CN115532296A - 一种复合型催化剂及其制备方法和在降解有机物中的应用 - Google Patents
一种复合型催化剂及其制备方法和在降解有机物中的应用 Download PDFInfo
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Abstract
本发明公开了一种复合型催化剂及其制备方法和在降解有机物中的应用,属于有机物降解技术领域。其中,该复合型催化剂为3DCoMn2O4/N‑rGA,制备方法如下:(1)制备GO;(2)以Mn、Co、DA和GO为原料,用水热法制备复合水凝胶;(3)冷冻干燥得到复合气凝胶;(4)煅烧得到3DCoMn2O4/N‑rGA。本发明的有益之处在于:(1)本发明通过简单的操作即可制备得到3DCoMn2O4@N‑rGA,且原料成本低、制备周期短;(2)制备得到的3DCoMn2O4@N‑rGA能够快速高效激活PMS产生自由基催化降解土霉素、加替沙星、布洛芬,且在活化PMS过程中可避免CoMn2O4溶解和团聚。
Description
技术领域
本发明涉及一种复合型催化剂及其制备方法和应用,具体涉及一种由氮(N)、还原氧化石墨烯(rGO)和钴锰氧体(CoMn2O4)组成的复合型催化剂及其制备方法和在降解土霉素、加替沙星等抗生素以及布洛芬这些有机物中的应用,属于有机物降解技术领域。
背景技术
作为20世纪最伟大的科学成就之一,抗生素被广泛用于治疗人类和动物的疾病。但是,抗生素的滥用形成的抗生素污染物破坏了生态平衡,造成了严重的环境危机,引起了越来越多的关注(Environmental Pollution,2019,253:100-110,Journal ofEnvironmental Management,2016,182:620-640)。土霉素(OTC)作为一种广谱抗生素,已广泛用于治疗人类和动物炎症。但是只有一小部分的OTC可以被人或动物吸收,大多数OTC通过排泄进入环境并出现在地表水、废水、土壤和沉积物中,这些OTC的存在对生态环境造成了严重的威胁(Water Research,2019,161:308-318,Environmental Pollution,2018,243:1550-1557)。因此必须探索和实施治疗技术,以应对灾难性的情况。
随着OTC降解成为学术研究的热点,高级氧化(AOP)过程在众多OTC去除方法中脱颖而出,其中,硫酸根自由基主导的AOP凭借还原电位较高(2.5~3.1V)、半衰期较长(30~40μs)、对抗生素有机污染物的选择性较高、pH范围较宽(3~11)等优势,在抗生素有机污染物降解研究中成为新的亮点(Chemical Engineering Journal,2018,334:1502-1517,Chemical Engineering Journal,2017,330:44-62)。钴(Co)基双金属多相催化剂凭借高催化活性和相对较慢的Co2+释放优势已被广泛用于PMS活化(Chemosphere,2018,210:877-888,Applied Catalysis B:Environmental,2016,181:103-117)。由于两种金属之间的紧密相互作用,钴锰双金属氧化物可以有效抑制金属离子的浸出。值得一提的是,CoMn2O4活化PMS产生自由基氧化降解有机污染物近几年引起了研究者的关注。但CoMn2O4在此过程中经常发生溶解和团聚,限制了有机污染物的降解(Chemical Engineering Journal,2018,337:101-109,Journal of Hazardous Materials,2015,296:128-137,Science of TheTotal Environment,2020,711:134715)。
发明内容
为解决现有技术的不足,本发明的目的在于提供一种既能避免CoMn2O4在活化PMS产生自由基过程中溶解和团聚,又能提高CoMn2O4催化降解有机物(土霉素、加替沙星、布洛芬)的活性的复合型催化剂,以及一种通过简单的操作即可制备得到该复合型催化剂的方法。
为了实现上述目标,本发明采用如下的技术方案:
一种复合型催化剂的制备方法,所述复合型催化剂为具有3D立体结构的、负载CoMn2O4的、N掺杂的还原氧化石墨烯气凝胶,记为3D CoMn2O4/N-rGA,其制备方法包括以下步骤:
(1)用Hummer法制备GO;
(2)以锰源、钴源、多巴胺和前面制备得到的GO为原料,钴和锰的物质的量比为1:2,用水热法制备复合水凝胶,反应温度为160~200℃,保温时间为10~14h;
(3)将前面制备得到的复合水凝胶冷冻干燥,得到复合气凝胶;
(4)煅烧前面制备得到的复合气凝胶,得到3D CoMn2O4/N-rGA,反应温度为500~700℃,保温时间为3~5h。
优选的,在步骤(1)中,用Hummer法制备GO具体包括以下步骤:将石墨、硝酸钠和浓硫酸混合并在冰水浴中搅拌,然后缓慢加入高锰酸钾,在35℃油浴条件下搅拌30min,之后加入超纯水,升温至90℃保温15min,再加入超纯水搅拌,然后缓慢加入浓度为30wt%的过氧化氢溶液搅拌30min,混合物由黑色变为棕黄色,将混合物离心并洗涤至pH中性,最后冷冻干燥,研磨得到GO。
优选的,在步骤(2)中,所述锰源选用的是醋酸锰或硝酸锰,所述钴源选用的是醋酸钴或硝酸钴;用水热法制备复合水凝胶具体包括以下步骤:(a)将GO和浓度为50mM、pH=8.5的Tris-HCl溶液混合,超声搅拌30min,制成均匀的GO分散液;(b)向GO分散液中加入多巴胺,超声溶解后再加入锰源和钴源,超声溶解后再剧烈搅拌30min,得到混合溶液;(c)将混合溶液加入到聚四氟乙烯做内衬的水热反应釜中,于160~200℃下反应10~14h,自然冷却至室温,得到复合水凝胶。
优选的,在步骤(4)中,煅烧复合气凝胶的方法具体如下:将复合气凝胶装于管式炉中,在氩气保护下,将管式炉以1~10℃/min的速度升温至500~700℃,煅烧3~5h,得到复合型催化剂。
一种复合型催化剂,所述复合型催化剂为具有3D立体结构的、负载CoMn2O4的、N掺杂的还原氧化石墨烯气凝胶,具体由上述方法制备得到。
本发明的有益之处在于:
(1)本发明提供的制备方法,利用化学还原法、冻干法和高温退火法,通过简单的操作即可制备得到3D CoMn2O4@N-rGA,并且制备周期较短;
(2)本发明提供的制备方法,所使用的原材料易得,成本低,便于广泛推广应用;
(3)本发明制备得到的3D CoMn2O4@N-rGA,比表面积较大,活性位点较多,能够快速、高效激活PMS产生自由基催化降解土霉素、加替沙星等抗生素以及布洛芬,并且在活化PMS产生自由基过程中有效避免了CoMn2O4溶解和团聚;
(4)本发明制备得到的3D CoMn2O4@N-rGA方便回收,可重复使用多次。
附图说明
图1是制备3D CoMn2O4@N-rGA的示意图;
图2是3D CoMn2O4@N-rGA的SEM图像;
图3是3D CoMn2O4@N-rGA的TEM图像及粒度分布图;
图4是3D CoMn2O4@N-rGA的HRTEM图像,右上角的插图是3D CoMn2O4@N-rGA的SAED图案;
图5是3D CoMn2O4@N-rGA的STEM图像和C、O、N、Mn、Co的相应元素映射图;
图6是GO和3D CoMn2O4@N-rGA的XRD谱图;
图7是GO和3D CoMn2O4@N-rGA的FT-IR谱图;
图8是3D CoMn2O4@N-rGA的N2吸附-脱附曲线;
图9是3D CoMn2O4@N-rGA的BJH孔径分布曲线;
图10是在不同催化剂体系下土霉素的降解曲线;
图11是3D CoMn2O4@N-rGA/PMS的紫外光谱图;
图12是3D CoMn2O4@N-rGA降解其他抗生素及实际废水的紫外光谱图,其中,(a)是3D CoMn2O4@N-rGA降解布洛芬(IBP)的紫外光谱图,(b)是3D CoMn2O4@N-rGA降解加替沙星(GFX)的紫外光谱图,(c)是3D CoMn2O4@N-rGA降解A公司稀释10倍的医药废水的紫外光谱图,(d)是3D CoMn2O4@N-rGA降解B公司稀释10倍的医药废水的紫外光谱图;
图13是3D CoMn2O4@N-rGA反应前后的SEM图,其中,(a)是反应前的3D CoMn2O4@N-rGA的SEM图,(b)是循环使用10次后的3D CoMn2O4@N-rGA的SEM图。
具体实施方式
一、制备由N、rGO和CoMn2O4组成的复合型催化剂
实施例1
1、制备氧化石墨烯(GO)
将1g石墨(325目)、0.5g硝酸钠和28mL浓度为98wt%的浓硫酸混合并在冰水浴中搅拌2min,然后缓慢加入3g高锰酸钾,在35℃油浴条件下搅拌30min,之后加入50mL超纯水,升温至90℃保温15min,再加入170mL超纯水搅拌2min,然后缓慢加入5mL浓度为30wt%的过氧化氢溶液搅拌30min,混合物由黑色变为棕黄色。将混合物在2500rpm条件下离心10min,然后用100mL浓度为1mol/L的HCl溶液洗涤并离心(用于除去金属离子),再用超纯水洗涤并离心直至pH中性,最后冷冻干燥36h,将干燥产物研磨,制备得到氧化石墨烯(GO)。
2、制备3D CoMn2O4@N-rGA
参照图1,制备3D CoMn2O4@N-rGA具体包括以下步骤:
(1)将0.1g GO和50mL Tris-HCl溶液(50mM,pH=8.5)混合,超声搅拌30min,制成均匀的GO分散液。
(2)向GO分散液中依次加入0.05g(0.3mmol)多巴胺(DA)、0.735g(3.0mmol)Mn(AC)2·4H2O和0.373g(1.5mmol)Co(AC)2·4H2O,超声溶解后再剧烈搅拌30min,得到混合溶液。
(3)将混合溶液加入到聚四氟乙烯做内衬的水热反应釜中,在烘箱中于180℃反应12h,自然冷却至室温,得到复合水凝胶。
(4)将复合水凝胶冷冻干燥36h,得到复合气凝胶。
(5)将复合气凝胶盛放在瓷舟中,在氩气保护下,于管式炉中以5℃/min的速度升温至600℃,煅烧4h,得到复合型催化剂,记为3D CoMn2O4@N-rGA。
实施例2
本实施例与实施例1的区别仅在于:在制备3D CoMn2O4@N-rGA时,将反应物的用量放大了2倍,具体的,用0.2g GO和50mL Tris-HCl溶液(100mM,pH=8.5)制备GO分散液,并向GO分散液中依次加入0.1g(0.6mmol)DA、1.470g(6.0mmol)Mn(AC)2·4H2O和0.746g(3.0mmol)Co(AC)2·4H2O。其余与实施例1完全一样,不再赘述。
实施例3
本实施例与实施例1的区别仅在于:在制备3D CoMn2O4@N-rGA时,将水热时间延长至24h。其余与实施例1完全一样,不再赘述。
实施例4
本实施例与实施例1的区别仅在于:在制备3D CoMn2O4@N-rGA时,将水热温度降低至100℃。其余与实施例1完全一样,不再赘述。
实施例5
本实施例与实施例1的区别仅在于:在制备3D CoMn2O4@N-rGA时,使用不同的锰源和钴源,具体的,使用1.133g(3.0mmol)Mn(NO3)2·6H2O和0.436g(1.5mmol)Co(NO3)2·6H2O。其余与实施例1完全一样,不再赘述。
二、表征上述复合型催化剂的结构
实施例1至实施例5都以rGO为载体,并且所选用的表面活性剂均为多巴胺,所以高温退火后制备得到的催化剂均具有3D立体结构并且均有N掺杂,虽然各实施例所使用的锰源和钴源不尽相同,但最终制备得到的催化剂的钴和锰的摩尔比均是1:2,此外,虽然各实施例的水热条件和高温退火条件有差别,但是此差别不会对催化剂的结构产生显著的影响,所以,实施例1至实施例5制备得到的催化剂具有相同的结构和基本相同的催化效果。
下面以实施例1制备得到的3D CoMn2O4/N-rGA为代表,对本发明制备得到的N掺杂复合型催化剂及其相关物质的结构进行表征。
1、形貌
观察3D CoMn2O4@N-rGA的实物可知,其是一种密度很小且具备三维宏观结构特性的复合材料。
3D CoMn2O4/N-rGA的SEM图像见图2,TEM图像及粒度分布图见图3,HRTEM图像和选取的SAED图案见图4,STEM图像和C、N、O、Mn、Co的相应元素映射图见图5。
由图2可知,3D CoMn2O4@N-rGA是具有连续大孔的互连多孔3D框架。
由图3可知,规则的矩形CoMn2O4纳米颗粒与N-rGA均匀附着,证明DA是一种优良的表面活性剂。
由图4可知,通过HRTEM测量的典型晶格间距为0.27nm,对应于CoMn2O4的(113)面,而SAED(插图)表明CoMn2O4纳米颗粒的晶体结构不受N-rGA的干扰。
由图5可知,Co、Mn、N和O元素的信号明显显示出规则的矩形,C、N和O信号作为背景噪声填充照片。确认DA成功完成了作为氮掺杂剂和表面活性剂的使命。
上述结构和形貌结果表明,成功制备了锚定具有三维网络结构的规则CoMn2O4纳米颗粒的N-rGA。
2、XRD谱
XRD谱图揭示了所制备样品的详细晶体结构。GO和3D CoMn2O4@N-rGA的XRD谱图见图6。
由图6可知,3D CoMn2O4@N-rGA中GO(001)及(100)消失,产生了rGO的(002)峰,同时出现了CoMn2O4(JCPDS,77-0471)中(101)、(112)、(200)、(103)、(211)、(220)、(204)、(105)、(321)、(224)和(400)的特征峰,故此可以证实目标材料是rGO与CoMn2O4的复合材料。
3、FT-IR谱
GO和3D CoMn2O4@N-rGA的FT-IR谱图见图7。
从图7中可观察到位于3404cm-1和1416cm-1对应GO的-OH官能团及-COOH官能团及其他特征伸缩振动峰,证实了氧化石墨烯的成功制备;在3D CoMn2O4@N-rGA的FT-IR谱中发现GO的1716cm-1、1220cm-1、1052cm-1、578cm-1特征峰消失,出现了新的1155cm-1、628cm-1、508cm-1特征峰,这些新的特征峰分别对应-C-N、-Mn-O、-Co-O的特征伸缩震动峰。证明了GO发生转化,N成功掺杂到石墨烯中,并且证实有CoMnxOy存在,对照其他数据说明3D CoMn2O4@N-rGA成功制备。
4、N2吸脱附曲线和孔径分布曲线
3D CoMn2O4@N-rGA的N2吸附-脱附曲线见图8,BJH孔径分布曲线见图9。
由图8可知,3D CoMn2O4@N-rGA的N2吸附-脱附等温曲线比较符合BET试验中IV型吸附等温线,且在相对压力为0.35~0.95之间有一个很明显的H3型回滞环,表明3D CoMn2O4@N-rGA内部存在介孔并在吸附中出现毛细凝聚现象,同时说明其属于孔结构不规整的裂隙孔材料。
由图9可知,根据IUPAC的孔径标准,3D CoMn2O4@N-rGA包含了介孔和大孔,与SEM数据相互印证。这样的孔径结构有助于CoMn2O4纳米催化剂附着和分布,同时有利于污染物的富集并且确保了催化剂与污染的充分接触。
三、检测上述复合型催化剂的性能
1、催化剂体系对土霉素降解的影响
为了进一步说明3D CoMn2O4@N-rGA/PMS催化剂体系对土霉素具有良好的去除性能,展开单独的3D CoMn2O4@N-rGA催化剂体系、单独的PMS催化剂体系和CoMn2O4/PMS催化剂体系降解土霉素的实验。
制备初始浓度C0为20mg/L的土霉素溶液,用0.1M NaOH调节溶液的pH值至11。
取40mL土霉素溶液,加入到100mL玻璃反应容器中,然后分别向玻璃反应容器中加入4mg CoMn2O4、3D CoMn2O4/N-rGA或不加入这些催化剂,再加入12mg PMS或者不加PMS,在25℃下以250rpm的速度持续搅拌,在加入催化剂4min、8min、12min、16min、20min后,通过注射器取出溶液样品并用孔径为0.22um的水注射器过滤器过滤,然后立即通过UV-Vis在358nm处分析土霉素的含量Ct,以Ct/C0为纵坐标、以反应时间为横坐标作图,得到的不同催化剂体系下土霉素的降解曲线见图10。
由图10可知,在单独的3D CoMn2O4@N-rGA催化剂体系和单独的PMS催化剂体系中,土霉素的降解效率均较低,降解率(1-Ct/C0)分别为35.9%和48.9%;在CoMn2O4/PMS催化剂体系中,土霉素的降解率达到了80.1%;在3D CoMn2O4@N-rGA/PMS催化剂体系中,土霉素的降解率达到了91.3%。
上述结果表明,CoMn2O4与N-rGA的结合,充分利用了N-rGA三维网络结构,加速了电子转移,避免了纳米催化剂堆积,最大限度发挥了催化剂效用。
针对3D CoMn2O4/N-rGA/PMS催化体系,对在0min、4min、8min、12min、16min、20min取得的样品进行UV-Vis检测,得到的随时间变化的土霉素紫外光谱见图11。
由图11可知,3D CoMn2O4/N-rGA/PMS催化体系能够有效去除土霉素。
2、3D CoMn2O4@N-rGA对其他抗生素及实际废水的适用性
为了进一步印证3D CoMn2O4@N-rGA/PMS催化剂体系的广泛适用性,又进行了IBP和GFX的降解实验。
分别制备初始浓度C0为20mg/L的布洛芬(IBP)溶液和加替沙星(GFX)溶液,用0.1MNaOH调节溶液的pH值至11。
取40mLIBP溶液和GFX溶液,分别加入到100mL玻璃反应容器中,然后分别向玻璃反应容器中加入4mg 3D CoMn2O4/N-rGA和12mg PMS,在25℃下以250rpm的速度持续搅拌,在加入催化剂0min、2min、5min、10min、20min后,通过注射器取出溶液样品并用孔径为0.22um的水注射器过滤器过滤,取样后立即进行UV-Vis检测,得到的随时间变化的IBP的紫外光谱见图12(a),GFX的紫外光谱见图12(b)。
由图12(a)和图12(b)可知,3D CoMn2O4@N-rGA/PMS催化剂体系在20min内基本可以完全去除IBP和GFX。
为了探索3D CoMn2O4@N-rGA/PMS催化剂体系对实际抗生素医药废水的降解效果,收集了A医药公司和B医药公司的含有多种抗生素的实际工业废水。
将收集到的A医药公司和B医药公司的工业废水用蒸馏水稀释10倍。取40mL稀释后的工业废水,分别加入到100mL玻璃反应容器中,然后分别向玻璃反应容器中加入4mg 3DCoMn2O4/N-rGA和12mgPMS,在25℃下以250rpm的速度持续搅拌,在加入催化剂0min、5min、10min、15min、20min、25min、30min后,通过注射器取出溶液样品并用孔径为0.22um的水注射器过滤器过滤,取样后立即进行UV-Vis检测,得到的随时间变化的A医药公司的工业废水的紫外光谱见图12(c),B医药公司的工业废水的紫外光谱见图12(d)。
由图12(c)和图12(d)可知,3D CoMn2O4@N-rGA/PMS催化剂体系在多种含水有机污染物的实际医用废水中表现出了优异的降解性能,具备实际应用的潜质。
3、3D CoMn2O4@N-rGA的稳定性
为了确定3D CoMn2O4@N-rGA在实际应用过程中的稳定性,对3D CoMn2O4@N-rGA进行了10次循环使用测试。
新制备得到的3D CoMn2O4@N-rGA的SEM图见图13(a),循环使用10次后的3DCoMn2O4@N-rGA的SEM图见图13(b)。
由图13(a)和图13(b)可知,3D CoMn2O4@N-rGA经过10次循环使用后,形貌发生了一定变化,但依然保持三维结构。因此,可以确定3D CoMn2O4@N-rGA结构比较稳定,具备实际应用的潜质。
需要说明的是,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无法对所有的实施方式予以穷举。凡是属于本发明技术方案所引申出的显而易见变化或变动仍处于本发明的保护范围之列。
Claims (7)
1.一种复合型催化剂的制备方法,其特征在于,所述复合型催化剂为具有3D立体结构的、负载CoMn2O4的、N掺杂的还原氧化石墨烯气凝胶,记为3D CoMn2O4/N-rGA,其制备方法包括以下步骤:
(1)用Hummer法制备GO;
(2)以锰源、钴源、多巴胺和前面制备得到的GO为原料,钴和锰的物质的量比为1:2,用水热法制备复合水凝胶,反应温度为160~200℃,保温时间为10~14h;
(3)将前面制备得到的复合水凝胶冷冻干燥,得到复合气凝胶;
(4)煅烧前面制备得到的复合气凝胶,得到3D CoMn2O4/N-rGA,反应温度为500~700℃,保温时间为3~5h。
2.根据权利要求1所述的制备方法,其特征在于,在步骤(1)中,用Hummer法制备GO具体包括以下步骤:
将石墨、硝酸钠和浓硫酸混合并在冰水浴中搅拌,然后缓慢加入高锰酸钾,在35℃油浴条件下搅拌30min,之后加入超纯水,升温至90℃保温15min,再加入超纯水搅拌,然后缓慢加入浓度为30wt%的过氧化氢溶液搅拌30min,混合物由黑色变为棕黄色,将混合物离心并洗涤至pH中性,最后冷冻干燥,研磨得到GO。
3.根据权利要求1所述的制备方法,其特征在于,在步骤(2)中,所述锰源选用的是醋酸锰或硝酸锰,所述钴源选用的是醋酸钴或硝酸钴。
4.根据权利要求1所述的,其特征在于,在步骤(2)中,用水热法制备复合水凝胶具体包括以下步骤:
(a)将GO和浓度为50mM、pH=8.5的Tris-HCl溶液混合,超声搅拌30min,制成均匀的GO分散液;
(b)向GO分散液中加入多巴胺,超声溶解后再加入锰源和钴源,超声溶解后再剧烈搅拌30min,得到混合溶液;
(c)将混合溶液加入到聚四氟乙烯做内衬的水热反应釜中,于160~200℃下反应10~14h,自然冷却至室温,得到复合水凝胶。
5.根据权利要求1所述的,其特征在于,在步骤(4)中,煅烧复合气凝胶的方法具体如下:
将复合气凝胶装于管式炉中,在氩气保护下,将管式炉以1~10℃/min的速度升温至500~700℃,煅烧3~5h,得到复合型催化剂。
6.一种复合型催化剂,其特征在于,所述复合型催化剂为具有3D立体结构的、负载CoMn2O4的、N掺杂的还原氧化石墨烯气凝胶,具体由权利要求1至5任意一项所述方法制备得到。
7.权利要求6所述的复合型催化剂与PMS构成协同体系在降解有机物中的应用,所述有机物包括土霉素、加替沙星和布洛芬。
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