CN108855191B - 可见光响应的杂化气凝胶及其制备方法与在废气处理中的应用 - Google Patents
可见光响应的杂化气凝胶及其制备方法与在废气处理中的应用 Download PDFInfo
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Abstract
本发明公开了可见光响应的杂化气凝胶及其制备方法与在废气处理中的应用,以双氰胺为前驱体,经过两次煅烧,制备氮化碳纳米片;将氮化碳纳米片分散于水中,原位生长偏钒酸银量子点,制备偏钒酸银量子点/氮化碳纳米片复合材料;将偏钒酸银量子点/氮化碳纳米片复合材料与氧化石墨烯进行水热反应,然后冷冻干燥,制备偏钒酸银量子点/氮化碳纳米片/石墨烯杂化气凝胶,为可见光响应的杂化气凝胶。本发明克服了传统烟气脱硝技术处理废气存在的还原剂量大,二次污染严重,操作复杂等问题,光催化氧化法反应条件温和,能耗低,去除效率高,在污染物降解领域已经得到广泛应用。
Description
技术领域
本发明属于纳米复合材料技术领域,具体涉及一种可见光响应的偏钒酸银量子点/氮化碳纳米片/石墨烯杂化气凝胶及其制备与在废气处理方面的应用。
背景技术
近年来,全球废气排放量迅速增加,环境容量基本饱和,导致了一系列区域和环境问题,如光化学烟雾,酸雨和臭氧层破坏。大多数废气的水溶性和反应性差,难以控制。目前使用的烟气脱硝技术还存在还原剂量大,二次污染严重,操作复杂等问题。
发明内容
本发明的目的是提供一种可见光响应的偏钒酸银量子点/氮化碳纳米片/石墨烯杂化气凝胶及其制备方法与在废气处理方面的应用。
为了达到上述目的,本发明采用如下具体技术方案:
一种可见光响应的杂化气凝胶的制备方法,包括以下步骤:
(1)以双氰胺为前驱体,经过两次煅烧,制备氮化碳纳米片;
(2)将氮化碳纳米片分散于水中,原位生长偏钒酸银量子点,制备偏钒酸银量子点/氮化碳纳米片复合材料;
(3)将偏钒酸银量子点/氮化碳纳米片复合材料与氧化石墨烯进行水热反应,然后冷冻干燥,制备偏钒酸银量子点/氮化碳纳米片/石墨烯杂化气凝胶,为可见光响应的杂化气凝胶。
本发明还公开了偏钒酸银量子点/氮化碳纳米片复合材料及其制备方法,包括以下步骤:
(1)以双氰胺为前驱体,经过两次煅烧,制备氮化碳纳米片;
(2)将氮化碳纳米片分散于水中,原位生长偏钒酸银量子点,制备偏钒酸银量子点/氮化碳纳米片复合材料。
本发明还公开了一种废气处理的方法,包括以下步骤:
(1)以双氰胺为前驱体,经过两次煅烧,制备氮化碳纳米片;
(2)将氮化碳纳米片分散于水中,原位生长偏钒酸银量子点,制备偏钒酸银量子点/氮化碳纳米片复合材料;
(3)将偏钒酸银量子点/氮化碳纳米片复合材料与氧化石墨烯进行水热反应,然后冷冻干燥,制备可见光响应的杂化气凝胶;
(4)将废气通过可见光响应的杂化气凝胶,光照,完成废气的处理。
本发明可见光响应的杂化气凝胶的制备方法可举例如下:
(1)以双氰胺为前驱体,在管式炉中经过两次煅烧,得到超薄的氮化碳纳米片;
(2)将氮化碳纳米片分散于去离子水中,先后加入硝酸银和偏钒酸铵,在氮化碳上原位生长偏钒酸银量子点,经过洗涤、离心和干燥后得到偏钒酸银量子点/氮化碳纳米片复合材料;
(3)将偏钒酸银量子点/氮化碳纳米片复合材料与氧化石墨烯通过反应釜水热反应,然后冷冻干燥,得到可见光响应的杂化气凝胶。
上述技术方案中,步骤(1)中,所述第一次煅烧在氩气中进行,煅烧时升温速率为5℃/min,煅烧的时间为4 h,煅烧的温度为550 ℃;所述第二次煅烧在空气中进行,煅烧时升温速率为5 ℃/min,煅烧的时间为2h,煅烧的温度为550 ℃。
上述技术方案中,步骤(2)中,所述氮化碳、硝酸银以及偏钒酸铵的质量比为(18~22):(1~2):(0.5~1),优选20:2:1。原位生长在避光条件下进行,原位生长的时间为8~12h,原位生长的温度为常温。优选的,将硝酸银分散于去离子水中,然后加入氮化碳纳米片,搅拌30min后再加入偏钒酸铵,继续搅拌;进一步优选的,将产物先后用去离子水和乙醇冲洗后烘干制备偏钒酸银量子点/氮化碳纳米片复合材料;优选烘干温度为60~90℃。形成的偏钒酸银的纳米尺寸小且均匀的负载到氮化碳载体的表面,利于高效的催化处理废气。
上述技术方案中,步骤(3)中,所述偏钒酸银量子点/氮化碳纳米片复合材料和氧化石墨烯的质量比为(4~5):(1~2),优选3:1;所述水热反应的温度为95 ℃,反应的时间为6h;所述冷冻干燥的温度为-50 ℃,冷冻干燥的时间为24h。
本发明进一步公开了上述偏钒酸银量子点/氮化碳纳米片/石墨烯杂化气凝胶复合材料在光催化处理废气方面的应用;上述偏钒酸银量子点/氮化碳纳米片在光催化处理废气方面的应用;上述氮化碳纳米片在光催化处理废气方面的应用。优选的,所述废气处理为烟气脱硝或者一氧化氮废气处理。
本发明的优点:
1、本发明采用简单易操作的水热法和冷冻干燥法,制得偏钒酸银量子点/氮化碳纳米片/石墨烯杂化气凝胶复合光催化剂,制备工艺简单,原料廉价易得,易于实现大规模生产;氮化碳的带隙约为2.7 eV,有较高可见光催化性能;但是现有技术表明,由于其较窄的带隙,其光生电子和空穴很容易复合,本发明在氮化碳上修饰偏钒酸银量子点,构成零维/二维异质结,抑制了电子-空穴对的重组,使其发挥协效的氧化还原作用;冷冻干燥后所得三维气凝胶具有规则的几何形貌,在空气中不易吹飞,易于回收利用。
2、本发明偏钒酸银量子点/氮化碳纳米片/石墨烯杂化气凝胶复合光催化剂,具有较大的比表面积,且孔径均一,具有优异的导电性。偏钒酸银量子点的尺寸可调,光稳定性高,禁带宽度窄,可均匀地负载于氮化碳纳米片上,分散电荷,促进光生载流子的转移;偏钒酸银量子点/氮化碳纳米片均匀地分散于石墨烯上,进一步促进了光生载流子的转移,使得体系的荧光强度明显降低,对氮化碳纳米片的逐步改性极大地增强了光催化处理废气方面的能力。
3、本发明克服了传统烟气脱硝技术处理废气存在的还原剂量大,二次污染严重,操作复杂等问题,光催化氧化法反应条件温和,能耗低,去除效率高,在污染物降解领域已经得到广泛应用。
附图说明
图1为氮化碳纳米片的透射电镜图;
图2为偏钒酸银量子点/氮化碳纳米片的透射电镜图;
图3为偏钒酸银量子点/氮化碳纳米片/石墨烯杂化气凝胶的透射电镜图;
图4为偏钒酸银量子点/氮化碳纳米片/石墨烯杂化气凝胶的扫描电镜图;
图5为不同负载质量的偏钒酸银量子点/氮化碳纳米片/石墨烯杂化气凝胶的催化效果图;
图6为不同负载质量的偏钒酸银量子点/氮化碳纳米片/石墨烯杂化气凝胶的催化效果图;
图7为偏钒酸银量子点/氮化碳纳米片/石墨烯杂化气凝胶催化循环图。
具体实施方式
实施例一
氮化碳纳米片的制备,具体步骤如下:
将10 g双氰氨放入管式炉中,在Ar气氛围下进行煅烧,以升温速率5℃/min升温至550℃,煅烧4h,得到块状氮化碳;所得块状氮化碳在空气中进行煅烧,以升温速率5℃/min升温至550℃,煅烧2h,本发明通过煅烧从而获得比表面积较大的氮化碳纳米片;附图1为氮化碳纳米片的透射电镜图。
实施例二
偏钒酸银量子点/氮化碳纳米片的制备,具体步骤如下:
用包裹铝箔的烧杯将硝酸银(0.0170g,0.1mmol)溶解于20ml去离子水中,然后将氮化碳纳米片(0.1g)加入到上述溶液中并搅拌30min,随后获得的悬浮液超声1小时。通过一次性注射器(20ml)以60ml / h的速率将20ml 偏钒酸铵水溶液(0.0117g,0.1mmol)加入到悬浮液中,调节pH至中性并超声处理1小时,油浴搅拌8小时,用去离子水和无水乙醇洗涤三次。 将产物置于80℃的烘箱中8h,制备得偏钒酸银量子点/氮化碳纳米片,记为AVO-CN,根据加入的氮化碳纳米片质量的不同,可得到不同钒酸银负载质量的复合材料AVO10-CN(钒酸银的负载质量为30 wt%)、AVO20-CN、AVO30-CN、AVO40-CN;附图2为偏钒酸银量子点/氮化碳纳米片的透射电镜图。
实施例三
偏钒酸银量子点/氮化碳纳米片/石墨烯杂化气凝胶的制备,具体步骤如下:
将15mg 氧化石墨烯加入玻璃瓶(20ml)中并加入4ml水使其均匀分散,然后将45mgAVO30-CN加入到氧化石墨烯分散体系中,超声混合后,加入30mg L-抗坏血酸,将混合物置于沸水浴中加热,半小时后,形成水凝胶并立即在-40℃冰箱中冷冻40分钟。 自然融化后,将其置于沸水浴中8小时,最后置于冷冻干燥器中冷冻干燥两天以获得形状规则的轻质气凝胶杂化体偏钒酸银量子点/氮化碳纳米片/石墨烯,记为AVO30-CN-GA-75(AVO30-CN的质量分数为75 wt%),根据加入氧化石墨烯质量的不同,可制备得到不同AVO30-CN质量负载的气凝胶,记为AVO30-CN-GA-50、AVO30-CN-GA-75、AVO30-CN-GA-90;附图3为偏钒酸银量子点/氮化碳纳米片/石墨烯杂化气凝胶的透射电镜图;附图4为偏钒酸银量子点/氮化碳纳米片/石墨烯杂化气凝胶的扫描电镜图。
实施例四
光催化降解,具体步骤如下:
在体积为1.6L的密闭圆柱形反应器中心放置50mg催化剂,氙灯垂直放置在反应器上方,一氧化氮气体由浓缩气瓶供应,经压缩空气缸提供的空气流稀释至600ppb,两个气流在三通阀中预混合,流速控制在2.4 L /min。当催化剂,气体和水蒸气在半小时内达到吸附-解吸平衡时,打开300w的氙灯,使用NOx分析仪,测量时间为30min,仪器检测的浓度间隔为1min,最后根据所测浓度数据计算去除效率。附图5、附图6为不同负载质量的偏钒酸银量子点/氮化碳纳米片/石墨烯杂化气凝胶的催化效果图;附图7为偏钒酸银量子点/氮化碳纳米片/石墨烯杂化气凝胶催化循环图。
本发明的光催化氧化法反应条件温和,能耗低,氧化路线与自然界具有正效应的氮固定过程一致,因此在污染物降解领域可得到广泛应用;其中,氮化碳在光催化处理废气方面具有较高的可见光吸收以及降解效率,对其进行改性可抑制电子-空穴对的复合,提高催化效率。
Claims (4)
1.一种可见光响应的杂化气凝胶的制备方法,包括以下步骤:
(1)以双氰胺为前驱体,经过两次煅烧,制备氮化碳纳米片;
(2)将氮化碳纳米片分散于水中,原位生长偏钒酸银量子点,制备偏钒酸银量子点/氮化碳纳米片复合材料;
(3)将偏钒酸银量子点/氮化碳纳米片复合材料与氧化石墨烯进行水热反应,然后冷冻干燥,制备偏钒酸银量子点/氮化碳纳米片/石墨烯杂化气凝胶,为可见光响应的杂化气凝胶;
步骤(1)中,第一次煅烧在氩气中进行,煅烧时升温速率为5 ℃/min,煅烧的时间为4h,煅烧的温度为550 ℃;第二次煅烧在空气中进行,煅烧时升温速率为5 ℃/min,煅烧的时间为2h,煅烧的温度为550 ℃;
步骤(2)中,将氮化碳纳米片分散于水中,加入硝酸银和偏钒酸铵,原位生长偏钒酸银量子点;氮化碳、硝酸银以及偏钒酸铵的质量比为(18~22):(1~2):(0.5~1);原位生长在避光条件下进行,原位生长的时间为8~12 h,原位生长的温度为常温;
步骤(3)中,偏钒酸银量子点/氮化碳纳米片复合材料和氧化石墨烯的质量比为(4~5):(1~2);水热反应的温度为95 ℃,反应的时间为6h;冷冻干燥的温度为-50 ℃,冷冻干燥的时间为24h。
2.根据权利要求1所述的方法,其特征在于,将氮化碳纳米片分散于去离子水中,然后加入硝酸银,搅拌30min后再加入偏钒酸铵,原位生长偏钒酸银量子点;氮化碳、硝酸银以及偏钒酸铵的质量比为20:2:1。
3.根据权利要求1所述的方法,其特征在于,偏钒酸银量子点/氮化碳纳米片复合材料和氧化石墨烯的质量比为3:1。
4.根据权利要求1所述的方法制备的可见光响应的杂化气凝胶。
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