CN111792700B - BiOBr或氧空位BiOBr在去除藻类有机物中的应用及去除方法 - Google Patents
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Abstract
本发明公开了BiOBr或氧空位BiOBr在去除藻类有机物中的应用,还公开了一种利用BiOBr或氧空位BiOBr去除藻类有机物的方法,包括如下步骤:在含有藻类有机物的污水中加入光催化材料BiOBr或氧空位BiOBr,然后污水在可见光下照射60分钟以上。本发明首次将溴氧化铋和氧空位溴氧化铋应用在去除藻类有机物的应用上,取得了良好的去除效果,氧空位溴氧化铋的去除效果更好,其中,2‑OVs‑BiOBr和3‑OVs‑BiOBr的处理效果最优,对于TOC(总有机碳)的去除较为彻底,3‑OVs‑BiOBr几乎去除所有蛋白质和多糖。本发明为去除水中的藻类有机物提供了新的方向,去除效果好,环保无二次污染。
Description
技术领域
本发明涉及光催化剂技术领域,具体涉及一种BiOBr或氧空位BiOBr在去除藻类有机物中的应用及去除方法。
背景技术
湖泊和水库是我国重要的饮用水水源,藻类引起的富营养化问题在湖泊和水库中频繁发生,从而导致全球水质的下降。藻类在其生长周期中会利用阳光以及周围环境中的营养物质进行光合作用,同时,由于呼吸作用的进行或大量死亡的过程中也代谢产生了藻类有机物(Algal Organic Matter,AOM)。现如今,藻类及其有机物的危害在饮用水源污染中已经有十分突出的表现。2015年环保部发布的环境状况公报表明:国家控制的62个重点湖泊和水库中,有35.5%的湖泊、水库属于Ⅳ~劣Ⅴ类水质,其中就有15个湖泊处于富营养化的状态。在饮用水的处理过程中水体消毒时所产生消毒副产物(Disinfection By-products,DBPs)的重要前体物就是AOM。
在处理含藻水的过程中,藻细胞被破坏,胞内外有机质释放到水中,与用来净化饮用水的消毒剂和氧化剂尤其是与氯离子的反应,生成包括卤乙酸,三卤甲烷和其它一些卤代消毒副产物,这些物质已被动物试验证明有致癌作用。而且后续饮用水处理过程中也很难被全部去除,对我们人体健康具有负面影响。另一方面,因为藻类释放的有机物如糖酸会与混凝剂反应,需要投加更多的混凝剂来实现反应,处理的难度增加,从而无形中增加了处理成本。在饮用水的城市管网运输中藻类有机胞外分泌物进入管网后,未被前处理工艺处理的微生物以及滋生的微生物会同化这些有机物质,利用其作为营养物质满足生长繁殖的需要,并在管网中迅速、大量地繁殖如线虫等等,其去除非常困难以至堵塞水龙头等给水附件。
铋是一种重金属元素,低毒且有微弱的放射性。近年来,Bi基化合物(如Bi2WO6、Bi2O2CO3、Bi2MoO6和Bi2O3)逐渐成为新型光催化剂开发的新方向,其中溴氧化铋BiOBr因其独特的层状结构、合适的禁带宽度、良好的可见光响应性而展现出较高的光催化活性,已成为光催化材料领域极具应用前景的材料体系之一。BiOBr是一种具有高度各向异性的层状结构半导体,其层状结构具有足够的空间来极化相应的原子和原子轨道,这就能够有效地分离空穴与电子,提高光催化性能;又因为BiOBr属于间接跃迁带隙,故激发电子需要穿过某些k层才能够跃迁到价带,从而降低了激发电子空穴对的再复合几率。
发明内容
本发明的目的是针对上述问题,提供一种BiOBr或氧空位BiOBr在去除藻类有机物中的应用。
本发明为了实现其目的,采用的技术方案是:
BiOBr或氧空位BiOBr在去除藻类有机物中的应用。
在上述技术方案中,所述氧空位BiOBr的含氧质量比(即氧空位BiOBr化合物中氧元素的质量比)为3~7.5%。
优选地,所述氧空位BiOBr的含氧质量比为4~7%。
进一步优选地,所述氧空位BiOBr的含氧质量比为5~6%。
在上述技术方案中,所述氧空位BiOBr的制备方法为:取BiOBr和铝粉,分别放入双区控温马弗炉中,充入惰性气体隔绝空气,其中BiOBr区升温程序以5-7℃/min由室温升至120-130℃持续反应1.5-2.5h;铝粉区域以8-10℃/min由室温升至350-400℃持续反应1-2h,得到的黑色固体即为氧空位BiOBr;所述BiOBr和铝粉的摩尔比为1~4﹕35。
优选地,所述BiOBr和铝粉的摩尔比为1.2~3.5﹕35。
进一步优选地,所述BiOBr和铝粉的摩尔比为1.8~2.5﹕35。
本发明的另一方面,还提供了一种利用BiOBr或氧空位BiOBr去除藻类有机物的方法,包括如下步骤:在含有藻类有机物的污水中加入光催化材料BiOBr或氧空位BiOBr,然后污水在可见光(420<λ<800nm)下照射60分钟以上。
优选地,污水在可见光下照射180分钟以上。
本发明的有益效果是:首次将溴氧化铋和氧空位溴氧化铋应用在去除藻类有机物的应用上,取得了良好的去除效果,氧空位溴氧化铋的去除效果更好,其中,2-OVs-BiOBr和3-OVs-BiOBr的处理效果最优,2-OVs-BiOBr和3-OVs-BiOBr对于TOC(总有机碳)的去除较为彻底,3-OVs-BiOBr几乎去除所有蛋白质和多糖。本发明为去除水中的藻类有机物提供了新的方向,去除效果好,环保无二次污染。在实际应用中,可以先将污水中的藻胞去除,然后在污水治理工艺中加入本发明方法即可去除污水中含有的藻类有机物。
附图说明
图1是不同氧空位含量的BiOBr的SEM照片,其中,(a)、(b)、(c)、(d)、(e)分别对应的是BiOBr、1-OVs-BiOBr、2-OVs-BiOBr、3-OVs-BiOBr和4-OVs-BiOBr的结果。
图2是不同氧空位含量BiOBr的EDS分析结果,其中,(a)、(b)、(c)、(d)、(e)分别对应的是BiOBr、1-OVs-BiOBr、2-OVs-BiOBr、3-OVs-BiOBr和4-OVs-BiOBr的结果。
图3是不同氧空位含量的BiOBr的吸光能力,其中,(a)是不同氧空位含量的BiOBr紫外可见漫反射紫外可见漫反射光谱,(b)是不同氧空位含量的BiOBr样品的带隙能计算图。
图4是不同氧空位含量的BiOBr对藻胞有机物中的多糖含量的去除率随时间的变化。
图5是不同氧空位含量的BiOBr对藻胞有机物中的蛋白质含量的去除率随时间的变化。
图6是不同氧空位含量的BiOBr对藻胞有机物中的脂质含量的去除率随时间的变化。
图7是不同氧空位含量的BiOBr对藻胞有机物中的TOC(总有机碳)的去除率随时间的变化。
具体实施方式
下面结合实施例对本发明作进一步说明,但并不因此而限制本发明。
下述实施例中的实验方法,如无特别说明,均为常规方法。
试剂来源:五水硝酸铋、冰醋酸、NaBr、铝粉均为分析纯,均可通过市售获得。
对数生长期的小球藻液来源:小球藻藻种(FACHB-1445)来自中国科学院淡水藻种库,
用BG-11培养基培养,取用对数生长期的小球藻藻液做实验。
实施例1
一、一步合成BiOBr
按照如下步骤操作:
(1)制备A溶液:
将0.01mol五水硝酸铋Bi(NO3)3·5H2O溶解到7mL冰醋酸(CH3COOH)中,充分搅匀,得到A溶液;
(2)制备B溶液:
将0.01mol的NaBr溶解到10mL水中,得到B溶液;
(3)在强磁力搅拌条件下,将A溶液迅速加入B溶液;
(4)将得到的混合溶液再继续磁力搅拌6h后转移至反应釜中,在恒温干燥箱中120℃反应6h;
(5)将反应后得到的溶液用超纯水洗涤过滤3至5遍;
(6)在110℃恒温红外干燥箱中烘12h得到BiOBr。
二、可控氧空位BiOBr的制备
按照如下步骤操作:
(1)分别称取1.2、1.8、2.5和3.2mmol由上述步骤得到的BiOBr,均匀分布在石英舟里;
(2)再称取35mmol的铝粉也均匀摊开装于另一石英舟中;
(3)分别放入双区控温管式马弗炉中,充入Ar气隔绝空气,其中BiOBr区升温程序以5℃/min由室温升至127℃持续反应2h;铝粉区域以10℃/min由室温升至400℃持续反应1h;
(4)最后得到的黑色固体即为氧空位BiOBr,由BiOBr区放入不同量BiOBr后得到的氧空位BiOBr分别记为1-OVs-BiOBr(1.2mmol BiOBr),2-OVs-BiOBr(1.8mmol BiOBr),3-OVs-BiOBr(2.5mmol BiOBr)和4-OVs-BiOBr(3.2mmol BiOBr)。
三、藻胞有机物的提取
取用对数生长期的小球藻液100mL,首先将细胞悬浮液以10000r/min离心10分钟,获得上清液,然后重悬于50mL超纯水中再以12000r/min离心10分钟,重复2次洗涤,均取其上清液备用。
四、藻胞有机物光催化去除反应
(1)称取前述制备得到的BiOBr、1-OVs-BiOBr、2-OVs-BiOBr、3-OVs-BiOBr和4-OVs-BiOBr光催化材料各0.2g;
(2)在每份光催化材料中加入100mL由前述步骤三得到的藻胞有机物溶液,溶液初始pH约为7.0;同时设置未添加光催化材料的空白对照组;
(3)将上述溶液分别放入1000mL的玻璃循环水冷却容器中,悬浮溶液先在黑暗条件下磁力搅拌30min,使藻胞有机物和光催化材料达到吸附-解吸平衡(因为所加光催化材料对藻类有机物有吸附去除和光解去除两个作用,为了在研究中区分光解作用和吸附作用去除的效果,因此在研究实验中先在黑暗条件下搅拌达到吸附-解吸平衡,在实际应用中不需要在黑暗条件下搅拌),然后利用500W氙灯模拟太阳光光源照射反应溶液,同时使用滤光片(420<λ<800nm)在实验中获得严格的可见光,反应溶液液面与氙灯光源距离为25cm,整个实验过程中用循环水冷却使得反应的温度不超过28℃;可见光照射反应中每隔30min取一次样;通过孔径0.45微米的注射器,除去取样得到的悬浮液中的光催化材料,将除去光催化材料后得到的液体用于接下来的去除效果测定。
在研究过程中,由于是采用100ml藻胞有机物溶液在模拟的太阳光下直射反应水体,温度较高,而做实验的水体体量小,温度高会导致水分蒸发,为了减小研究过程中的实验误差,所以实验在玻璃循环水冷却容器中进行。而实际应用中,水体体量大,反应本身并不放热,并不需要降温处理。
五、去除效果测定
由于藻类有机物属于天然有机物混合物,包括多种化合物,例如低聚糖,多糖,蛋白质,肽,氨基酸以及痕量的其他有机酸,因此,本申请通过测定反应前后的多糖、蛋白质、脂质以及总有机碳(TOC)含量的差值来表征藻类有机物的去除效果。
(1)使用蒽酮-硫酸法测定多糖含量:具体操作为将反应后的溶液取1mL放入棕色玻璃瓶中浸入冰水中。冰浴6分钟后,加入4mL蒽酮-硫酸溶液,在沸水浴中煮10min,然后用自来水冷却10min。最后用紫外可见分光光度计在620nm处测定样品吸光度。
(2)蛋白质浓度含量使用BCA蛋白浓度测定试剂盒(增强型)(Beyotime公司,中国)来分析。
(3)藻类脂肪通过尼罗红法测定:取1mL反应后的溶液在离心机中以10000rmp·min-1的速度离心10min,再重悬于20%的DMSO(dimethylsulfoxide)中,再40℃水浴20min,加入体积比200﹕3的藻液和NR(0.1mg·ml-1尼罗红染液)混匀染色5min。最后用F-7000荧光分光光度计在激发波长500-700nm,发射波长575nm处以10nm的间隔2400nm·min-1收集数据。
(4)使用TOC分析仪(Elementar Vario,德国)测定反应溶液前后的总有机碳含量的变化。测定模式为NPOC-precise,cal.16060650ppm,在900~950℃温度下,以铂和三氧化钴为催化剂,将有机物燃烧裂解转化为二氧化碳,用红外线气体分析仪测定二氧化碳含量。将高低温炉中测得的总碳TC和无机碳TIC相减就得总有机碳TOC,TOC=NPOC+POC≈NPOC。六、结果与分析
(1)图1是不同氧空位含量的BiOBr的SEM照片,图(a)、(b)、(c)、(d)、(e)分别为BiOBr、1-OVs-BiOBr、2-OVs-BiOBr、3-OVs-BiOBr和4-OVs-BiOBr,很明显地可以看出成功制备出了OVs-BiOBr微纳米球,其中,可以清晰看到图(d)、(e)的两组材料微球形成比(b)和(c)好,规则的微观结构有利于增加材料表面的比表面积,更易吸附藻胞有机物,而且更易进一步发生光催化反应,从而使有机物的去除效果更好。
(2)图2是不同氧空位含量BiOBr的EDS分析结果,(a)、(b)、(c)、(d)、(e)分别对应BiOBr、1-OVs-BiOBr、2-OVs-BiOBr、3-OVs-BiOBr和4-OVs-BiOBr的EDS图谱分析。从图中可以得到含氧质量比由(b)到(e)依次递增约1%左右,说明BiOBr的氧空位含量可控且成功制备出来。所添加的BiOBr质量与铝粉质量的比值是控制氧空位含量的关键。
(3)图3是不同氧空位含量的BiOBr紫外可见漫反射光谱。如图3(a)所示,1-OVs-BiOBr、2-OVs-BiOBr和3-OVs-BiOBr在可见光区400-500nm范围内均有显著的强吸收和宽吸收,表现出较强的吸光能力,而4-OVs-BiOBr的吸收宽度相对较窄。可以发现,2-OVs-BiOBr、3-OVs-BiOBr和4-OVs-BiOBr的光吸收范围比1-OVs-BiOBr有非常明显的红移,这意味着可见光吸收范围得到了改善。通过公式αhv=A(hv-Eg)n/2计算得到所有样品的带隙值,如图3(b),带隙能2-OVs-BiOBr<3-OVs-BiOBr<4-OVs-BiOBr<1-OVs-BiOBr<BiOBr,分别为2.12eV、2.51eV、3.62eV、2.95eV和3.0eV,证明2-OVs-BiOBr、3-OVs-BiOBr和4-OVs-BiOBr表现出更好的吸收吸光性能,同时证明并不是氧空位含量愈多光吸收效果最好,由于4-OVs-BiOBr的吸收宽度较窄,因此综合得出材料性能最好的是2-OVs-BiOBr和3-OVs-BiOBr。
(4)图4是不同氧空位含量的BiOBr对藻胞有机物中的多糖含量的去除率随时间的变化,由图4可以看出,在空白对比组中光照对多糖的除去没有明显作用,BiOBr对多糖有较好的去除效果,氧空位BiOBr去除多糖的效果是十分明显的,效果最好的是3-OVs-BiOBr,也就是含氧质量比(即氧的质量比)控制在6%左右的效果最佳。
(5)图5是不同氧空位含量的BiOBr对藻胞有机物中的蛋白质含量的去除率随时间的变化,由图5可以看出,光照对蛋白质有一定的去除作用,但由于氧空位BiOBr对藻胞有机物中的蛋白质去除效果远大于光照的效果,因此光解部分可忽略不计,BiOBr对蛋白质去除效果也较好。从图中得出3-OVs-BiOBr的去除效果最好,几乎去除所有蛋白质。
(6)图6是不同氧空位含量的BiOBr对藻胞有机物中的脂质含量的去除率随时间的变化,由图6可以看出,光照对脂质没有去除作用,而不同氧空位含量的BiOBr对藻胞有机物中的脂质去除效果也不如其他组分,这是由于本研究制备的材料具备亲水性,对于脂质的吸附作用较小,导致后续去除以及催化作用也较差,但仅这一组分不影响对藻胞有机物的总体去除效果,可以参考以下总有机碳的去除效果。
(7)图7是不同氧空位含量的BiOBr对藻胞有机物中的TOC(总有机碳)的去除率随时间的变化。由图7可以看出,光照对总有机碳没有去除作用,而BiOBr和氧空位BiOBr一系列材料对TOC的去除效果十分明显,特别是2-OVs-BiOBr和3-OVs-BiOBr几乎对其进行了较为彻底的去除。
综上结果可见,氧空位BiOBr材料对藻胞有机物的去除效果良好,是一种十分具有潜力的处理饮用水的材料。
Claims (2)
1.氧空位BiOBr在去除藻类有机物中的应用,其特征在于:所述氧空位BiOBr的含氧质量比为5~6%;所述氧空位BiOBr的制备方法为:取BiOBr和铝粉,分别放入双区控温马弗炉中,所述BiOBr和铝粉的摩尔比为1.8~2.5﹕35,充入惰性气体隔绝空气,其中BiOBr区升温程序以5-7℃/min由室温升至120-130℃持续反应1.5-2.5 h;铝粉区域以8-10℃/min由室温升至350-400℃持续反应1-2 h,得到的黑色固体即为氧空位BiOBr;
所述藻类有机物包括多糖、蛋白质、脂质和总有机碳,藻类有机物为藻类在其生长周期中利用阳光以及周围环境中的营养物质进行光合作用,以及由于呼吸作用的进行或大量死亡的过程中代谢产生的藻类有机物;
所述应用包括如下步骤:在含有藻类有机物的污水中加入光催化材料氧空位BiOBr,然后污水在可见光下照射60分钟以上。
2.如权利要求1所述的应用,其特征在于,污水在可见光下照射180分钟以上。
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