CN115301292A - 一种利用Co等离子体结构制备复合催化剂的方法 - Google Patents
一种利用Co等离子体结构制备复合催化剂的方法 Download PDFInfo
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Abstract
用于光催化降解有机废水催化剂及制备方法，涉及一种处理废水催化剂及制备方法，将g‑C3N4、Co‑ZIF‑67、MnO2利用水热合成法和热聚合法制备并相结合，利用Co等离子体结构，通过转移等离激元能量来激发半导体中的电子‑空穴对由金属到半导体，实现光生电子和空穴的分离；以ZIF‑67为框架制备Co‑ZIF‑67材料，优化热稳定和化学性质，且Co‑ZIF‑67具有一定磁性，有利于解决实际应用中回收分离问题；同时在g‑C3N4引入MnO2进行修饰改性，使该复合催化剂具有光催化‑磁性分离‑催化为一体的特性，解决了g‑C3N4因电子‑空穴对的快速复合率和回收再利用问题。
Description
技术领域
本发明属于催化材料制备领域，具体涉及到一种利用Co等离子体结构制备g-C3N4/Co-ZIF-67/MnO2复合催化剂方法。
背景技术
光催化技术是基于光照作用下的光化学反应技术，利用太阳辐射降解有机污染物、氢气光解、二氧化碳还原及气体污染物的脱除。与其他复杂的物理或化学方法相比，用于处理有机污染物的光催化技术具有价格低、安全、简单以及避免二次污染的优点。光催化技术为解决人类面临的水污染和缺水问题提供了一种可持续的、经济高效的技术途径。在众多光催化材料中，g-C3N4因其易于合成、合适的带隙、热稳定性、可靠的化学惰性以及电化学组织良好的光催化性能受到人们的广泛研究，但电子-空穴对的快速复合率和回收再利用问题，在很大程度上限制实际应用中的活性。目前研究人员通过如掺杂元素、形貌调控和异质结构建等方法不同程度提高光催化活性。
近年来，表面等离激元共振技术的不断发展为解决光催化剂的瓶颈问题带来新契机。在特定频率的光辐照射下，具有表面等离激元共振效应的金属粒子会引起抵抗正电荷回复力的电子发生集体振荡从而增加光的吸收峰。在此基础上，通过增加光的散射，改善光的传输；通过转移等离激元能量来激发半导体中的电子-空穴对由金属到半导体，阻碍光生电子和空穴的复合，可以显著提高光催化剂的活性和效率。金属纳米颗粒的化学性质、光响应频段、载流子浓度等都会对其产生的催化作用产生一定影响，目前被认为适合实际应用的金属纳米粒子有Pt、Au、Co等。ZIF-67（沸石类金属有机框架）是MOFS（金属有机框架）一个分支，在有机合成的催化反应、吸附、光催化降解、超级电容器等许多领域都有广泛的应用。ZIF-67既具有MOFS材料较大比表面积和高孔隙率的特性，又因为金属离子与咪唑配体之间较强的相互作用力，使其具有优异的化学和热稳定性。因此选取ZIF-67为前驱体制备具有等离激元效应Co-ZIF-67具有重要意义。
MnO2具有绿色环保，价格低廉等优点．有研究表明，将MnO2引入g-C3N4进行修饰改性，能有效提高g-C3N4的光催化活性，并保持材料的高稳定性。
发明内容
本发明的目的在于提供一种利用Co等离激元效应用于光催化降解有机废水催化剂及制备方法，本发明将g-C3N4、Co-ZIF-67、MnO2利用水热合成法和热聚合法制备并相结合，制备出光催化-磁性分离-催化为一体的催化剂，解决了g-C3N4因电子-空穴对的快速复合率和回收再利用问题，本发明制备方法简单高效，所得催化剂活性高，性质稳定，能多次重复利用。
本发明的目的是通过以下技术方案实现的：
1. 水热合成制备MnO2：将蒸馏水加入KMnSO4、MnSO4，其中n(KMnSO4)：n(MnSO4)为2：3，在常温下搅拌均匀后移至反应釜中；将反应釜放入干燥箱并设置加热温度90-110℃，反应4-6小时。反应结束后过滤混合物得灰黑色固体，用蒸馏水和乙醇分别洗涤3次，至滤液pH为6-7；将得到的固体放入干燥箱并设置加热温度60℃干燥12小时得到MnO2；
2. ZIF-67/MnO2制备：将步骤1)中制备的MnO2超声分散在50mL甲醇中，然后加入Co(
NO3)2·6H2O，室温下磁力搅拌30min，得到溶液a；将2-甲基咪唑分散在50mL甲醇中并超声30min，得到溶液b；将溶液b快速倒入溶液a中并充分搅拌，静置24h后对沉淀物进行离心、洗涤、干燥处理，得到ZIF-67/MnO2；
3. g-C3N4/Co-ZIF-67/MnO2制备：将尿素和步骤2)中制备好的ZIF-67/MnO2定量称量，放在研钵均匀研磨后倒入石英坩埚，放置于马弗炉，在475-550℃煅烧并保温3小时。待冷却至室温所得粉末经研磨后，加入100mL去离子水，超声处理5-8小时后放入干燥箱80℃干燥9-12小时得到g-C3N4/Co-ZIF-67/MnO2。
本发明的优点与效果是：
1.本发明的一种利用Co等离子体结构制备g-C3N4/Co-ZIF-67/MnO2复合催化剂，通过转移等离激元能量来激发半导体中的电子-空穴对由金属到半导体，实现光生电子和空穴的分离；以ZIF-67为框架制备Co-ZIF-67材料，优化了热稳定和化学性质，且Co-ZIF-67具有一定磁性，有利于解决实际应用中回收分离问题；同时MnO2是一种环保高效、氧化活性好的过渡金属氧化物，在引入g-C3N4进行修饰改性，能有效提高g-C3N4的光催化活性，并保持材料的高稳定性，使该复合催化剂具有光催化-磁性分离-催化为一体的特性；
2.本发明方法操作简单，成分易于控制，所制得的材料均一，为工业化生产奠定了基础，具有很好的推广价值。
具体实施方式
下面结合具体实施例，进一步阐述本发明。
实施例1
本发明提供一种利用Co等离子体结构制备g-C3N4/Co-ZIF-67/MnO2复合催化剂方法，具体步骤如下：
1. 水热合成制备MnO2：将蒸馏水加入KMnSO4、MnSO4，其中n(KMnSO4)：n(MnSO4)为2：3，在常温下搅拌均匀后移至反应釜中；将反应釜放入干燥箱并设置加热温度90℃，反应6小时。反应结束后过滤混合物得灰黑色固体，用蒸馏水和乙醇分别洗涤3次，至滤液pH为6-7；将得到的固体放入干燥箱并设置加热温度60℃干燥12小时得到MnO2；
2. ZIF-67/MnO2制备：将步骤1)中制备的MnO2超声分散在50mL甲醇中，然后加入Co(NO3)2·6H2O，室温下磁力搅拌30min，得到溶液a；将2-甲基咪唑分散在50mL甲醇中并超声30min，得到溶液b；将溶液b快速倒入溶液a中并充分搅拌，静置24h后对沉淀物进行离心、洗涤、干燥处理，得到ZIF-67/MnO2；
3. g-C3N4/Co-ZIF-67/MnO2制备：取25毫克步骤2)中制备的ZIF-67/MnO2与5克尿素，放在研钵均匀研磨后倒入石英坩埚，放置于马弗炉，在475℃煅烧并保温3小时。待冷却至室温所得粉末经研磨后，加入100mL去离子水，超声处理5小时后放入干燥箱80℃干燥12小时得到g-C3N4/Co-ZIF-67/MnO2。
实施例2
本发明提供一种利用Co等离子体结构制备g-C3N4/Co-ZIF-67/MnO2复合催化剂方法，具体步骤如下：
1. 水热合成制备MnO2：将蒸馏水加入KMnSO4、MnSO4，其中n(KMnSO4)：n(MnSO4)为2：3，在常温下搅拌均匀后移至反应釜中；将反应釜放入干燥箱并设置加热温度100℃，反应5小时。反应结束后过滤混合物得灰黑色固体，用蒸馏水和乙醇分别洗涤3次，至滤液pH为6-7；将得到的固体放入干燥箱并设置加热温度60℃干燥12小时得到MnO2；
2. ZIF-67/MnO2制备：将步骤1)中制备的MnO2超声分散在50mL甲醇中，然后加入Co(NO3)2·6H2O，室温下磁力搅拌30min，得到溶液a；将2-甲基咪唑分散在50mL甲醇中并超声30min，得到溶液b；将溶液b快速倒入溶液a中并充分搅拌，静置24h后对沉淀物进行离心、洗涤、干燥处理，得到ZIF-67/MnO2；
3. g-C3N4/Co-ZIF-67/MnO2制备：取30毫克步骤2)中制备的ZIF-67/MnO2与10克尿素，放在研钵均匀研磨后倒入石英坩埚，放置于马弗炉，在500℃煅烧并保温3小时。待冷却至室温所得粉末经研磨后，加入100mL去离子水，超声处理6小时后放入干燥箱80℃干燥10小时得到g-C3N4/Co-ZIF-67/MnO2。
实施例3
本发明提供一种利用Co等离子体结构制备g-C3N4/Co-ZIF-67/MnO2复合催化剂方法，具体步骤如下：
1. 水热合成制备MnO2：将蒸馏水加入KMnSO4、MnSO4，其中n(KMnSO4)：n(MnSO4)为2：3，在常温下搅拌均匀后移至反应釜中；将反应釜放入干燥箱并设置加热温度110℃，反应4小时。反应结束后过滤混合物得灰黑色固体，用蒸馏水和乙醇分别洗涤3次，至滤液pH为6-7；将得到的固体放入干燥箱并设置加热温度60℃干燥12小时得到MnO2；
2. ZIF-67/MnO2制备：将步骤1)中制备的MnO2超声分散在50mL甲醇中，然后加入Co(NO3)2·6H2O，室温下磁力搅拌30min，得到溶液a；将2-甲基咪唑分散在50mL甲醇中并超声30min，得到溶液b；将溶液b快速倒入溶液a中并充分搅拌，静置24h后对沉淀物进行离心、洗涤、干燥处理，得到ZIF-67/MnO2；
3. g-C3N4/Co-ZIF-67/MnO2制备：取35毫克步骤2)中制备的ZIF-67/MnO2与15克尿素，放在研钵均匀研磨后倒入石英坩埚，放置于马弗炉，在550℃煅烧并保温3小时。待冷却至室温所得粉末经研磨后，加入100mL去离子水，超声处理8小时后放入干燥箱80℃干燥9小时得到g-C3N4/Co-ZIF-67/MnO2。
Claims (3)
1.用于光催化降解有机废水催化剂及制备方法，其特征在于，该方法是利用Co等离子体结构制备g-C3N4/Co-ZIF-67/MnO2复合催化剂材料，所述方法包括以下过程：
(1) 水热合成制备MnO2：将蒸馏水加入KMnSO4、MnSO4，其中n(KMnSO4)：n(MnSO4)为2：3，在常温下搅拌均匀后移至反应釜中；将反应釜放入干燥箱并设置加热温度90-110℃，反应4-6小时，反应结束后过滤混合物得灰黑色固体，用蒸馏水和乙醇分别洗涤3次，至滤液pH为6-7；将得到的固体放入干燥箱并设置加热温度60℃干燥12小时得到MnO2；
(2) ZIF-67/MnO2制备：将步骤1)中制备的MnO2超声分散在50mL甲醇中，然后加入Co(NO3)2·6H2O，室温下磁力搅拌30min，得到溶液a；将2-甲基咪唑分散在50mL甲醇中并超声30min，得到溶液b；将溶液b快速倒入溶液a中并充分搅拌，静置24h后对沉淀物进行离心、洗涤、干燥处理，得到ZIF-67/MnO2；
(3) g-C3N4/Co-ZIF-67/MnO2制备：将5-15克尿素和步骤2)中制备好的ZIF-67/MnO2定量称量，放在研钵均匀研磨后倒入石英坩埚，放置于马弗炉，在475-550℃煅烧并保温3小时，待冷却至室温所得粉末经研磨后，加入100mL去离子水，超声处理5-8小时后放入干燥箱80℃干燥9-12小时得到g-C3N4/Co-ZIF-67/MnO2复合催化剂。
2.根据权利要求1所述的复合材料，其特征在于：步骤2）中Co(NO3)2·6H2O：2-甲基咪唑摩尔比为0.01：0.04，离心机速率为15 000 r/min，离心时间4-6min。
3.根据权利要求1所述的复合材料，其特征在于：所述ZIF-67/MnO2复合物加入量为25-35毫克。
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