CN113275023A - 一种Bi3O4Br/CuBi2O4双金属异质结催化剂的制备方法及应用 - Google Patents
一种Bi3O4Br/CuBi2O4双金属异质结催化剂的制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种Bi3O4Br/CuBi2O4双金属异质结催化剂的制备方法:将Bi(NO3)3·5H2O、NaBr和PVP溶于甘露醇水溶液中,将所得混合溶液1的pH值调节为11‑12,再转移到反应釜中进行水热合成,自然冷却后用去离子水和乙醇交替洗涤,烘干,得到Bi3O4Br粉末;将Bi3O4Br粉末、Cu(NO3)2·3H2O、Bi(NO3)3·5H2O和NaOH依次添加到水中搅拌得混合溶液2,再将混合溶液2转移到反应釜中进行水热合成,自然冷却,洗涤,烘干,得到的双金属异质结催化剂能够降低光生电子空穴复合的速率,其制备方法简单且制得的催化剂催化效能高,能够产生多种活性氧物种。
Description
技术领域
本发明属于环境修复与污染治理技术领域,更具体的说是涉及一种Bi3O4Br/CuBi2O4双金属异质结催化剂的制备方法及应用,该催化剂用于在可见光下耦合过一硫酸盐去除水体中残留的抗生素。
背景技术
近年来,抗生素广泛应用于人类疾病治疗,畜牧业和水产养殖业,如果不能得到有效的处理,大量的抗生素将残留在水环境中,污水处理厂是抗生素释放到环境中的主要来源,然而,许多研究已经报道抗生素,特别是四环素在污水处理厂中频繁检出,而通过常规污水处理工艺难以有效去除这些新出现的污染物,因此,寻找去除水环境中残留抗生素的有效途径是十分必要的。
基于硫酸根自由基(·SO4 -)的高级氧化技术具有强氧化能力、pH适用范围广、自由基半衰期长等优势,能有效去除难降解有机污染物,但是存在矿化能力低,过渡金属离子溶出等问题。另一个具有应用前景的技术是光催化技术,因其反应条件温和、能耗低、二次污染少等优点,在水环境污染物处理中扮演着重要的角色,但光生电子空穴复合速率过快、氧化能力不足等问题严重制约着其发展前景。因此如果能将基于·SO4 -的高级氧化技术和光催化技术两者耦合,不但能增加活性氧物种的产生,而且还能降低光生电子空穴复合的速率,大大提高了污染物的降解性能。
作为一种典型的Bi基双金属催化剂,CuBi2O4具有良好的光催化性能,然而,由于禁带宽度较窄,光生电荷的复合速度较快,限制了CuBi2O4的广泛应用,而如果将CuBi2O4与合适能带的半导体的偶联形成异质结可以大大降低光生电子和空穴复合效率,提高CuBi2O4的催化性能。
申请号为201510234345.8的发明申请公开了一种光助多孔铋酸铜活化过硫酸盐水处理高级氧化技术的构筑与应用方法,该发明首先通过共沉淀法和高温煅烧得到多孔铋酸铜,利用紫外光作为光源,活化PMS降解香豆素。但是紫外光作为光源不能充分利用太阳光中的可见光,而且单一催化剂在合成过程中会很容易发生颗粒的聚集,使得光生电子空穴对容易重组,导致催化剂的活性位点数量减少和催化效率降低。
申请号为202011271552.8的发明申请公开了一种可见光辅助类芬顿活化过硫酸盐的光催化材料及其制备方法和应用,该发明首先通过光还原mBVO{010}晶面上选择性负载金纳米颗粒和非晶态硫化钴得到GNPs@A-CoSx核壳结构,使用350W氙灯模拟太阳光,活化PMS降解罗丹明B。但是材料制备方法复杂,需要贵金属掺杂,而且污染物降解时间较长。
因此,研发一种能够既保持单一催化剂的优势又能降低光生电子空穴复合率,从而快速高效降解污染物的双金属异质结催化剂的是本领域技术人员亟需解决的问题。
发明内容
有鉴于此,本发明提供了一种简易的既能改善CuBi2O4的催化性能,又能同时保持高效快速降解污染物的Bi3O4Br/CuBi2O4双金属异质结催化剂的制备方法及应用。
为了实现上述目的,本发明采用如下技术方案:
一种Bi3O4Br/CuBi2O4双金属异质结催化剂的制备方法,包括以下步骤:
(1)将Bi(NO3)3·5H2O、NaBr和PVP溶于甘露醇水溶液中得混合溶液1,然后将所得混合溶液1的pH值调节为11-12,再将混合溶液1转移到反应釜中进行水热合成,自然冷却后用去离子水和乙醇交替洗涤,烘干,得到Bi3O4Br粉末;
(2)将所得Bi3O4Br粉末、Cu(NO3)2·3H2O、Bi(NO3)3·5H2O和NaOH依次添加到水中搅拌得混合溶液2,再将混合溶液2转移到反应釜中进行水热合成,自然冷却后用去离子水和乙醇交替洗涤,烘干,得到所述Bi3O4Br/CuBi2O4双金属异质结催化剂。
本发明的有益效果:
1.本发明通过两次简单的水热合成法制备了Bi3O4Br/CuBi2O4双金属异质结催化剂,合成方法简单,原材料成本低廉。
2.本发明的Bi3O4Br/CuBi2O4双金属异质结催化剂在高浓度四环素溶液(40mg/L)降解过程中表现出优异的催化活性,15分钟内能达到95%以上的去除效率;30分钟内达到80%以上的矿化率。
进一步,步骤(1)中,每45-55mL甘露醇水溶液加入Bi(NO3)3·5H2O0.70-0.90g、NaBr0.6-0.75g,PVP0.6-0.75g,所述甘露醇水溶液的浓度为0.1-0.15mol/L。
采用上述进一步技术方案的有益效果为:增加溶液的粘结力,更容易使材料形成缺陷。
进一步,步骤(1)中,上述NaOH水溶液的浓度为1-3mol/L。
采用上述进一步技术方案的有益效果为:调节溶液pH,改变晶面结构。
进一步,步骤(1)中,上述水热合成的温度为150-170℃,水热合成的时间为18-24h。
进一步,步骤(1)中,上述自然冷却至60℃以下后用去离子水和乙醇交替洗涤3-4次,烘干温度为60-80℃,烘干时间为8-12h。
进一步,步骤(2)中,每30-40mL水中加入Bi3O4Br0.02-0.04g,Cu(NO3)2·3H2O0.2-0.3g,Bi(NO3)3·5H2O0.9-1.0g,NaOH0.3-0.4g。
进一步,步骤(2)中,上述Bi3O4Br溶液的浓度为0.6-1g/L。
采用上述进一步技术方案的有益效果为:适量的Bi3O4Br掺杂有利于Bi3O4Br和CuBi2O4界面之间紧密接触,加快Bi3O4Br/CuBi2O4异质结内部的电子传输,降低光生电子空穴对复合的速率。
进一步,步骤(2)中,上述水热合成的温度为160-180℃,水热合成的时间为18-24h。
进一步,步骤(2)中,上述自然冷却至60℃以下后用去离子水和乙醇交替洗涤3-4次,烘干温度为60-80℃,烘干时间为8-12h。
本发明还提供上述Bi3O4Br/CuBi2O4双金属异质结催化剂在可见光耦合过一硫酸盐体系中降解抗生素的应用,应用于四环素、土霉素等抗生素的催化降解。
附图说明
图1实施例1中CuBi2O4的TEM图像(a),Bi3O4Br的TEM图像(b),5%Bi3O4Br/CuBi2O4的TEM图像(c)和HRTEM图像(d);
图2采用实施例2中的Bi3O4Br/CuBi2O4双金属异质结催化剂在不同反应体系中对TC的去除效率;
图3实施例3中Bi3O4Br,CuBi2O4,和5%Bi3O4Br/CuBi2O4的XRD图谱;
图4实施例4中5%Bi3O4Br/CuBi2O4对TC的矿化程度及其降解效率。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
Bi3O4Br/CuBi2O4双金属异质结催化剂的制备方法,包括以下步骤:
(1)将0.7gBi(NO3)3·5H2O、0.6gNaBr和0.6gPVP溶于45mL甘露醇水溶液中得混合溶液1,甘露醇水溶液的浓度为0.1mol/L,然后使用浓度为1mol/L的NaOH水溶液调节上述混合溶液1的pH值为11,再将混合溶液1转移到100mL特氟龙内衬不锈钢高压釜中150℃水热合成24h,自然冷却至60℃以下后用去离子水和乙醇交替洗涤3次,60℃烘干12h,得到Bi3O4Br粉末;
(2)将0.02gBi3O4Br粉末、0.2gCu(NO3)2·3H2O、0.9gBi(NO3)3·5H2O和0.3gNaOH依次添加到30mL去离子水中混合搅拌得混合溶液2,再将混合溶液2转移到50mL特氟龙内衬不锈钢高压釜中180℃水热合成24h,自然冷却至60℃以下后用去离子水和乙醇交替洗涤3次,60℃烘干12h,得到Bi3O4Br/CuBi2O4双金属异质结催化剂。
对步骤(1)制备的Bi3O4Br粉末和步骤(2)制备的Bi3O4Br/CuBi2O4双金属异质结催化剂进行TEM表征,由图1可知,制备的Bi3O4Br粉末为纳米片结构,CuBi2O4为纳米棒结构,Bi3O4Br/CuBi2O4复合材料中可以明显观察到Bi3O4Br的晶格间距为0.285nm,CuBi2O4的晶格间距为0.318nm。同时,CuBi2O4和Bi3O4Br之间可以明显地观察到明显的相互接触界面,有利于加快Bi3O4Br/CuBi2O4异质结内部的电子传输,降低光生电子空穴复合率。
实施例2
Bi3O4Br/CuBi2O4双金属异质结催化剂的制备方法,包括以下步骤:
(1)将0.8gBi(NO3)3·5H2O、0.65gNaBr和0.65gPVP溶于50mL甘露醇水溶液中得混合溶液1,甘露醇水溶液的浓度为0.15mol/L,然后使用浓度为2mol/L的NaOH水溶液调节上述混合溶液1的pH值为11.5,再将混合溶液1转移到100mL特氟龙内衬不锈钢高压釜中160℃水热合成24h,自然冷却至60℃以下后用去离子水和乙醇交替洗涤3次,70℃烘干12h,得到Bi3O4Br粉末;
(2)将0.03gBi3O4Br粉末、0.25gCu(NO3)2·3H2O、0.95gBi(NO3)3·5H2O和0.35gNaOH依次添加到35mL去离子水中混合搅拌得混合溶液2,再将混合溶液2转移到50mL特氟龙内衬不锈钢高压釜中160℃水热合成24h,自然冷却至60℃以下后用去离子水和乙醇交替洗涤3次,70℃烘干12h,得到Bi3O4Br/CuBi2O4双金属异质结催化剂。
将步骤(2)制备的Bi3O4Br/CuBi2O4双金属异质结催化剂用于降解四环素(TC)。配制40mg/L的TC溶液50mL置于光反应装置中,加入25mgBi3O4Br/CuBi2O4,黑暗条件下反应30min达到吸附平衡,使用300W氙灯模拟可见光,开灯同时加入1mMPMS,每隔5min取样测定TC剩余浓度,15分钟内在可见光(Vis)、PMS、Bi3O4Br/CuBi2O4吸附、Vis+PMS、Bi3O4Br/CuBi2O4+Vis、Bi3O4Br/CuBi2O4+PMS和Bi3O4Br/CuBi2O4+Vis+PMS体系下TC降解效果如图2所示。单独Vis和Bi3O4Br/CuBi2O4吸附体系对TC的去除可以忽略不计。在PMS体系中,TC的降解率为25%。只引入可见光,发现在Vis+PMS和Bi3O4Br/CuBi2O4+Vis体系只有35%和16%TC被去除。而只加入PMS后发现TC去除率显著提高。特别是Bi3O4Br/CuBi2O4+PMS体系,TC去除率在15分钟内达到83%,说明Bi3O4Br/CuBi2O4有利于PMS活化产生氧化能力强的·SO4 -和·OH自由基。更重要的是,在PMS和可见光的共同作用下,Bi3O4Br/CuBi2O4+Vis+PMS体系的TC去除率高达95%以上,比Bi3O4Br/CuBi2O4+PMS体系和Bi3O4Br/CuBi2O4+Vis体系分别提高了1.15和5.94倍。以上结果说明,Bi3O4Br/CuBi2O4+Vis+PMS体系具有较好的协同效应,能够诱导多种活性氧物种的生成,从而快速高效的降解污染物。
实施例3
Bi3O4Br/CuBi2O4双金属异质结催化剂的制备方法,包括以下步骤:
(1)将0.85gBi(NO3)3·5H2O、0.7gNaBr和0.7gPVP溶于50mL甘露醇水溶液中得混合溶液1,甘露醇水溶液的浓度为0.1mol/L,然后使用浓度为2mol/L的NaOH水溶液调节上述混合溶液1的pH值为11.5,再将混合溶液1转移到100mL特氟龙内衬不锈钢高压釜中160℃水热合成18h,自然冷却至60℃以下后用去离子水和乙醇交替洗涤3次,70℃烘干8h,得到Bi3O4Br粉末;
(2)将0.03gBi3O4Br粉末、0.25gCu(NO3)2·3H2O、0.95gBi(NO3)3·5H2O和0.35gNaOH依次添加到35mL去离子水中混合搅拌得混合溶液2,再将混合溶液2转移到50mL特氟龙内衬不锈钢高压釜中180℃水热合成24h,自然冷却至60℃以下后用去离子水和乙醇交替洗涤3次,70℃烘干8h,得到Bi3O4Br/CuBi2O4双金属异质结催化剂。
对步骤(1)制备的Bi3O4Br粉末和步骤(2)制备的Bi3O4Br/CuBi2O4双金属异质结催化剂进行XRD表征,由图3可知,Bi3O4Br的所有峰值都与标准卡片(JCPDSNo.84-0793)一致,CuBi2O4所有的峰都与标准卡片(JCPDSNo.42-0334)一致,表明Bi3O4Br和CuBi2O4纳米材料成功制备。对于Bi3O4Br/CuBi2O4,在2θ=23.9°观察到明显的Bi3O4Br特征衍射峰,表明成功地将Bi3O4Br引入了CuBi2O4中。
实施例4
Bi3O4Br/CuBi2O4双金属异质结催化剂的制备方法,包括以下步骤:
(1)将0.9gBi(NO3)3·5H2O、0.75gNaBr和0.75gPVP溶于55mL甘露醇水溶液中得混合溶液1,甘露醇水溶液的浓度为0.15mol/L,然后使用浓度为3mol/L的NaOH水溶液调节上述混合溶液1的pH值为12,再将混合溶液1转移到100mL特氟龙内衬不锈钢高压釜中170℃水热合成18h,自然冷却至60℃以下后用去离子水和乙醇交替洗涤3次,80℃烘干8h,得到Bi3O4Br粉末;
(2)将0.04gBi3O4Br粉末、0.3gCu(NO3)2·3H2O、1.0gBi(NO3)3·5H2O和0.4gNaOH依次添加到40mL去离子水溶液中混合搅拌得混合溶液2,再将混合溶液2转移到50mL特氟龙内衬不锈钢高压釜中180℃水热合成18h,自然冷却至60℃以下后用去离子水和乙醇交替洗涤3次,80℃烘干8h,得到Bi3O4Br/CuBi2O4双金属异质结催化剂。
将步骤(2)制备的Bi3O4Br/CuBi2O4双金属异质结催化剂用于降解四环素(TC)。配制40mg/L的TC溶液50mL置于光反应装置中,加入25mgBi3O4Br/CuBi2O4,黑暗条件下反应30min达到吸附平衡,使用300W氙灯模拟太阳光,开灯同时加入1mMPMS,每隔5min取样测定TC剩余浓度以及TOC浓度,降解效果如图4所示。反应15分钟TC降解效率达到95%以上,TOC去除率达到50%以上;延长反应到30分钟发现TC完全被降解的同时矿化率达到80%以上。说明延长反应时间有利于将TC的结构进一步破坏,形成短链或小分子的降解产物。
对所公开的实施例的说明,使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (9)
1.一种Bi3O4Br/CuBi2O4双金属异质结催化剂的制备方法,其特征在于,包括以下步骤:
(1)将Bi(NO3)3·5H2O、NaBr和PVP溶于甘露醇水溶液中得混合溶液1,然后将所得混合溶液1的pH值调节为11-12,再将混合溶液1转移到反应釜中进行水热合成,自然冷却后用去离子水和乙醇交替洗涤,烘干,得到Bi3O4Br粉末;
(2)将所得Bi3O4Br粉末、Cu(NO3)2·3H2O、Bi(NO3)3·5H2O和NaOH依次添加到水中搅拌得混合溶液2,再将混合溶液2转移到反应釜中进行水热合成,自然冷却后用去离子水和乙醇交替洗涤,烘干,得到所述Bi3O4Br/CuBi2O4双金属异质结催化剂。
2.根据权利要求1所述一种Bi3O4Br/CuBi2O4双金属异质结催化剂的制备方法,其特征在于,步骤(1)中,每45-55mL所述甘露醇水溶液加入Bi(NO3)3·5H2O0.70-0.90g、NaBr0.6-0.75g,PVP0.6-0.75g,所述甘露醇水溶液的浓度为0.1-0.15mol/L。
3.根据权利要求1所述一种Bi3O4Br/CuBi2O4双金属异质结催化剂的制备方法,其特征在于,步骤(1)中,所述NaOH水溶液的浓度为1-3mol/L。
4.根据权利要求1所述一种Bi3O4Br/CuBi2O4双金属异质结催化剂的制备方法,其特征在于,步骤(1)中,所述水热合成的温度为150-170℃,水热合成的时间为18-24h。
5.根据权利要求1所述一种Bi3O4Br/CuBi2O4双金属异质结催化剂的制备方法,其特征在于,步骤(1)中,所述自然冷却至60℃以下后用去离子水和乙醇交替洗涤3-4次,烘干温度为60-80℃,烘干时间为8-12h。
6.根据权利要求1所述一种Bi3O4Br/CuBi2O4双金属异质结催化剂的制备方法,其特征在于,步骤(2)中,每30-40mL水中加入Bi3O4Br0.02-0.04g,Cu(NO3)2·3H2O0.2-0.3g,Bi(NO3)3·5H2O0.9-1.0g,NaOH0.3-0.4g。
7.根据权利要求1所述一种Bi3O4Br/CuBi2O4双金属异质结催化剂的制备方法,其特征在于,步骤(2)中,所述水热合成的温度为160-180℃,水热合成的时间为18-24h。
8.根据权利要求1所述一种Bi3O4Br/CuBi2O4双金属异质结催化剂的制备方法,其特征在于,步骤(2)中,所述自然冷却至60℃以下后用去离子水和乙醇交替洗涤3-4次,烘干温度为60-80℃,烘干时间为8-12h。
9.一种权利要求1-8任一项所述Bi3O4Br/CuBi2O4双金属异质结催化剂在可见光耦合过一硫酸盐体系中降解抗生素的应用,其特征在于,应用于四环素、土霉素等抗生素的催化降解。
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CN115069282A (zh) * | 2022-07-26 | 2022-09-20 | 陕西科技大学 | 一种铋酸铜/碳酸氧铋异质结光催化剂及制备方法和应用 |
CN115069282B (zh) * | 2022-07-26 | 2023-09-15 | 陕西科技大学 | 一种铋酸铜/碳酸氧铋异质结光催化剂及制备方法和应用 |
CN115304100A (zh) * | 2022-08-29 | 2022-11-08 | 徐州联禾升钢结构工程有限公司 | 一种金属防腐保护材料及其制备方法 |
CN116673050A (zh) * | 2023-06-15 | 2023-09-01 | 南开大学 | 具有近红外光响应的Bi2O2CO3@CuBi2O4异质结及其原位合成方法和应用 |
CN116673050B (zh) * | 2023-06-15 | 2024-01-09 | 南开大学 | 具有近红外光响应的Bi2O2CO3@CuBi2O4异质结及其原位合成方法和应用 |
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