矿相的特征衍射峰,峰位于2θ=°是金红石相的特征衍射峰。从图中可知,TiO2 纳晶在800 °C 烧结前,晶型没有发生变化。在800 °C 烧结之后,才出现了金红石相晶型,这一结果与Young 等人的研究结果一致[18]。据报道在酸性条件下制备的TiO2 纳晶,在烧结温度达600 °C 时,锐钛矿晶型就开始向金红石晶型转变[19]。而用有机碱TEAOH 做胶溶剂制备的TiO2 纳晶从锐钛矿相向金红石相转变的温度有所提高,这说明用有机碱TEAOH 做胶溶剂制备的TiO2 纳晶热稳定性提高了,这一稳定性说明,可以对锐钛矿型TiO2 纳晶在较高的温度下进行烧结,而不改变其晶型,即没有金红石型纳晶出现。 BET 和吸附染料能力的研究用不同的有机碱做胶溶剂所制备的TiO2 纳晶粉的表面积进行分析,实验得出,在使用有机碱TMAOH 做胶溶剂时制备的TiO2 纳晶粉的比表面积为66 m2·g-1,但是当使用TEAOH和TBAOH 做胶溶剂时,制备的TiO2 纳晶粉的比表面积为78 m2·g-1 和82 m2·g-1。这一结果与粒径越大比表面积越小相一致,颗粒大小如图1 所示,这说明颗粒越小比表面积越大。研究发现,吸附的染料(RuL2(SCN)2)的多少并不一定随着比表面积的增大而增大。为了研究用于染料敏化太阳能电池测试的TiO2 纳晶多孔薄膜吸附染料的多少,把敏化的电极在5 mL mol/L NaOH 溶液中让染料进行脱附,之后对染料的碱性溶液进行吸光度的分析,UV-vis 吸收光谱的结果如图5 所示。图中a、b 和c 三条曲线分别是采用TMAOH、TEAOH和TBAOH 做胶溶剂时制备的TiO2 纳晶。根据朗伯-比尔定律可知吸光度随浓度增加而增大,结果显示,采用TMAOH 做胶溶剂时制备的TiO2 纳晶吸收的染料最少,这与比表面积越小吸附的染料越少相吻合,但比其它两种纳晶的吸附量要少很多。虽然采用TBAOH 做胶溶剂时制备的TiO2 纳晶的比表面积比用TEAOH 做胶溶剂所制备的TiO2 纳晶的比表面积大,但是后者却比前者所吸附的染料多,这里可能的解释就是因其用TBAOH 做胶溶剂时制备的TiO2 纳晶的颗粒太小还不足10nm,所以用其制备的纳晶多孔薄膜太致密而使得吸附的染料减小。 染料敏化太阳能电池光电性能研究采用有机碱制备的三种不同形貌和粒径大小的TiO2 纳晶,并用其制备了敏化电极应用于染料敏化太阳能电池光电性能的研究,如图6 所示。表1 给出了三种不同电极的所组装的电池的短路电流、开路电压、填充因子和光电转换效率的值。在100 mW/cm2 光照条件下,三种电池的短路电流分别为、、 mA/cm2,开路电压分别为、、,填充因子分别为,光电转换效率分别达到了。从实验结果可知,采用有机碱TEAOH 制备的TiO2 纳晶所组装的电池的光电转换效率比其它两种电池的光电转换效率要高。可知,采用有机碱TEAOH 所制备的TiO2 所制备的电池的开路电压要比采用有机碱TMAOH 所制备的TiO2 所制备的电池的要低,但是其电池的短路电流和填充因子都要比其它两种有机碱所制备TiO2 所组装的电池要高。这可能是因为(1)用有机碱TEAOH 所制备的TiO2 纳晶粒经比较适中,制备的多孔薄膜粒子与粒子之间结合比较紧密,这样就提高了电子在薄膜中的传播速度;(2)较其它两种多孔薄膜吸附的染料要多,研究表明吸附的染料的量与所产生的光电流成正比,吸附的染料越多,则产生的光电流越大,用有机碱TEAOH 做胶溶剂所制备的TiO2 多孔薄膜所吸附的染料最多,所以用其所组装的染料敏化太阳能电池的短路电流最高,电池的光电转换效率也达到最好。5 结论本章采用了钛酸四正丁酯为原料,以三种有机碱做胶溶剂来制备TiO2 纳晶,以三种制备的敏化的纳晶多孔薄膜为电极组装了染料敏化太阳能电池,并对其进行了电池光电性能的测试。研究了这三种有机胶溶剂对TiO2 纳晶晶体生长的影响,采用三种不同烷基链的有机碱做胶溶剂制备的纳晶形貌和大小有很大的不同,研究发现,随着烷基链的加长,纳晶的形貌开始变得规整,粒径也减小,但是有机碱的浓度不能太大,浓度过高时,会使制备的纳晶出现团聚,所以在使用有机碱做胶溶剂时,采用的是在pH= 的条件下制备的。通过热稳定性分析发现,吸附在TiO2 纳晶表面的有机碱在450 °C 热处理后,有机物分解完全,这说明在制备纳晶多孔薄膜时,有机物分解完全,多孔薄膜中为纯的TiO2 纳晶。因为三种TiO2纳晶形貌和大小不同所以制备的多孔薄膜吸附染料的量也不相同。实验发现采用有机碱TEAOH 做胶溶剂时制备的TiO2 的敏化电极吸附的染料最多,电池光电性能测试也显示用此TiO2 纳晶制备的电池开路电流达到 mA cm-2,光电转换效率达到,比其它两种电池的光电转换效率要高,这说明用有机碱TEAOH 做胶溶剂所制备的TiO2 纳晶的形貌和大小比其它两种有机碱胶溶剂制备的TiO2 更适合应用于染料敏化太阳能电池。更多毕业论文请到
二氧化钛(TO2)又称钛白粉,无毒、化学性质稳定,广泛用于化工、涂料、塑料、橡胶、纤维、造纸、油墨、搪瓷、电子等行业,是电子、化工、轻工、冶金等行业不可缺少的工业原料。二氧化钛主要晶型有金红石型(R)和锐钛型(A),两种晶型的二氧化钛硬度、密度、折光指数、光催化活性等都有所不同。
TiO2在浆料槽或酯化釜两处分别投料,切片中二甘醇含量差别很大,只要在浆料配制槽中加入TiO2总量的20%,切片中二甘醇的质量分数就可降至%以下。(2019·新课标)近年来,随着聚酯工业的快速发展,氯气的需求量和氯化氢的产出量也随之迅速增长。因此,将氯化氢转化为氯气的技术成为科学研究的热点。(1)Deacon发明的直接氧化法为:4HCl(g)+O2(g)=2Cl2(g)+2H2O(g)。
森态美TPX光触媒TPX系列产品是日本森态美窑业技术研究中心研究开发的在可视光条件下具有高性能分解反应的专利产品。在早期的光触媒TiO2水溶液的实际应用中发现,水溶液中的TiO2在与有机材的结合中会产生氧化分解反应,在一周左右会破坏基材并产生脱落,失去光触媒技术的应用效果,给消费者造成损失。于是现在,日本产业综合技术研究所,研制出新一代的高性能的TiO2光触媒水溶液,在二氧化钛纳米粒子表面加工上不具有活性反应的磷灰石等陶瓷成分,作为日本光触媒的高科技含量的核心技术。制造出混合型的复合二氧化钛光触媒水溶液,可以直接喷植在有机基材的表面,喷植在建筑物外壁有机涂料表面,其耐酸性,耐风化,防裂变,防褪色,温度越高其氧化分解反应越强,并具有永久性效果。在保持建筑物价值防污自洁,美化城市环境,净化大气污染方面得到了广泛的应用。
发1篇 氮氟掺杂二氧化钛光催化微囊藻毒素 (如有需要可以帮翻译一部分 此类文章在线翻译一般不准) 还有部分无法发出,把邮箱留下,我发给你。题目:Visible light-activated N-F-codoped TiO2 nanoparticles for the photocatalytic degradation of microcystin-LR in water正文:1. IntroductionThe development of nanotechnology for the synthesis ofnanomaterials is providing unprecedented opportunities to dealwith emerging environmental problems associated with watercontamination along with worldwide energy-related concerns [1].Currently, advanced oxidation technologies (AOTs) and nanotechnologies(AONs) have been extensively investigated for thedestruction of toxic and recalcitrant organic compounds andinactivation of microorganisms in water and air [2–12]. Titaniumdioxide (TiO2), a well-known semiconductor with photocatalyticproperties, is a widely used AON for water and air remediation [6–10]. It has proven to be highly effective in the nonselectivedegradation of organic contaminants due to high decompositionand mineralization rates. However, conventional TiO2 requiresultraviolet (UV) radiation (l < 400 nm) to overcome its wide bandgap energy ( eV for anatase phase) for photocatalyticactivation [4,11]. This is a technological limitation when aimingat implementation of large scale sustainable technologies withrenewable energy sources such as solar light, since UV radiationaccounts only for 5% of the total solar spectrum compared to thevisible region (45%) [12,13]. Several attempts have been directedtowards the development of modified TiO2 with visible lightresponse by dye sensitization, metal (Fe, Co, Ag) [14,15] andnonmental (N, F, C, S) [4,16–23] doping of the catalyst to reduceTiO2 band gab energy requirements for photocatalytic some metal doping approaches, the resulting visible lightphotocatalytic activity has some drawbacks including increase inthe carrier-recombination centers (electron–hole pair speciesgenerated after photo-excitation of the catalyst) and low thermalstability of the modified material [14]. Moreover, metal leachingand possible toxicity diminish the potential of employing metaldopedTiO2 for drinking and wastewater treatment applications. Amore successful approach involves nonmetal doping of doping of TiO2 for visible-light driven photocatalysisrevealed band gap narrowing from the mixing of nitrogen 2pstates with oxygen 2p states on the top of the valence band atsubstitutional lattice sites in the form of nitride (Ti–N) oroxynitride (Ti–O–N). A different arrangement is the formation ofoxyanion species at the interstitial lattice sites creating localizedintergap states [24]. Both configurations make it possible to shiftthe optical absorption towards visible light, thus, allowingphotocatalytic activity in the visible region [11,22,23]. Fluorinedoping is also effective to induce modifications of the electronicstructure of TiO2 by the creation of surface oxygen vacancies due tocharge compensation between F and Ti4+ but without producing asignificant change in the optical absorption of TiO2 [21]. Moreover,codoping of TiO2 with nitrogen and fluorine has demonstrated highphotocatalytic activity in the visible region with beneficial effectsinduced by both dopants [25–27]. Huang et al. confirmed strongvisible-light absorption and high photocatalytic activity of N-FTiO2for p-chlorophenol and Rhodamine B degradation undervisible light irradiation [26]. Xie et al. effectively decomposedmethyl orange with visible light-induced N-F-TiO2 photocatalyst[27]. Both attributed their findings to the synergistic effect ofnitrogen and fluorine addition to nonmetal doping, structural properties of TiO2 areof significant importance to enhance its physicochemical propertiesand photocatalytic response. For instance, the use of self-assemblysurfactant-based sol–gel methods has been reported as an effectiveapproach to tailor-design the structural properties of TiO2 nanoparticlesand films from molecular precursors [6,8–10]. Thehydrocarbon surfactant is used as pore directing agent and tocontrol the hydrolysis and condensation rates of the titaniumprecursor in the sol formulation. This method has the capacity toyieldtailor-designedTiO2withhighsurface area,highporosity, smallcrystal size with narrow pore size distribution and high photocatalyticactivity under UV [8–10] and visible light irradiation [4].One of the aims of this work is to develop highly efficient N-FcodopedTiO2 nanoparticles with enhanced structural propertiesand high photocatalytic activity under visible light irradiationusing a novel sol–gel route employing a nonionic fluorosurfactantas pore directing agent and fluorine dopant and ethylenediamineas nitrogen source. Fluorosurfactants or fluorinated surfactants,have been used mainly as antistatic, antifogging and wettingagents, and paint coating additives [28]. Only recent studies havefocused on the use of fluorinated surfactants as pore template formesoporous silica materials [29–32], signifying a great potentialfor novel ceramic second aim of this work is to focus on the application ofsuch nanoparticles in engineered water treatment processes forthe destruction of environmental contaminants of worldwideconcern. Drinking water treatment plants are facing moreprevalent occurrence of cyanobacterial harmful algae blooms(Cyano-HABs) and the release of their toxins in their water toxins are considered a serious health risk due to their highsolubility in water, toxicity (., hepatotoxicity, neurotoxicity, andcarcinogenicity) and chemical stability. Among them, microcystin-LR (MC-LR) is one of the most commonly found cyanotoxins inCyano-HABs and the most toxic derivative of the group ofmicrocystins [33]. Conventional TiO2 has been proven to beeffective in the treatment of MC-LR under UV radiation [34,35].Recent work demonstrated high degradation rates of MC-LR withnitrogen-doped TiO2 nanoparticles [4]. In this study, we presentresults on the destruction of MC-LR with N-F-TiO2 nanoparticlesunder visible light . . Synthesis of visible light-activated TiO2 nanoparticlesTo prepare the modified sol–gel solution, a nonionic fluorosurfactant(Zonyl FS-300 (FS), 50% solids in H2O, RfCH2CH2O(CH2CH2O)xH; Rf = F(CF2CF2)y where x = 14 and y = 3, Fluka), acting asboth pore directing agent and fluorine source, dissolved inisopropanol (i-PrOH), was used. Acetic acid (Fisher) was addedto maintain a low pH (). Before adding the titania precursor,anhydrous ethylenediamine (EDA, Fisher) was added in thesolution as nitrogen source. Then, titanium(IV) isopropoxide (TTIP,97%, Aldrich) was added dropwise under vigorous stirring andmore acetic acid was added for peptidization. The final sol obtainedwas transparent, homogeneous and stable after stirred overnightat room temperature. Afterwards, the sol was dried at roomtemperature for 24 h and then calcined in a multi-segmentprogrammable furnace (Paragon HT-22-D, Thermcraft) wherethe temperature was increased at a ramp rate of 60 8C/h to 100 8Cand maintained for 1 h. Then it was increased up to 400 8C underthe same ramp rate, maintained for 2 h and cooled down naturallyto finally obtain a yellowish powder. The FS:i-PrOH:aceticacid:EDA:TTIP molar ratio employed in the sol–gel for thepreparation of the denoted Particle 1 was , the i-PrOH/EDA molar ratio was and 14 forParticles 2, and 3, respectively. Nitrogen-doped TiO2 (Particle 4)and fluorine-doped TiO2 (Particle 5) where synthesized without FSand EDA, respectively, maintaining the same final volume by theaddition of more isopropanol. Reference TiO2 was synthesizedusing the same procedure but without the addition of nitrogen andfluorine sources. The synthesized nanoparticles were comparedwith Kronos vlp 7000, a commercially available visible lightactivatedTiO2 photocatalyst (Kronos International Inc., D-51373).. Characterization of synthesized TiO2An X-ray diffraction (XRD) analysis was performed with aKristalloflex D500 diffractometer (Siemens) using Cu Ka(l = ˚ ) radiation, to study the crystal structure andcrystallinity of the TiO2 nanoparticles. The Brunauer–Emmett–Teller (BET) surface area, pore volume, porosity, Barret–Joyner–Halenda (BJH) pore size and distribution (based on nitrogenadsorption and desorption isotherms) were determined by Tristar300 (Micromeritics) porosimeter analyzer. The samples werepurged with nitrogen gas for 2 h at 150 8C using Flow prep 060(Micromeritics). A high resolution-transmission electron microscope(HR-TEM) with field emission gun at 200 kV was employedto obtain crystal size and crystal structure at the nanoscale. Thesamples in ethanol were dispersed using an ultrasonicator (2510RDH,Bransonic) for 15 min and fixed on a carbon-coated copper grid(LC200-Cu, EMS). The particle morphology was characterized by anenvironmental scanning electron microscope (ESEM, Philips XL 30ESEM-FEG) at an accelerating voltage of 30 kV. The point of zerocharge (PZC) was measured using a Zetasizer (Malvern Instruments).The fine elemental composition and electronic structurewas determined with an X-ray photoelectron spectroscope (XPS,PerkinElmer Model 5300) with Mg Ka X-rays at a takeoff angle of458 and vacuum pressure of 108 to 109 Torr. The bindingenergies were calibrated with respect to C1s core level peak eV. To investigate the optical band gap of the synthesizedTiO2 nanoparticles, the UV–vis absorption spectra were obtainedwith a UV–vis spectrophotometer (Shimadzu 2501 PC) mountedwith an integrating sphere accessory (ISR1200) using BaSO4 asreference . Photocatalytic evaluation with microcystin-LR under visible lightThe photocatalytic activity of the synthesized TiO2 nanoparticleswas evaluated for the degradation of MC-LR. A borosilicatevessel (. cm) was employed as photocatalytic reactor. Anaqueous solution, previously adjusted at the desired pH withH2SO4 or NaOH without any buffer, was spiked with an aliquot ofMC-LR standard (Calbiochem Cat #. 475815) to achieve an initialconcentration of mg/L. A solution with TiO2 nanoparticleswas dispersed using an ultrasonicator (2510R-DH, Bransonic) for 24 hand transferred to the reactor containing MC-LR for a final volumesolution of 10 ml. The reactor was completely sealed and mixed tominimize mass transfer limitations. Two 15W fluorescent lamps(Cole-Parmer) mounted with UV block filter (UV420, Opticology) toeliminate spectral range below 420 nm were employed to irradiatethe reactors. The intensity of the radiation was below the detectionlimit when employing an IL 1700 radiometer (International Light)with a 365 nm sensor. The light intensity was determined using abroadband radiant power meter (Newport Corporation) for a totalvisible light intensity of 105Wcm2. During irradiation, a fanwas positioned near the reactor to cool it down. Sampling was done atspecific periods of time and the samples were quenched withmethanol to stop any further reaction, filtered (L815, Whatman) toremove the suspended nanoparticles, transferred to ml glassinserts and placed in sample vials. MC-LR samples were analyzed byliquid chromatography (LC, Agilent Series 1100) equipped with aphotodiode array detector set at 238 nm under isocratic conditions:60% (v/v) of trifluoroacetic acid (TFA) in MilliQ water and 40%(v/v) of TFA in acetonitrile with a flow rate of 1 ml/ column employed was a C18 Discovery (Supelco) column( mm 150 mm, 3 mm particle size) kept at 40 8C with aninjection volume of 50 ml [7]. The handling of the toxin must bedone with extreme care since it is highly toxic and irritant if , all the experiments were conducted in an AdvanceSterilchemgard III Class II biological safety cabinet (Baker Company,Sanford, ME) with full exhaust.
3400,1600,为OH的吸收峰,500-700为二氧化钛特征峰
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