CN114011411B - 一种CoO-Co3O4碳复合物的制备方法及其应用 - Google Patents
一种CoO-Co3O4碳复合物的制备方法及其应用 Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
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- C02F2101/00—Nature of the contaminant
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Abstract
本发明涉及一种CoO‑Co3O4碳复合物的制备方法及其应用,属于水污染处理技术领域。本发明利用廉价的β‑环糊精(β‑CD)和醋酸钴为原料,NN二甲基甲酰胺为溶剂,通过简单的物理搅拌后,以丙酮作为沉淀剂,制备出β‑CD‑醋酸钴加合物。最后通过空气煅烧,制备获得CoO‑Co3O4/碳复合物。并以此复合物为催化剂,活化K2S2O8分解BPA分子,利用超分子‑金属离子间的若相互作用分散钴离子,一步法制备出复合价态的氧化钴/碳复合物,实现BPA分子高效分解。
Description
技术领域
本发明涉及水污染处理技术领域,具体涉及一种CoO-Co3O4碳复合物的制备方法及其应用。
背景技术
双酚A,又叫BPA,是一种重要的化工原料,也是塑料的成分之一,对环境和人体具有一定的毒性。双酚A90%以上用于塑料工业,如合成聚碳酸酯、苯乙烯树脂和阻燃剂中。BPA在环境中具有内分泌干扰性、雌激素特性和生物积累性,可通过直接接触或食物链等途径进入生物体内,干扰生物体内天然激素的合成、分泌、代谢等过程,从而影响生物的生殖、免疫神经等功能。由于其化学性质稳定,BPA的处理通常基于高级氧化技术。通过活化过一硫酸盐和过二硫酸盐获得的硫酸根自由基由于具有较高的高活性而受到广泛开发。在催化剂存在下,自由基的产生具有较高的效率。因此,过渡金属离子被用来活化过硫酸盐。但是由于高浓度的过渡金属离子会带来二次污染,过渡金属氧化物被开发并应用于过硫酸盐活化和分解BPA分子。(Bai, L.,Guan, Z. Y., Li, S. J., Zhang, S. Q., Huang, Q. X.,Li, Z. R. Nest-like Co3O4 and PdOx/Co3O4 synthesized via metal organicframework with cyclodextrin for catalytic removal of Bisphenol A bypersulfate, Sep. Purif. Technol. 2021, 255, 117718.)(Yuan,R.X.,Hu,L.,Yu,P.,Wang,H.Y., Wang, Z. H., Fang, J.Y.Nanostructured Co3O4 grown on nickel foam:An efficient and readily recyclable 3D catalyst for heterogeneousperoxymonosulfate activation. Chemosphere,2018,198,204–215.)等目前研究发现钴氧化物具有良好的催化活性,但是通过化学反应或煅烧钴的前驱体获得的钴氧化物颗粒不均一且物象不纯含有杂质,例如中国专利CN100408483A一种亚纳米级氧化钴的生产方法、CN100408483C一种纳米氧化钴的制备方法。为了克服金属钴离子活化过硫酸盐分解BPA可能引入的金属离子污染和分离金属离子带来的时间和经济成本,本领域技术人员亟待开发一种CoO-Co3O4碳复合物的制备方法及其应用方法。
发明内容
针对上述现有技术存在的问题,本发明旨在提供一种CoO-Co3O4碳复合物的制备方法及其应用。
一种CoO-Co3O4碳复合物的制备方法,包括如下步骤:1)将乙酸钴溶解于DMF中经超声充分分散后,再将一定比例的β-环糊精加入上述溶液中,转入三口瓶中;2)在搅拌下缓慢加入丙酮于三口瓶中,搅拌反应8h后,用无水乙醇、二次水洗涤1~2次,离心,60~70℃下干燥1~2h,得到固体混合物;3)将步骤2)中的固体混合物置于马弗炉中进行煅烧,即可得到CoO-Co3O4碳复合物。
进一步的,步骤1)中,所述混合液中乙酸钴与β-环糊精的摩尔比为(6~8):1,所述超声频率25KHz~130KHz,所述乙酸钴占DMF质量分数1%~1.2%。
进一步的,所述丙酮与DMF的体积比为1~1.2∶2。
进一步的,步骤2)中,所述搅拌转速600~800rpm。
进一步的,步骤3)中,所述煅烧的条件为:在空气气氛中,煅烧温度为300~400℃,煅烧时长为2h。
以上所述CoO-Co3O4碳复合物的制备方法制备得到的CoO-Co3O4碳复合物,作为活化剂活化过二硫酸钾分解双酚A进行应用,将在圆底烧瓶中加入40mL25ppmBPA溶液,称取10mgCoO-Co3O4/碳加入上述溶液,经过超声处理10分钟后将圆底烧瓶升温至30℃,加入尺寸合适的磁子进行搅拌,10分钟后,将10mL含有14mgK2S2O8的溶液加入上述圆底烧瓶中,10~20min后完成。
本发明的有益效果:
本发明基于环糊精与金属离子之间的弱相互作用,形成加合物并通过煅烧获得钴基碳复合物并用于活化过二硫酸钾(K2S2O8)分解BPA分子。与现有技术相比,方便快捷的合成颗粒为10nmCoO-Co3O4/碳复合物室温下,在K2S2O8与BPA摩尔比为15,BPA浓度为10ppm,20分钟可以实现80%BPA分子的分解三次循环实验结果显示活性基本无损失,制备方法简便,具有良好的催化活性。
附图说明
下面结合附图对本发明进行详细说明,图1为实施例1CoO-Co3O4/碳的粉末衍射图像,图2为实施例1CoO-Co3O4/碳的透射电镜图和高分辨电镜图;图3为实施例1CoO-Co3O4/碳高角环形暗场扫描透射图和元素分布图,其中(C)为HAADF-STEM图像,(D)为Co元素分布图,(E)为O元素分布图,(F)为C元素分布图和(G)为Co、O与C元素分布重叠图;图4为实施例1CoO-Co3O4/碳的Co2p的电子能谱图;图5实施例1为CoO-Co3O4/碳活化K2S2O8分解BPA紫外吸收图。图6实施例1为CoO-Co3O4/碳连续三次活化K2S2O8分解BPA效率图。
具体实施方式
下面用具体实施例说明本发明,但并不是对本发明的限制。
实施例1
首先,将150mg乙酸钴溶解于10mL的DMF中经超声频率25KHz超声10min充分分散均匀后,再将120mg的β-环糊精加入上述溶液中,转入三口瓶中;2)在搅拌下缓慢加入20mL丙酮于三口瓶中,搅拌转速800rpm,搅拌反应8h后,用无水乙醇、二次水洗涤2次,离心,70℃下干燥2h,得到固体混合物;3)将步骤2)中的固体混合物置于马弗炉中进行煅烧,在空气气氛中,煅烧温度为400℃,煅烧时长为2h,即可得到CoO-Co3O4碳复合物。
活化分解BPA活性测试:
在圆底烧瓶中加入40mL25ppmBPA溶液,称取10mgCoO-Co3O4/碳加入上述溶液,经过超声处理10分钟后将圆底烧瓶升温至30℃,加入直径3mm×6mm聚四氟乙烯磁力搅拌转子进行搅拌。10分钟后,将10mL含有14mgK2S2O8的溶液加入上述圆底烧瓶中,开始计时并在确定的时间,5min、10min、15min、20min移取1mL反应液,加入1mL甲醇后离心,取上清液UV-2600分光光度计做紫外可见光谱检测,结果见于附图5。
其中,图1粉末衍射图证实Co3O4的存在,晶面(111),(220),(311),(222),(400),(422),(511)和(111)吻合Co3O4(JCPDSNo.43-1003)。42.38°的峰对应于CoO(JCPDSNo.48-1719)并且21°宽峰为无定形碳。证明CoO-Co3O4/碳的形成。X射线行射:充分干燥制备的样品,研磨压成较细的粉末置于载玻片上,放入XD-3型X射线衍射仪上进行测试分析,射线为Cu~Kα,管压为36 kV,管流为25mA,设置X射线衍射角度为10~70°,扫描间隔为0.05°。
图2和图3能够说明 CoO-Co3O4/碳的透射电镜和高分辨电镜图像,证明了均匀颗粒测形成,并且Co,C和O是均匀分布的。使用JEOL JEM-2010进行透射电镜图和高分辨电镜图、高角环形暗场扫描透射图和元素分布图,在200KV下进行。X射线光电子能谱(XPS)是使用带有单色Al Kα(hv=1486.6eV)的Thermo ESCALAB 250的X射线源。
附图4说明CoO-Co3O4/碳的Co2p电子能谱显示了钴有+2和+3价态,通过计算可知,在样品表面二价的钴含量较正常的Co3O4理论值(33%)要高出近一倍。X射线光电子能谱(XPS)是使用带有单色Al Kα(hv=1486.6eV)的Thermo ESCALAB 250仪器进行的X射线源。在安捷伦ICP-OES 720ES上进行了电感耦合等离子体光发射光谱(ICP-AES)分析。
实施例2
首先,将112.5mg乙酸钴溶解于12mL的DMF中经130KHz超声4min充分分散后,再将120mg的β-环糊精加入上述溶液中,转入三口瓶中;2)在搅拌下缓慢加入20mL丙酮于三口瓶中,搅拌转速600rpm,搅拌反应8h后,用无水乙醇、二次水洗涤1次,离心,60℃下干燥1h,得到固体混合物;3)将步骤2)中的固体混合物置于马弗炉中进行煅烧,在空气气氛中,煅烧温度为300℃,煅烧时长为2h,即可得到CoO-Co3O4碳复合物。
以上所述仅为本申请的优选实施例,并不用于限制本申请,对于本领域的技术人员来说,本申请可以有各种更改和变化。凡在本申请的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本申请的保护范围之内。
Claims (8)
1.一种CoO-Co3O4碳复合物的制备方法,其特征在于,包括如下步骤:1)将乙酸钴溶解于DMF中经超声充分分散后,再将一定比例的β-环糊精加入上述溶液中,转入三口瓶中;2)在搅拌下缓慢加入丙酮于三口瓶中,搅拌反应8h后,用无水乙醇、二次水洗涤1~2次,离心,60~70℃下干燥1~2h,得到固体混合物;3)将步骤2)中的固体混合物置于马弗炉中进行煅烧,即可得到CoO-Co3O4碳复合物。
2.如权利要求1所述的CoO-Co3O4碳复合物的制备方法,其特征在于:步骤1)中,所述混合液中乙酸钴与β-环糊精的摩尔比为(6~8):1,所述超声频率25kHz~130kHz,所述乙酸钴占DMF质量分数1%~1.6%。
3.如权利要求1所述的CoO-Co3O4碳复合物的制备方法,其特征在于:所述丙酮与DMF的体积比为1~1.2∶2。
4.如权利要求1所述的CoO-Co3O4碳复合物的制备方法,其特征在于:步骤2)中,所述搅拌转速600~800rpm。
5.如权利要求1所述的CoO-Co3O4碳复合物的制备方法,其特征在于:步骤3)中,所述煅烧的条件为:在空气气氛中,煅烧温度为300~400℃,煅烧时长为2h。
6.权利要求1~5任一权利要求所述CoO-Co3O4碳复合物的制备方法制备得到的CoO-Co3O4碳复合物。
7.权利要求6所述CoO-Co3O4碳复合物作为活化剂活化过二硫酸钾分解双酚A的应用。
8.根据权利要求7所述的CoO-Co3O4碳复合物作为活化剂活化过二硫酸钾分解双酚A的应用,其特征在于:将在圆底烧瓶中加入40mL25ppmBPA溶液,称取10mgCoO-Co3O4/碳加入上述溶液,经过超声处理10分钟后将圆底烧瓶升温至30℃,加入尺寸合适的磁子进行搅拌,10分钟后,将10mL含有14mgK2S2O8的溶液加入上述圆底烧瓶中,10~20min后完成。
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