CN110559983B - 一种用于污染物吸附的钴掺杂多孔ZnO的制备方法 - Google Patents
一种用于污染物吸附的钴掺杂多孔ZnO的制备方法 Download PDFInfo
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- HRRZMSYYJGHKQS-UHFFFAOYSA-J zinc cobalt(2+) dicarbonate Chemical compound [Zn+2].C([O-])([O-])=O.[Co+2].C([O-])([O-])=O HRRZMSYYJGHKQS-UHFFFAOYSA-J 0.000 description 1
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- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种用于污染物吸附的钴掺杂多孔ZnO的制备方法,包括步骤如下:(1)将乙酸锌、乙酸钴与碳酸氢铵混合得到碱式碳酸锌钴复合物,干燥;(2)将步骤(1)得到的混合物煅烧,得钴掺杂多孔氧化锌复合材料。该方法利用直接沉淀法,将过渡金属钴掺杂在氧化锌晶格中,制备了钴掺杂氧化锌复合物多孔纳米片,提高了纯氧化锌的吸附性能,并拓展了氧化锌的光吸收范围。该材料可用于染料污水的净化吸附及光催化降解,材料合成方法绿色简便,成本低,是一种可规模制造和应用的工艺。
Description
技术领域
本发明涉及一种用于水中污染物吸附的过渡金属钴掺杂多孔ZnO的合成方法,属于无机微纳米材料制备领域。
背景技术
随着工业技术的发展,水污染已经成为一个全球性的环境问题。其中,染料具有很强的毒性、诱变性和致癌性,是目前公认的废水中的第一污染物。因此,如何在染料废水排放前快速、高效地处理染料废水就显得尤为重要。生物降解、光催化、膜、化学氧化、吸附等多种技术都可以用于水溶液中染料的脱除,但由于其简单、高效、低成本,吸附被认为是最方便、最有前途的方法。
多孔材料如活性炭、纤维素基材料、二氧化硅、天然矿物等,可提供高比表面积、丰富的活性位点和层次结构,用于转移电子和捕获污染物分子。此外,孔径是比表面积的决定因素,是影响分子通过通道扩散和吸附的主要因素。氧化锌作为一种无毒、经济、环保的半导体金属氧化物,在光催化、吸附和气体传感器等领域得到了广泛的研究和应用。近年来,一些重点研究工作报道了多孔氧化锌的合成、改性及其在废水处理中的应用。
多孔氧化锌的合成方法有水热法、直接沉淀法、气相沉淀法、溶胶凝胶法等,为了提高吸附性能,引入有机溶剂或表面活性剂等,但此类方法合成过程中涉及废水的产生,从而提高了生产成本。相关研究表明其他金属元素的加入可以提高氧化锌的比表面积,拥有多级孔结构以及较高的静电吸引力,从而提高其对污水中染料分子的吸附性能(AppliedSurface Science,2018,435:1002-1010;Applied Surface Science,2019,473:251-260)。
发明内容
针对现有技术的不足,本发明提供了一种利用过渡金属钴掺杂多孔氧化锌的方法,工艺简单,成本低,不产生工艺废水,得到的钴掺杂氧化锌拥有多级孔结构,比纯氧化锌有较高的吸附性能。
本发明的技术方案如下:
(1)将乙酸锌、乙酸钴与碳酸氢铵混合得到碱式碳酸锌钴复合物,干燥;
(2)将步骤(2)得到的混合物煅烧,得钴掺杂多孔氧化锌复合材料。
根据本发明优选的,所述步骤(1)中碱式碳酸锌钴复合物的制备方法包括步骤如下:在磁力搅拌下,将碳酸氢铵溶液逐滴滴加到乙酸锌和乙酸钴溶液中,滴加完成后继续搅拌30min,停止搅拌,静置陈化6-12h,用循环水多用真空泵进行减压过滤,将白色固体置于坩埚中,放入电热恒温鼓风干燥箱,得到以碳酸氢铵为沉淀剂的氧化锌前驱体。
进一步优选的,所述乙酸锌和碳酸氢铵的摩尔比为2:5,乙酸钴和乙酸锌的摩尔比为(0.12-0.16):1,尤其优选为0.14:1。
进一步优选的,所述静置陈化时间为12h,干燥条件为80℃,6h。
根据本发明优选的,所述步骤(2)中钴掺杂多孔氧化锌复合材料的制备方法如下:将烘干好的碱式碳酸锌钴复合物放入马弗炉中经过程序升温至400-600℃,恒温1-3h,于空气中自然冷却至室温。
进一步优选的,所述程序升温速度为6-7℃/min,煅烧温度为400℃,煅烧时间为2h。
本发明同时提供上述钴掺杂多孔ZnO在染料污染物吸附中的应用,优选的,所述染料污染物为茜素红。
本发明借助于前驱体煅烧获得三维多孔复合材料,通过煅烧,前驱体产生二氧化碳气体,生成片状多级孔结构。其中,过渡金属钴掺杂在氧化锌晶格中,占据Zn2+的位置,改变了氧化锌的孔结构和比表面积,提高了对茜素红污染物的吸附能力。
本发明的有益效果:
1.本发明制备的钴掺杂氧化锌为多孔片状结构组成的纳米微球,煅烧后保留了纯氧化锌的结构。通过调控过渡金属钴的掺杂量,所制备的钴掺杂氧化锌的平均孔径可控,孔径大小包括大孔(>50nm)、介孔(2-50nm)以及微孔(<2nm),属于多级孔结构。大孔主要起污染物分子运输通道的作用,提高吸附速度;介孔的孔径较小、数目较多,可吸附分子直径较大的污染物;微孔孔径较小,可吸附污水中的小分子污染物。各种孔相互协同作用,优化吸附性能。
2.本发明制备的钴掺杂氧化锌中,氧化锌和钴的氧化物具有一定的光催化能力,钴元素的加入可提高氧化锌在可见光范围的吸收能力,对污染物吸附量的增加可促进光催化效率。
3.该方法制备的钴掺杂氧化锌对茜素红的吸附性能明显优于纯氧化锌材料。
4.该制备方法绿色简便,重复性好,成本低,是一种可规模制造和应用的工艺。
附图说明
图1为实施例1制备的钴掺杂氧化锌的透射电镜照片。
图2为实施例1制备的钴掺杂氧化锌的X射线能谱分析照片。
图3为实施例1制备的钴掺杂氧化锌的选区电子衍射照片。
图4为实施例1制备的钴掺杂氧化锌的X射线衍射花样。
图5为实施例1制备的钴掺杂氧化锌的氮气吸附/脱附等温线及孔径分布图。
图6为实施例2制备的钴掺杂氧化锌的氮气吸附/脱附等温线及孔径分布图。
图7为实施例3制备的钴掺杂氧化锌的氮气吸附/脱附等温线及孔径分布图。
具体实施方式
下面结合具体实施例对本发明做进一步的说明,但不限于此。
同时下述实施例中所述实验方法,如无特殊说明,均为常规方法;所述试剂和材料,如无特殊说明,均可从商业途径获得。
实施例1
一种用于水中污染物吸附的过渡金属钴掺杂多孔氧化锌的合成方法,包括步骤如下:
(1)称取乙酸锌0.439g(2mmoL)、乙酸钴0.0697g(0.28mmol)(Co:Zn=0.14:1)溶于30mL蒸馏水,磁力搅拌30min;称取碳酸氢铵0.3953g(0.005moL)溶于30mL蒸馏水,磁力搅拌30min;在磁力搅拌下,将碳酸氢铵溶液逐滴滴加到乙酸锌和乙酸钴混合溶液中,滴加完成后继续搅拌30min。将滴加完成后的溶液静置陈化12h,过滤,80℃下烘干6h,得碱式碳酸锌钴复合物。
(2)将步骤(1)得到的碱式碳酸锌钴于马弗炉中400℃煅烧恒温2h,得钴掺杂氧化锌复合材料。
图1为本实施例制备的钴掺杂氧化锌的扫描电镜照片,由图1可知合成的钴掺杂氧化锌为多孔片状结构组装的椭圆微球。
图2为本实施例制备的钴掺杂氧化锌的X射线能谱分析照片,说明合成的材料为锌钴复合氧化物。
图3为本实施例制备的钴掺杂氧化锌的选区电子衍射照片,由图3可知合成的钴掺杂氧化锌为单晶晶体,晶格间距为0.178nm、0.149nm及0.282nm对应于(110)、(11-2)及(002)晶面。
图4为本实施例制备的钴掺杂氧化锌的X射线衍射花样,由图4可知,合成的复合物符合纤锌矿氧化锌结构,对应标准卡片JCPDS No.36-1451,无其他杂峰出现,说明过渡金属钴掺杂在氧化锌晶格里。
图5为本实施例制备的钴掺杂氧化锌的氮气吸附/脱附等温线及孔径分布图,根据IUPAC规定,等温线符合第Ⅳ类型,H3滞后环,比表面积为49.21m2/g,平均孔径为15.3nm,孔体积为0.263cm3/g。
实施例2
如实施例1所述,不同的是步骤1中乙酸钴0.0597g(0.24mmol)(Co:Zn=0.12:1)代替乙酸钴0.0697g(0.28mmol)(Co:Zn=0.14:1)。
图6为本实施例制备的钴掺杂氧化锌的氮气吸附/脱附等温线及孔径分布图,根据IUPAC规定,等温线符合第Ⅳ类型,H3滞后环,比表面积为52.95m2/g,平均孔径为18.6nm,孔体积为0.304cm3/g。
实施例3
如实施例1所述,不同的是步骤1中乙酸钴0.0796g(0.32mmol)(Co:Zn=0.16:1)代替乙酸钴0.0697g(0.28mmol)(Co:Zn=0.14:1)。
图7为本实施例制备的钴掺杂氧化锌的氮气吸附/脱附等温线及孔径分布图,根据IUPAC规定,等温线符合第Ⅳ类型,H3滞后环,比表面积为53.36m2/g,平均孔径为24.5nm,孔体积为0.299cm3/g。
通过上述实施例,制备出的钴掺杂氧化锌比表面积可达50m2/g以上,平均孔径在15-25nm之间可控,孔径大小包括大孔、介孔以及微孔,属于多级孔结构,各种孔相互协同作用,提高了吸附速度,扩展了吸附分子范围,优化了吸附性能,钴元素的加入可提高氧化锌在可见光范围的吸收能力,对污染物吸附量的增加可促进光催化效率,制备的钴掺杂氧化锌对染料污染物(茜素红)的吸附性能明显优于纯氧化锌材料。
Claims (10)
1.一种用于污染物吸附的钴掺杂多孔ZnO的制备方法,包括步骤如下:
(1)将乙酸锌、乙酸钴与碳酸氢铵混合得到碱式碳酸锌钴复合物,干燥,得到以碳酸氢铵为沉淀剂的氧化锌前驱体;混合时将碳酸氢铵溶液逐滴滴加到乙酸锌和乙酸钴溶液中;
(2)将步骤(1)得到的氧化锌前驱体煅烧,得钴掺杂多孔氧化锌复合材料,材料为片状多级孔结构的锌钴复合氧化物,过渡金属钴掺杂在氧化锌晶格中,占据Zn2+的位置。
2.根据权利要求1所述的用于污染物吸附的钴掺杂多孔ZnO的制备方法,其特征在于,所述步骤(1)中在磁力搅拌下,将碳酸氢铵溶液逐滴滴加到乙酸锌和乙酸钴溶液中,滴加完成后继续搅拌一定时间,停止搅拌,静置陈化6-12h,经过滤、干燥,得到以碳酸氢铵为沉淀剂的氧化锌前驱体。
3.根据权利要求2所述的用于污染物吸附的钴掺杂多孔ZnO的制备方法,其特征在于,所述步骤(1)中在磁力搅拌下,将碳酸氢铵溶液逐滴滴加到乙酸锌和乙酸钴溶液中,滴加完成后继续搅拌30min,停止搅拌,静置陈化6-12h,用循环水多用真空泵进行减压过滤,将白色固体置于坩埚中,放入电热恒温鼓风干燥箱,得到以碳酸氢铵为沉淀剂的氧化锌前驱体。
4.根据权利要求2所述的用于污染物吸附的钴掺杂多孔ZnO的制备方法,其特征在于,所述步骤(1)中乙酸锌和碳酸氢铵的摩尔比为2:5,乙酸钴和乙酸锌的摩尔比为(0.12-0.16):1。
5.根据权利要求4所述的用于污染物吸附的钴掺杂多孔ZnO的制备方法,其特征在于,所述乙酸钴和乙酸锌的摩尔比为0.14:1。
6.根据权利要求2或3所述的用于污染物吸附的钴掺杂多孔ZnO的制备方法,其特征在于,所述步骤(1)中静置陈化时间为12h,干燥条件为80℃,6h。
7.根据权利要求1所述的用于污染物吸附的钴掺杂多孔ZnO的制备方法,其特征在于,所述步骤(2)中钴掺杂多孔氧化锌复合材料的制备方法如下:将烘干好的氧化锌前驱体放入马弗炉中经过程序升温至400-600℃,恒温1-3h,于空气中自然冷却至室温。
8.根据权利要求7所述的用于污染物吸附的钴掺杂多孔ZnO的制备方法,其特征在于,所述步骤(2)中程序升温速度为6-7℃/min,煅烧温度为400℃,煅烧时间为2h。
9.一种钴掺杂多孔ZnO在染料污染物吸附中的应用,其特征在于,所述钴掺杂多孔ZnO是根据权利要求1-8任一项所述的制备方法制备得到。
10.根据权利要求9所述的钴掺杂多孔ZnO在染料污染物吸附中的应用, 其特征在于,所述染料污染物为茜素红。
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