CN109970098B - 不同形貌羟基氟化锌纳米材料的可控合成方法及其环境光催化应用 - Google Patents
不同形貌羟基氟化锌纳米材料的可控合成方法及其环境光催化应用 Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 68
- KUYTVLLQSDQEMR-UHFFFAOYSA-L [H]O[Zn]F Chemical compound [H]O[Zn]F KUYTVLLQSDQEMR-UHFFFAOYSA-L 0.000 title claims abstract description 20
- 238000001308 synthesis method Methods 0.000 title claims abstract description 9
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 26
- 239000011701 zinc Substances 0.000 claims description 26
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
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Abstract
本发明公开了不同形貌羟基氟化锌纳米材料的可控合成方法及其环境光催化应用,是采用水热反应,通过控制锌源、溶剂、碱及水热反应的温度和时间,控制羟基氟化锌纳米材料的形貌,获得不同形貌羟基氟化锌纳米材料。本发明的制备方法简便、反应条件温和、产率高;通过本发明方法所获得的羟基氟化锌纳米材料的形貌特征丰富多样并可调控,具有明显的催化活性,可用于光催化降解多种有机污染物(如灿烂甲酚蓝、罗丹明B、二甲酚橙、溴甲酚绿、刚果红、亚甲基蓝、苯酚和苯)。
Description
技术领域
本发明属于纳米材料制备和光催化技术领域,具体涉及不同形貌羟基氟化锌纳米材料的可控合成方法及其在环境光催化领域上的应用。
背景技术
纳米材料由于其独特的物理、化学性质而受到广泛关注,其中纳米材料的可控合成是纳米材料领域的研究热点之一。羟基氟化锌(ZnF(OH))作为一种重要的锌基纳米材料,不仅是合成特殊形貌氧化锌(ZnO)纳米材料的重要前驱体,而且是一种有效光催化分解有机染料和催化合成吡啶的有效催化剂。众所周知,纳米材料的化学和物理特性强烈依赖于其形态、维度、尺寸和表面等性质。发展纳米材料的可控制备方法对于纳米材料的理论发展和实际应用都有着重大意义。
目前,多种制备方法被用来合成ZnF(OH)纳米材料,包括水热方法、液相合成法、电化学方法和微波辐射法等。因此,一系列ZnF(OH)纳米结构,如纳米棒、网状、花状、带状等形貌被合成。然而,关于如何采用一种简单高效及相对温和实验条件的路径可控合成不同形貌ZnF(OH)纳米结构仍然是一个重大挑战。
发明内容
针对现有技术的不足,本发明的目的在于提供不同形貌羟基氟化锌纳米材料的可控合成方法及其环境光催化应用,旨在可控获得多种形貌的羟基氟化锌纳米材料。
为解决上述问题,本发明采取如下技术方案:
本发明不同形貌羟基氟化锌纳米材料的可控合成方法,包括如下步骤:
(1)称取0.83g氟化铵和0.31-0.66g锌源,于塑料烧杯中;
(2)向烧杯中加入82mL的溶剂,搅拌至氟化铵和锌源完全溶解;
(3)再向烧杯中加入加入0.18g碱源,搅拌2h,得悬浊液;
(4)将所述悬浊液转移到100mL聚四氟乙烯内衬中,密封,20-140℃水热反应1-16小时,所得产物经洗涤、烘干,即获得羟基氟化锌纳米材料。
进一步地,通过控制锌源、溶剂、碱源及水热反应的温度和时间,控制羟基氟化锌纳米材料的形貌,获得不同形貌羟基氟化锌纳米材料。
进一步地,所述锌源为醋酸锌、氯化锌、七水合硫酸锌、六水合硝酸锌或乙酰丙酮锌。
进一步地,所述溶剂为水和乙醇按任意比例的混合液。
进一步地,所述碱源为氢氧化钠、三正丁胺或乙二胺四乙酸钠。
本发明所述可控合成方法所合成的羟基氟化锌纳米材料,可用于光催化降解有机污染物。
与现有技术相比,本发明的有益效果体现在:
本发明的制备方法简便、反应条件温和、产率高;通过本发明方法所获得的羟基氟化锌纳米材料的形貌特征丰富多样并可调控,具有明显的催化活性,可用于光催化降解多种有机污染物(如灿烂甲酚蓝、罗丹明B、二甲酚橙、溴甲酚绿、刚果红、亚甲基蓝、苯酚和苯),有效地保护环境,为人们的生活提供了保障。
附图说明
图1为实施例1使用不同锌源所制备的羟基氟化锌纳米材料的X射线粉末衍射图;
图2为实施例1使用不同锌源所制备的羟基氟化锌纳米材料的SEM图:(a)醋酸锌,(b)氯化锌,(c)七水合硫酸锌,(d)六水合硝酸锌,(e)乙酰丙酮锌和(f)e图的局部放大图;
图3为实施例2以三正丁胺作为碱源所得羟基氟化锌纳米材料的SEM图;
图4为实施例3以乙二胺四乙酸钠作为碱源所得羟基氟化锌纳米材料的SEM图;
图5为实施例4不同水反应时间所得羟基氟化锌纳米材料的SEM图:(a)1h,(b)1.5h,(c)3h,(d)4h,(e)5h,(f)6h,(g)7h,(h)9h,(i)9h(h图中虚线框部分放大图),(j)12h,(k)16h;
图6为实施例5所得羟基氟化锌纳米材料的SEM图;
图7为实施例6所得羟基氟化锌纳米材料的SEM图;
图8为实施例1中是用硝酸锌合成的羟基氟化锌纳米材料光催化降解灿烂甲酚蓝、罗丹明B、二甲酚橙、刚果红、溴甲酚绿和亚甲基蓝的曲线图;
图9为灿烂甲酚蓝、罗丹明B、二甲酚橙、刚果红、溴甲酚绿和亚甲基蓝的分子结构式;
图10为实施例1中用硝酸锌合成的羟基氟化锌纳米材料光催化降解无色难降解有机污染物苯酚的曲线图;
图11为实施例1中用硝酸锌合成的羟基氟化锌纳米材料与P25光催化降解挥发性有机物(VOC)苯生成CO2的曲线图;
图12实施例1中用硝酸锌合成的氟化氢氧化锌纳米材料与P25光催化降解挥发性有机物(VOC)苯的矿化率曲线图。
具体实施方式
下面结合具体实施例对本发明进一步说明,具体实施例的描述本质上仅仅是范例,以下实施例基于本发明技术方案进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
实施例1
本实施例按如下步骤制备羟基氟化锌纳米材料:
(1)称取0.83g氟化铵和一定量的锌源(0.49g醋酸锌或0.31g氯化锌或0.64g七水合硫酸锌或0.66g六水合硝酸锌或0.59g乙酰丙酮锌),于塑料烧杯中;
(2)向烧杯中加入82mL的溶剂去离子,搅拌至氟化铵和锌源完全溶解;
(3)再向烧杯中加入加入0.18g碱源氢氧化钠,搅拌2h,得悬浊液;
(4)将悬浊液转移到100mL聚四氟乙烯内衬中,密封,140℃水热反应6小时,所得产物经洗涤、烘干,即获得羟基氟化锌纳米材料。
对本实施例制备的羟基氟化锌纳米材料进行表征,结果如图1和图2所示。其中,图1为使用不同锌源所得羟基氟化锌纳米材料的X射线衍射图,与标准卡片(JCPDS号:74-1816)对比,衍射图中所有的衍射峰均很好的对应于ZnF(OH),说明几种锌源均能得到纯相的ZnF(OH)。图2为使用不同锌源所得羟基氟化锌纳米材料的场发射扫描电镜(FESEM)照片。如图2a所示(锌源为醋酸锌),所制备的ZnF(OH)纳米材料为茅草叶形状;如图2b所示(锌源为氯化锌),所制备的ZnF(OH)纳米材料为无规则纳米片状;如图2c所示(锌源为七水合硫酸锌),所制备的ZnF(OH)纳米材料为刚性纳米棒,并交叉汇编网状结构;如图2d所示(锌源为六水合硝酸锌),所制备的ZnF(OH)纳米材料为柔性可弯曲纳米带;如图2e和2f所示,所制备的ZnF(OH)纳米材料是由剑状组成的刺球状分级结构。由此可见,通过控制锌源就可以制备不同形貌的ZnF(OH)纳米材料,尤其当所采用的锌源为硝酸锌、硫酸锌和乙酰丙酮锌时,ZnF(OH)纳米材料形貌特征明显。
实施例2
本实施例与实施例1(以硝酸锌为锌源)方法相同,不同之处在于步骤(3)中所使用的碱源为三正丁胺。
如图3所示,当其它条件不变,用三正丁胺替换氢氧化钠后,所制备的ZnF(OH)纳米材料是由大量纳米带构成的扁平斗笠状分级结构。
实施例3
本实施例与实施例1(以硝酸锌为锌源)方法相同,不同之处在于步骤(3)中所使用的碱源为乙二胺四乙酸钠。
如图4所示,当其它条件不变,用乙二胺四乙酸钠替换氢氧化钠后,可以得到十字花状ZnF(OH)微纳米分级材料。
由图2d、图3和图4可以看到,当步骤(3)中添加的碱分别为氢氧化钠、三正丁胺和乙二胺四乙酸钠时,可分别得到一维纳米带、二维偏平斗笠状分级结构和三维十字花状微纳分级结构。由此可见,通过控制碱的种类亦可以实现对ZnF(OH)材料形貌的调控。
实施例4
本实施例与实施例3的方法相同,不同之处在于步骤(4)中水热时间为1-16小时。
如图5所示,所制备的ZnF(OH)纳米材料在不同的反应时间下先生成纳米短棒(图5a),然后纳米短棒中间部分生长出小的分枝,随着时间的延长,小枝的数量增多的同时已经长出的小枝长大(图5b-g),当反应时间达到9小时时,超级结构开始自溶解-结构重构(图5h-j),最终生长成纳米带结构(图5k)。由此可见,通过控制反应时间,不仅可以实现对ZnF(OH)材料形貌的控制,而且可以看到ZnF(OH)材料的形成机制为生长-溶解-生长。从反应1小时形成的一维棒状形貌经历二维分级结构最终变成一维纳米带结构。
实施例5
本实施例与实施例1(以硝酸锌为锌源)方法相同,不同之处在于步骤(3)中所使用的溶剂为水-乙醇混合液(乙醇所占体积比为30%)。
如图6所示,本实施例所制备的ZnF(OH)纳米材料由大量纳米短棒构成。通过对比图6和图2d可见,改变反应的溶剂亦可实现对ZnF(OH)纳米材料的形貌进行调控:当以水为溶剂(图2d)时,得到ZnF(OH)为柔性可弯曲纳米带;当以水-乙醇混合液为溶剂时,得到ZnF(OH)为纳米短棒。
实施例6
本实施例与实施例5方法相同,不同之处在于反应温度为20℃(即室温)。
如图7所示,本实施例所制备的ZnF(OH)纳米材料是由扁平狭长披针形片状组成的花状球形分级结构。通过对比图6和图7,可见通过调变反应温度亦可实现对ZnF(OH)纳米材料形貌的调控。
性能测试
将本发明实施例1用硝酸锌合成的ZnF(OH)样品分别用于光催化降解水体中有机污染物(有色染料:灿烂甲酚蓝、罗丹明B、二甲酚橙、刚果红、溴甲酚绿和亚甲基蓝;无色难降解有机污染物苯酚)和挥发性有机物(VOC,以苯为例),具体过程和步骤如下:
光催化降解水体中有机污染物:分别配制模拟有机污染物溶液:100mL 10ppm的灿烂甲酚蓝、罗丹明B、二甲酚橙、溴甲酚绿、刚果红、亚甲基蓝和苯酚水溶液,分别加入0.1g的ZnF(OH)纳米材料。结果如图8所示,紫外光照射15分钟后对灿烂甲酚蓝、罗丹明B、二甲酚橙和溴甲酚绿的降解率达到100%;光照20分钟后,对刚果红和亚甲基蓝的降解率亦可达到100%。由此可见本发明制备的ZnF(OH)纳米材料对于不同类型的染料有机污染物(图9)均具有较好的光催化降解效果。
然而,水体中除了肉眼可见的有色污染物外,还有肉眼不可见的、无色的、难降解的有机污染物,比如苯酚。苯酚作为广泛使用的化工原料,广泛存在于工业废水中,苯酚属高毒物质,由于其对环境有严重危害,对水体和大气可造成污染,如苯酚对皮肤、粘膜有强烈的腐蚀作用,可抑制中枢神经或损害肝、肾功能。因此为了进一步的考察本发明制备的ZnF(OH)纳米材料的光催化性能,对ZnF(OH)光催化降解苯酚的活性进行测试。如图10所示,光照20分钟后,苯酚的降解率约达到90%;光照30分钟后,苯酚基本被降解完全,降解率达到100%。由此可见,本发明制备的ZnF(OH)纳米材料不仅可以有效的降解有色有机污染物,而且对无色难降解的有机物苯酚亦有很好的降解效果。
目前各种各样的光催化剂被广泛报道,然而催化剂的活性较为单一,如对液相有机污染物有很好的降解效果,但是对气相有机物的降解活性则较差。因此发展具有普适性、高活性的光催化剂依然是个亟待解决的技术问题。为了进一步考察本发明合成的ZnF(OH)纳米材料的气相光催化性能,对ZnF(OH)光催化降解气相苯的活性进行测试。苯(Benzene,C6H6)在常温下是甜味、可燃、有致癌毒性的无色透明液体,具有挥发性并带有强烈的芳香气味。苯是一种石油化工基本原料,其产量和生产的技术水平是一个国家石油化工发展水平的标志之一。因此苯的过量使用,使其广泛存在于大气中,尤其是化工和加工制造等车间。而其由于苯环的共轭结构,苯表现出非常好的稳定性,因此广泛存在的气相苯在大气中很难被降解,并对人类生命健康造成严重危害。2017年10月27日,世界卫生组织国际癌症研究机构公布的致癌物清单初步整理参考,苯在一类致癌物清单中。
测试ZnF(OH)光催化降解气相苯的活性的方法如下:将催化剂粉末压片过筛获取50目-70目的催化剂颗粒;称取0.3个催化剂装入石英管中(长10cm、内径2.4mm),通入160ppm的苯气体;暗态吸附-脱附平衡后,开灯光照,采用在线气相色谱检测苯和CO2。ZnF(OH)光催化降解气相苯的活性如图11和图12所示,在光照35小时后,ZnF(OH)依然对苯有很好的降解作用和活性稳定性,其矿化率高达约90%,CO2生成量大于120ppm。为了对比本发明制备的ZnF(OH)降解苯的性能,以商品的P25(二氧化钛,P25是被广泛应用的光催化剂和常被来用作光催化性能比较的标准)为参考。由图11和图12可见,随着光照时间的延长,P25光催化降解苯生成CO2的量在逐渐减少,而其对苯的矿化率仅仅约为10%左右。可见ZnF(OH)光催化降解气相苯的活性明显优越于商品化的P25。
从上述结果可知,本发明羟基氟化锌纳米材料形貌可控、光催化降解效果好,且制备方法简单、易行,适合产业化。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (1)
1.不同形貌羟基氟化锌纳米材料的可控合成方法,其特征在于,包括如下步骤:
(1)称取0.83g氟化铵和0.31-0.66g锌源,于塑料烧杯中;
(2)向烧杯中加入82 mL的溶剂,搅拌至氟化铵和锌源完全溶解;
(3)再向烧杯中加入0.18g碱源,搅拌2h,得悬浊液;
(4)将所述悬浊液转移到100mL聚四氟乙烯内衬中,密封,水热反应,所得产物经洗涤、烘干,即获得羟基氟化锌纳米材料;
可通过控制锌源,控制羟基氟化锌纳米材料的形貌,获得不同形貌羟基氟化锌纳米材料:当所述溶剂为去离子水、所述碱源为氢氧化钠,所述水热反应的温度为140℃、时间为6小时,若分别采用醋酸锌、氯化锌、七水合硫酸锌和乙酰丙酮锌作为锌源,所得羟基氟化锌纳米材料的形貌分别为茅草叶形状、无规则纳米片状、由刚性纳米棒交叉汇编成网状结构、由剑状组成的刺球状分级结构;
或者,可通过控制碱源,控制羟基氟化锌纳米材料的形貌,获得不同形貌羟基氟化锌纳米材料:当所述溶剂为去离子水、所述锌源为六水合硝酸锌,所述水热反应的温度为140℃、时间为6小时,若分别采用三正丁胺和乙二胺四乙酸钠作为碱源,所得羟基氟化锌纳米材料的形貌分别为二维偏平斗笠状分级结构、三维十字花状微纳分级结构。
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