CN113856704B - 一种高效降解抗生素的光催化剂及其制备方法和应用 - Google Patents
一种高效降解抗生素的光催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种高效降解抗生素的光催化剂及其制备方法和应用,该制备方法包括以下步骤:(1)先后将质量比为0.25~4:1的纳米硫化锌和纳米复合材料CuO@Cu2O@Cu均匀分散于去离子水中形成混合液;(2)将步骤(1)中得到的混合液置于微波反应器中进行微波辐照反应,反应结束后自然冷却至室温,然后经过滤、洗涤、干燥,即得到CuO@Cu2O@Cu‑ZnO‑CuS光催化剂。本发明的制备方法简单、操作方便,重复性好,且制备得到的光催化剂能充分吸收可见光和紫外光高效、稳定地降解抗生素。
Description
技术领域
本发明属于半导体光催化剂材料技术领域,具体涉及一种高效降解抗生素的光催化剂及其制备方法和应用。
背景技术
抗生素是微生物的代谢产物,在较低浓度时即可抑制或杀死其他微生物,因而可以治疗和预防由细菌等微生物感染所引起的疾病,被广泛用于人体医疗、水产和畜牧养殖等方面。虽然抗生素的分子量低,但是半衰期短,生物活性高,难以在传统污污水处理工艺中被去除,会随着出水进入地表水,再经补给污染地下水乃至饮用水。人类通过饮用水和食物集聚抗生素,当超过一定浓度时,会导致人体的耐药性增加,更甚者出现肾功能障碍、溶血性贫血、基因突变、癌症等。
抗生素类废水的处理方法有生物、化学和物理处理技术。相比较而言,化学氧化几乎无选择性,可以降解各种抗生素,但是会造成二次污染。近年来兴起的半导体光催化技术直接利用太阳能在常温下降解各种有机污染物,并且因来源广、投入低、制备容易、效率高、无二次污染等特点倍受关注。硫化物和多价过渡金属氧化物的能带合适、催化性能良好,且具有形貌易于调控、矿藏丰富等特点,因而成为光催化降解各种有机污染物的首要选择。但是,多数纯金属氧化物、硫化物中光生电子-空穴对的快速结合限制了其在光催化领域的实际应用。
发明内容
针对现有技术存在的上述不足,本发明的目的就在于提供一种高效降解抗生素的光催化剂及其制备方法和应用,该制备方法简单、操作方便,重复性好,且制备得到的光催化剂能充分吸收可见光和紫外光高效、稳定地降解抗生素。
本发明的技术方案是这样实现的:
一种高效降解抗生素的光催化剂的制备方法,包括以下步骤:
(1)先后将质量比为0.25~4:1的纳米硫化锌和纳米复合材料CuO@Cu2O@Cu均匀分散于去离子水中形成混合液;
(2)将步骤(1)中得到的混合液置于微波反应器中进行微波辐照反应,反应结束后自然冷却至室温,然后经过滤、洗涤、干燥,即得到CuO@Cu2O@Cu-ZnO-CuS光催化剂。
进一步地,所述纳米复合材料CuO@Cu2O@Cu按以下步骤得到:
S1:将可溶性铜盐、氢氧化钠和抗坏血酸或葡萄糖分别溶于去离子水中配制得到溶液A、溶液B和溶液C,备用;
S2:在搅拌的条件下,依次将溶液B和溶液C加入到溶液A中,形成A、B、C的混合液;
S3:将步骤S2得到的A、B、C的混合液置于微波反应器内经微波辐照反应得到CuO@Cu2O溶液;
S4:往CuO@Cu2O溶液中加入甲脒亚磺酸溶液,混合均匀后转移至微波反应器中进行微波辐照反应,反应结束后自然冷却至室温,静置隔夜,最后经过滤、洗涤、干燥即得纳米复合材料CuO@Cu2O@Cu。
进一步地,所述可溶性铜盐为乙酸铜、硝酸铜、氯化铜和硫酸铜中的一种或多种。
进一步地,氢氧化钠和可溶性铜盐的摩尔比4~10:1;抗坏血酸或葡萄糖和可溶性铜盐的摩尔比1:0.5~16;甲脒亚磺酸和可溶性铜盐的摩尔比1:0.25~4。
进一步地,步骤S3和步骤S4中微波辐照反应的功率均为130~650W,其中步骤S3微波辐照反应的时间为5~15min;步骤S4微波辐照反应的时间为3~15min。
进一步地,步骤(1)中采用超声分散纳米硫化锌和纳米复合材料CuO@Cu2O@Cu。
进一步地,步骤(2)中微波辐照反应的功率为130~650W,反应时间为5~15min。
进一步地,步骤(2)中微波辐照反应的功率为130W,反应时间为10min。
一种高效降解抗生素的光催化剂能用于降解含有环丙沙星、诺氟沙星、四环素、磺胺甲恶唑中的一种或多种的废水。
与现有技术相比,本发明具有如下有益效果:
1、本发明采用窄能隙的纳米ZnS和纳米复合材料CuO@Cu2O@Cu为初始原料,纳米复合材料CuO@Cu2O@Cu中的CuO、Cu2O都是能隙比较窄的半导体,不仅吸收紫外光,还能吸收可见光,特别是能隙特别窄的Cu2O,具有超强吸收紫外光和可见光的能力;在微波作用下,纳米ZnS和纳米复合材料CuO@Cu2O@Cu反应,ZnS被消耗掉,产生新组元ZnO和CuS,从而制备使得得到的五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS,使得该光催化剂对可见光和紫外光都有较强的吸收,从而能够充分利用太阳能高效降解抗生素。
2、本发明分两步还原CuO制备纳米复合材料CuO@Cu2O@Cu,便于有效控制每个组分的含量,然后与纳米ZnS反应制备得到的五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS,这时的光催化剂中各组分含量也得到有效控制,使得在太阳光辐照下,导带最负的ZnO作为电子贡体将光生电子转移至CuO、Cu2O和CuS的导带中,相反,自身的价带则聚集大量光生空穴。作为良导体,Cu也会不断接收来自ZnO的光生电子。通过多步迁移,五元复合半导体光催化剂中光生电子和空穴的再结合被有效抑制。
3、本发明采用微波辐照制备五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS,一方面,微波辐照能提高反应速率,从而可以加速晶体结晶,另一方面,因为微波是利用介电作用对纳米硫化锌和纳米复合材料CuO@Cu2O@Cu形成的前驱体溶液进行能量传递,因而加热是均匀的、快速的,加速了纳米晶的成核和生长,能够促使原子快速进入晶格中形成间隙缺陷,并形成相应的空位缺陷,从而有利于纳米ZnS和纳米复合材料CuO@Cu2O@Cu形成晶格缺陷,调节能隙,进而有利于增强最终五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS对太阳光的吸收。
4、本发明制备得到的五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS用于降解含盐酸四环素(120mg/L)、诺氟沙星(40mg/L)、环丙沙星(40mg/L)和磺胺甲恶唑(20mg/L)的溶液,其对含盐酸四环素、诺氟沙星、环丙沙星和磺胺甲恶唑的降解效率分别达到99.01%,95.43%,95.12%和97.35%。
5、本发明制备方法简单,操作简便,重复性好,所制备的五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS在太阳光照下能高效、稳定地降解高浓度的典型抗生素,并且所述光催化剂对环境友好,具有广泛的应用价值。
附图说明
图1-实施例1制备得到的五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS的X射线衍射(XRD)分析图。
图2-实施例1制备得到的五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS的场发射扫描电子显微镜(FESEM)图片;
图3-实施例1制备得到的五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS催化降解盐酸四环素、诺氟沙星、环丙沙星和磺胺甲恶唑的降解效率曲线图。
具体实施方式
下面结合附图和具体实施方式对本发明作进一步详细说明。
实施例1
(1)制备纳米复合材料CuO@Cu2O@Cu:分别称取0.9983g乙酸铜,1.0000g氢氧化钠,0.4403g抗坏血酸,1.0812g甲脒亚磺酸溶于去离子水中得到乙酸铜溶液、氢氧化钠溶液、抗坏血酸溶液和甲脒亚磺酸溶液,然后先后将氢氧化钠溶液和抗坏血酸溶液加入乙酸铜溶液中形成前驱体溶液,在130W的功率下微波辐照10分钟后取出反应混合液,再加入甲脒亚磺酸溶液,并在混合均匀后再次于130W下微波反应10分钟,反应结束后冷却至室温,静置隔夜,过滤沉淀物,分别用去离子水和无水乙醇洗涤3次,干燥6小时以上即得到黑色的纳米复合材料CuO@Cu2O@Cu;
(2)制备五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS:称取0.0500g纳米复合材料CuO@Cu2O@Cu于30mL去离子水中超声分散均匀,然后加入0.0250g纳米ZnS,并继续超声分散形成混合液,CuO@Cu2O@Cu与ZnS的质量比为2:1,最后将混合液移至微波反应器中于130W下加热10分钟,加热结束后冷却至室温,经过滤、洗涤、干燥,得到五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS。
1、本实施例制备得到五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS的X射线衍射(XRD)分析图如图1所示,由图可知:五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS的衍射峰与Cu2O(JCPDS 05-0667)、CuO(JCPDS 48-1548)、Cu(JCPDS 04-0836)、ZnO(JCPDS 36-1451)、和CuS(JCPDS 06-0464)的衍射峰一一对应,表明成功地制备了五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS。
2、本实施例制备得到五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS的发射扫描电子显微镜(FESEM)照片如图2所示,从图中可以看出,五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS主要由微米球和纳米棒组成,并且微米球表面比较粗糙。
3、称取0.0500g五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS分散于50mL的抗生素溶液中,其中抗生素溶液中含有0.12g/L的四环素、0.04g/L诺氟沙星、0.04g/L环丙沙星、0.02g/L磺胺甲恶唑,暗吸附30分钟以后,在300W无滤波片的氙灯下辐照1.5小时,每隔10分钟利用紫外可见分光光度计记录四环素、诺氟沙星、环丙沙星和磺胺甲恶唑溶液的紫外可见光谱,根据浓度与吸光度呈正比的关系,计算四种抗生素的降解效率。所得到的五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS对抗生素的降解效率曲线如图3所示。从图中可以看出五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS对四环素的暗吸附效率较高,达到75.11%,在光照1.5小时后,对四环素的去除效率达到99.01%。五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS对诺氟沙星、环丙沙星和磺胺甲恶唑的吸附效率则较低,但是在经过光照后,降解效率分别为95.43%,95.12%和97.35%。说明五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS能够在太阳光照下快速高效地去除典型的高浓度抗生素。
实施例2
(1)制备纳米复合材料CuO@Cu2O@Cu:分别称取0.9983g乙酸铜,0.8000g氢氧化钠,0.4403g抗坏血酸,0.5406g甲脒亚磺酸溶于去离子水中得到乙酸铜溶液、氢氧化钠溶液、抗坏血酸溶液和甲脒亚磺酸溶液,然后先后将氢氧化钠溶液和抗坏血酸溶液加入乙酸铜溶液中形成前驱体溶液,在130W的功率下微波辐照8分钟后取出反应混合液,再加入甲脒亚磺酸溶液,并在混合均匀后再次于130W下微波反应8分钟,反应结束后冷却至室温,静置隔夜,过滤沉淀物,分别用去离子水和无水乙醇洗涤3次,干燥6小时以上即得到黑色的纳米复合材料CuO@Cu2O@Cu;
(2)制备五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS:称取0.0600g纳米复合材料CuO@Cu2O@Cu于30mL去离子水中超声分散均匀,然后加入0.0200g纳米ZnS,并继续超声分散形成混合液,CuO@Cu2O@Cu与ZnS的质量比为3:1,最后将混合液移至微波反应器中于130W下加热15分钟,加热结束后冷却至室温,经过滤、洗涤、干燥,得到五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS。
1、本实施例得到的五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS用SEM观察,其主要为微米球、纳米棒以及纳米球组成的团聚体,其中纳米棒的长径比相差较大。
2、称取0.0500g本实施例制备得到五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS分散于50mL的抗生素溶液中,其中抗生素溶液中含有0.12g/L的四环素、0.04g/L诺氟沙星、0.04g/L环丙沙星、0.02g/L磺胺甲恶唑,暗吸附30分钟以后,在300W无滤波片的氙灯下辐照1.5小时,对四环素、诺氟沙星、环丙沙星和磺胺甲恶唑的降解效率分别为97.31%,91.76%,90.32%和92.02%。说明五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS能够在太阳光照下快速高效地去除典型的高浓度抗生素。
实施例3
(1)制备纳米复合材料CuO@Cu2O@Cu:分别称取1.2484g硫酸铜,0.4000g氢氧化钠,0.8806g抗坏血酸,0.5406g甲脒亚磺酸溶于去离子水中得到乙酸铜溶液、氢氧化钠溶液、抗坏血酸溶液和甲脒亚磺酸溶液,然后先后将氢氧化钠溶液和抗坏血酸溶液加入乙酸铜溶液中形成前驱体溶液,在130W的功率下微波辐照10分钟后取出反应混合液,再加入甲脒亚磺酸溶液,并在混合均匀后再次于130W下微波反应10分钟,反应结束后冷却至室温,静置隔夜,过滤沉淀物,分别用去离子水和无水乙醇洗涤3次,干燥6小时以上即得到黑色的纳米复合材料CuO@Cu2O@Cu;
(2)制备五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS:称取0.0500g纳米复合材料CuO@Cu2O@Cu于30mL去离子水中超声分散均匀,然后加入0.0500g纳米ZnS,并继续超声分散形成混合液,CuO@Cu2O@Cu与ZnS的质量比为1:1,最后将混合液移至微波反应器中于130W下加热5分钟,加热结束后冷却至室温,经过滤、洗涤、干燥,得到五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS。
1、本实施例得到的五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS用SEM观察,其主要由微米球、纳米棒和不规则纳米颗粒组成,但是微米球较少,且纳米棒的长径比相对于实施例1得到的五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS更大。
2、称取0.0500g本实施例制备得到五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS分散于50mL的抗生素溶液中,其中抗生素溶液中含有0.12g/L的四环素、0.04g/L诺氟沙星、0.04g/L环丙沙星、0.02g/L磺胺甲恶唑,暗吸附30分钟以后,在300W无滤波片的氙灯下辐照1.5小时,对四环素、诺氟沙星、环丙沙星和磺胺甲恶唑的降解效率分别为97.16%,93.32%,92.88%和95.15%。说明五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS能够在太阳光照下快速高效地去除典型的高浓度抗生素。
实施例4
(1)制备纳米复合材料CuO@Cu2O@Cu:分别称取0.9983g乙酸铜,1.0000g氢氧化钠,0.9008g葡萄糖,0.2703g甲脒亚磺酸溶于去离子水中,然后先后将氢氧化钠和抗坏血酸溶液加入乙酸铜溶液中,形成前驱体溶液,在130W的功率下微波辐照15分钟后取出反应混合液,再加入甲脒亚磺酸溶液,并在混合均匀后再次于130W下微波反应15分钟,反应结束后冷却至室温,静置隔夜,过滤沉淀物,分别用去离子水和无水乙醇洗涤3次,干燥6小时以上即得到黑色的纳米复合材料CuO@Cu2O@Cu;
(2)制备五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS:称取0.0500g纳米复合材料CuO@Cu2O@Cu于30mL去离子水中超声分散均匀,然后加入0.0500g纳米ZnS,并继续超声分散形成混合液,CuO@Cu2O@Cu与ZnS的质量比为1:1,最后将混合液移至微波反应器中于130W下加热8分钟,加热结束后冷却至室温,经过滤、洗涤、干燥,得到五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS。
1、本实施例得到的五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS用SEM观察,其主要为微米球、纳米棒以及不规则纳米颗粒组成的团聚体,但是纳米棒较少,微米球较多。
2、称取0.0500g本实施例制备得到五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS分散于50mL的抗生素溶液中,其中抗生素溶液中含有0.12g/L的四环素、0.04g/L诺氟沙星、0.04g/L环丙沙星、0.02g/L磺胺甲恶唑,暗吸附30分钟以后,在300W无滤波片的氙灯下辐照1.5小时,对四环素、诺氟沙星、环丙沙星和磺胺甲恶唑的降解效率分别为98.55%,97.43%,98.44%和98.48%。说明五元复合光催化剂CuO@Cu2O@Cu-ZnO-CuS能够在太阳光照下快速高效地去除典型的高浓度抗生素。
最后需要说明的是,本发明的上述实施例仅是为说明本发明所作的举例,而并非是对本发明实施方式的限定。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他不同形式的变化和变动。这里无法对所有的实施方式予以穷举。凡是属于本发明的技术方案所引申出的显而易见的变化或变动仍处于本发明的保护范围之列。
Claims (9)
1.一种高效降解抗生素的光催化剂的制备方法,其特征在于,包括以下步骤:
(1)先后将质量比为0.25~1:1的纳米硫化锌和纳米复合材料CuO@Cu2O@Cu均匀分散于去离子水中形成混合液;
(2)将步骤(1)中得到的混合液置于微波反应器中进行微波辐照反应,反应结束后自然冷却至室温,然后经过滤、洗涤、干燥,即得到CuO@Cu2O@Cu-ZnO-CuS光催化剂。
2.根据权利要求1所述的一种高效降解抗生素的光催化剂的制备方法,其特征在于,所述纳米复合材料CuO@Cu2O@Cu按以下步骤得到:
S1:将可溶性铜盐、氢氧化钠和抗坏血酸或葡萄糖分别溶于去离子水中配制得到溶液A、溶液B和溶液C,备用;
S2:在搅拌的条件下,依次将溶液B和溶液C加入到溶液A中,形成A、B、C的混合液;
S3:将步骤S2得到的A、B、C的混合液置于微波反应器内经微波辐照反应得到CuO@Cu2O溶液;
S4:往CuO@Cu2O溶液中加入甲脒亚磺酸溶液,混合均匀后转移至微波反应器中进行微波辐照反应,反应结束后自然冷却至室温,静置隔夜,最后经过滤、洗涤、干燥即得纳米复合材料CuO@Cu2O@Cu;
其中,氢氧化钠和可溶性铜盐的摩尔比4~5:1;抗坏血酸或葡萄糖和可溶性铜盐的摩尔比1:0.5~2;甲脒亚磺酸和可溶性铜盐的摩尔比1:0.5~4。
3.根据权利要求2所述的一种高效降解抗生素的光催化剂的制备方法,其特征在于,所述可溶性铜盐为乙酸铜、硝酸铜、氯化铜和硫酸铜中的一种或多种。
4.根据权利要求3所述的一种高效降解抗生素的光催化剂的制备方法,其特征在于,步骤S3和步骤S4中微波辐照反应的功率均为130~650W,其中步骤S3微波辐照反应的时间为5~15min;步骤S4微波辐照反应的时间为3~15min。
5.根据权利要求1所述的一种高效降解抗生素的光催化剂的制备方法,其特征在于,步骤(1)中采用超声分散纳米硫化锌和纳米复合材料CuO@Cu2O@Cu。
6.根据权利要求1所述的一种高效降解抗生素的光催化剂的制备方法,其特征在于,步骤(2)中微波辐照反应的功率为130~650W,反应时间为5~15min。
7.根据权利要求6所述的一种高效降解抗生素的光催化剂的制备方法,其特征在于,步骤(2)中微波辐照反应的功率为130W,反应时间为10min。
8.一种高效降解抗生素的光催化剂,其特征在于,按权利要求1~7任一所述的制备方法制备得到。
9.权利要求8所述的一种高效降解抗生素的光催化剂用于降解抗生素的应用,所述抗生素为环丙沙星、诺氟沙星、四环素、磺胺甲恶唑中的一种或多种。
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