CN110756223A - 一种吸附催化复合材料及其在污染物处理中的应用 - Google Patents
一种吸附催化复合材料及其在污染物处理中的应用 Download PDFInfo
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Abstract
本发明公开了一种硒化铜‑聚多巴胺‑石墨相氮化碳吸附催化复合材料及其制备方法和在污染物处理中的应用,属于光催化材料技术领域。其中硒化铜是良好的半导体材料,因其带隙宽,有利于更好的吸收太阳光。石墨相氮化碳具有热稳定性好,化学性质和光学性质稳定,并且具有较大的比表面积,增加了其吸附性能。聚多巴胺含有大量亲水的羟基、氨基官能团,其表面电荷可以通过质子化和去质子化来调节,聚多巴胺的亲水性和丰富的π电子系统,易与苯环形成强烈的π‑π堆积作用,对含有芳香环的化合物有较强的吸附作用,同时聚多巴胺可以加速光生电子和质子的分离和转移,减少电子‑空穴复合,提高催化反应的效率。在相同条件下硒化铜‑聚多巴胺‑石墨相氮化碳吸附催化复合材料比硒化铜和硒化铜‑聚多巴胺纳米材料表现出更高的光催化吸附性能。
Description
技术领域
本发明属于光催化材料技术领域,具体涉及一种硒化铜-聚多巴胺-石墨相氮化碳吸附催化复合材料及其制备方法和在污染物处理中的应用。
背景技术
光催化和吸附技术作为目前公认的处理污染物的快速有效方法,引起了广泛的关注和探索。光催化技术可以利用太阳光作为能源进行物质转化,可使污染物得到去除和降解。吸附催化剂对污染物优秀的吸附作用兼具光催化剂对污染物优秀的降解能力,可以实现高效和连续性的吸附降解。
硒化铜(CuSe)是良好的半导体材料,因其带隙宽,有利于更好的吸收太阳光,可以作为优良的光催化材料,但其吸附性较差,不利于催化剂与污染物之间的充分接触。石墨相氮化碳(g-C3N4)作为一种具有类石墨结构的稳定化合物具有热稳定性好,比表面积大,可以吸收太阳能、化学性质和光学性质稳定、价格便宜、组成简单、环境友好等优良性质,被认为是一种有前途的非金属半导体光催化剂,引起人们极大的关注。但由于其对光的吸收不高,而且光生电子-空穴对也极易复合,因此选择合适的半导体与其复合形成异质结可以改善其光电性能。多巴胺可以比较容易地在无机和有机材料表面上自聚合形成聚多巴胺(PDA)薄膜层,聚多巴胺含有大量亲水的羟基、氨基官能团,其表面电荷可以通过质子化和去质子化来调节,能够与多种分子结合而无需进一步的表面活化或处理,PDA的亲水性和丰富的π电子系统,易与苯环形成强烈的π-π堆积作用,对含有芳香环的化合物有较强的吸附作用,同时PDA可以加速g-C3N4光生电子和质子的分离和转移,减少电子-空穴复合,提高催化反应的效率。本发明以制备的CuSe、PDA和g-C3N4为基础制备复合材料,其可用于污染物的吸附催化降解处理。
发明内容
本发明的目的是提供一种具有较高吸附性能和可见光响应的硒化铜-聚多巴胺-石墨相氮化碳吸附催化复合材料及其制备方法和在污染物处理中的应用,通过该方法得到的硒化铜-聚多巴胺-石墨相氮化碳吸附催化复合材料具有吸附和可见光催化性能,可用于污染物的吸附和在可见光条件下催化降解污染物。
本发明所采用的技术方案是将多巴胺与硒化铜按一定比例混合,使多巴胺自聚合在硒化铜上,然后负载在石墨相氮化碳上制得。具体包括如下步骤:
(1)将一定量的模板剂加入到反应瓶中,将由亚硫酸钠和硒粉反应得到的亚硒酸钠与硫酸铜和氨水反应得到的硫酸四氨合铜溶液以一定比例加入到反应瓶中,控制一定的温度并不断搅拌,反应结束后过滤,用无水乙醇和去离子水洗涤,干燥后得到硒化铜(化学组成式为CuSe);
(2)称取一定量制备的CuSe加入到100mL去离子水中,加入一定量的多巴胺,搅拌,加入Tris-HCl溶液,然后调节pH到一定值,搅拌。反应结束后离心,洗涤,干燥,得到硒化铜-聚多巴胺(表示为CuSe-PDA)。
(3)称取一定量的三聚氰胺平铺在有盖的氧化铝坩埚中,置于程序升温电炉中以一定温度焙烧,并持续一定时间,冷却至室温后将得到的样品研磨成粉末得到石墨相氮化碳(表示为g-C3N4)。
(4)称取一定量的石墨相氮化碳分散于一定量的去离子水中,加入一定量制备的CuSe-PDA搅拌,然后加入到高压反应釜中,在一定温度下反应一定时间,冷却,过滤,洗涤,真空干燥,得到光催化吸附材料。
具体的,步骤(1)中,模板剂为乙二醇,三乙醇胺;
具体的,步骤(1)中,反应温度保持在40-80℃;
具体的,步骤(2)中,pH为8-10;
具体的,步骤(2)中,所述多巴胺与硒化铜的质量比为2:1~1:5;
具体的,步骤(3)中,焙烧温度保持在450-650℃,焙烧时间为2-6小时,升温速率为2-10℃/min;
具体的,步骤(4)中,高压反应釜中的混合溶液保持温度在120-200℃下密闭反应8-14小时;
具体的,步骤(4)中,所述石墨相氮化碳与硒化铜-聚多巴胺的质量比为2:1~1:3;
具体的,步骤(4)中,所述真空干燥温度为20-60℃。
上述硒化铜-聚多巴胺-石墨相氮化碳复合材料制备方法制备的吸附催化复合材料可应用于吸附光催化降解污染物,其吸附催化性能优越。
本发明的有益效果在于该制备方法得到的硒化铜-聚多巴胺-石墨相氮化碳吸附催化复合材料具有吸附和可见光催化性能,可见光响应频率范围宽,对污染物具有优异的吸附性能,可用于可见光下污染物尤其是有机染料的吸附和光催化降解处理。通过实验结果可知,其对亚甲基蓝的去除效果较好。
附图说明
图1为本发明制备的硒化铜-聚多巴胺-石墨相氮化碳吸附催化复合材料的扫描电镜图。
图2为本发明制备的硒化铜-聚多巴胺-石墨相氮化碳吸附催化复合材料的氮气吸附-解吸等温线。
图3为本发明制备的硒化铜-聚多巴胺-石墨相氮化碳吸附催化复合材料对亚甲基蓝溶液的光催化降解效果。
具体实施方式
下面通过实施例具体说明本发明,但本发明不受下述实施例的限定。
实施例1
本发明硒化铜-聚多巴胺-石墨相氮化碳吸附催化复合材料的制备方法,具体步骤如下:
1)硒化铜材料的制备
在装有200mL去离子水的圆底烧瓶中加入2.52g亚硫酸钠和0.79g硒粉,70℃下水浴加热并不断搅拌,反应3h后过滤,滤液避光保存,滤液为亚硒酸钠(Na2SeO3)。称取6.25g五水硫酸铜溶于250mL去离子水中,向该溶液中逐滴加入25%氨水,至生成的蓝色沉淀消失时停止加入,得到硫酸四氨合铜(Cu(NH3)4SO4)。
量取40mL乙二醇加入到反应瓶中,加入制备的亚硒酸钠(Na2SeO3)与硫酸四氨合铜(Cu(NH3)4SO4)溶液,保持反应温度在60℃,并不断搅拌。反应0.5h后过滤,用无水乙醇和去离子水洗涤,干燥,得到硒化铜(化学组成式为CuSe)。
2)CuSe-PDA的制备
称取0.5g制备的CuSe加入到100mL去离子水中,超声分散30min,加入0.5g盐酸多巴胺,室温下搅拌60min后加入100mL的Tris-HCl溶液,并用NaOH调节pH到8.5,室温下搅拌24h。离心,收集固体,去离子水洗涤,干燥后得到硒化铜-聚多巴胺(表示为CuSe-PDA)。
3)石墨相氮化碳的制备
称取10g三聚氰胺,平铺在有盖的氧化铝坩埚中,置于程序升温电炉中,保持升温速率为5℃/min,然后在动态空气气氛下加热至500℃焙烧,持续4小时,冷却至室温后将得到的样品研磨成粉末得到石墨相氮化碳(表示为g-C3N4)。
4)硒化铜-聚多巴胺-石墨相氮化碳吸附催化复合材料的制备
分别称取300mg制备的CuSe-PDA和g-C3N4于烧杯中,并加入70mL水,超声分散,然后置于高压反应釜中在温度180℃的烘箱中反应6h,待冷却到室温后,过滤,洗涤,60℃真空干燥,得到吸附催化复合材料硒化铜-聚多巴胺-石墨相氮化碳(表示为CuSe-PDA-g-C3N4)。
图1为实施例1制备的硒化铜-聚多巴胺-石墨相氮化碳吸附催化复合材料的扫描电镜图。
实施例2
采用全自动比表面积和孔径分析仪记录复合材料对氮气的吸附-解吸等温线,用比表面积分析法得到吸附催化复合材料的比表面积为186.6m2·g-1,平均孔径为3.2nm,孔体积为0.151cm3·g-1。吸附催化材料的比表面积较大,吸附性能较好。
图2为实施例1制备的硒化铜-聚多巴胺-石墨相氮化碳吸附催化复合材料的氮气吸附-解吸等温线。
实施例3
实施例1得到的吸附催化复合材料对亚甲基蓝的吸附催化降解效果实验
1)称取0.05g复合吸附催化材料放入试管内,加入50mL浓度为6.0×10-5mol/L的亚甲基蓝溶液,放入光化学反应器中,打开搅拌,先进行暗反应,然后打开光源进行光催化反应。每隔十分钟取一次样,用紫外-可见分光光度计于亚甲基蓝最大吸收波长664nm处测其吸光度,计算亚甲基蓝的浓度。
2)亚甲基蓝的光降解率D按如下公式计算:
C0:初始浓度;Ct:在时间为t时的浓度。所得实验结果如图3所示。
从图3中可以看出吸附催化复合材料可以在可见光下催化降解亚甲基蓝,随时间变化降解率逐渐增加,呈上升趋势。相同条件下吸附催化复合材料对于亚甲基蓝的降解效率明显高于单纯的CuSe和CuSe-PDA纳米材料的降解效率。20min时吸附催化材料对于亚甲基蓝的降解率超过95%,可以很好地处理污染物。
Claims (3)
1.一种硒化铜-聚多巴胺-石墨相氮化碳吸附催化复合材料,其特征在于,包括如下原料:
亚硫酸钠、硒粉、五水硫酸铜、氨水、乙二醇、盐酸多巴胺、Tris-HCl、三聚氰胺。
制备方法包括以下步骤:
(1)将一定量的模板剂加入到反应瓶中,将由亚硫酸钠和硒粉反应得到的亚硒酸钠与硫酸铜和氨水反应得到的硫酸四氨合铜溶液以一定比例加入到反应瓶中,控制一定的温度并不断搅拌,反应结束后过滤,用乙醇和去离子水洗涤,干燥后得到硒化铜(化学组成式为CuSe)。
(2)称取一定量制备的CuSe加入到100mL去离子水中,加入一定量的盐酸多巴胺,搅拌,加入Tris-HCl溶液,然后调节pH到一定值,搅拌。反应结束后离心,洗涤,干燥,得到硒化铜-聚多巴胺(表示为CuSe-PDA)。
(3)称取一定量的三聚氰胺平铺在有盖的氧化铝坩埚中,置于程序升温电炉中以一定温度焙烧,并持续一定时间,冷却至室温后将得到的样品研磨成粉末得到石墨相氮化碳(表示为g-C3N4)。
(4)称取一定量的石墨相氮化碳分散于一定量的去离子水中,加入一定量制备的CuSe-PDA搅拌,然后加入到高压反应釜中,在一定温度下反应一定时间,冷却,过滤,洗涤,真空干燥,得到吸附催化复合材料。
所述模板剂为乙二醇,三乙醇胺;所述多巴胺与硒化铜的质量比为2:1~1:5;所述石墨相氮化碳与硒化铜-聚多巴胺的质量比为2:1~1:3。
2.含有权利要求1所述的硒化铜-聚多巴胺-石墨相氮化碳吸附催化复合材料。
3.含有权利要求1所述的硒化铜-聚多巴胺-石墨相氮化碳吸附催化复合材料在吸附降解污染物方面的应用。
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