CN116173979A - 一种钼酸铋和钨酸钴异质结光催化材料的制备方法及应用 - Google Patents
一种钼酸铋和钨酸钴异质结光催化材料的制备方法及应用 Download PDFInfo
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Abstract
本发明属于光催化材料技术领域及环境治理领域,公开了一种钼酸铋和钨酸钴异质结光催化材料的制备方法及应用,所述催化材料为Z型光催化材料,该异质结光催化材料可通过简单的水热法来进行制备,通过控制钨酸钴添加量,得到不同组分含量的Bi2MoO6/CoWO4异质结。实验结果表明,本发明制备的Bi2MoO6/CoWO4(BMC‑30)光催化材料应用于光催化降解水体中的诺氟沙星时,在可见光的照射下,光照60分钟后能够降解97.1%的诺氟沙星。此外,所制备材料对于实际水体中的诺氟沙星也具有良好的光催化降解性能。本发明具有制备方法操作简单、异质结材料具有较强的可见光吸收能力、光催化性能稳定、降解效率高等优点,在光催化领域具有潜在的应用前景。
Description
技术领域
本发明涉及一种钼酸铋和钨酸钴异质结光催化材料的制备方法及应用,属于光催化材料技术领域及环境治理领域。
背景技术
抗生素作为一类新兴污染物,在水环境中存在高度的稳定性,对人类健康和整个生态系统的稳定造成严重威胁。诺氟沙星是一种具有代表性的氟喹诺酮类抗生素,由于其广谱抗生素特性而被广泛使用。然而,由于诺氟沙星的生物降解性较低,在各种水体中均检测出其存在。令人沮丧的是,长期暴露在存在诺氟沙星环境中,即使是在浓度极低的环境中,也会导致水生生物和人类的潜在健康风险。因此,寻找一种技术高效去除废水中的诺氟沙星已成为当务之急。
目前,已经开发了各种技术来去除不同水体中的抗生素,如生物降解、化学氧化、吸附和光催化。其中,光催化法作为一种高级氧化工艺,因其效率高、二次污染低、环境友好而得到广泛应用。然而,由于光利用率不足和带隙宽,许多传统的半导体光催化剂在废水中的实际应用受到限制。此外,对于大多数单组分半导体来说,在光激发下产生的电子-空穴对的高重组率仍然是实际应用中的常见问题。因此,构建二元异质结结构以加强电子和空穴对的分离已被认真考虑。
铋基光催化剂由于其独特的能带结构和特性一直是人们关注的焦点。在这些化合物中,钼酸铋带隙为2.5~2.8eV,因其具有有机污染物降解性能而引起广泛关注。钼酸铋可以在光照下与水反应生成超氧自由基和羟基自由基,可去除抗生素。然而,单一组分钼酸铋仍然存在一些缺点,如可见光响应性差和光生电子-空穴对的快速重组,阻碍了其在废水净化中的大规模应用。钨酸钴作为一种可见光响应的过渡金属钨酸盐,因其窄带隙、生态友好和优异的稳定性而受到广泛关注。此外,钨酸钴具有优异的电化学性能,这是由于钨酸盐结构中的钨原子与单一金属氧化物相比显著提高了导电性。更重要的是,钨酸钴的能带结构与钼酸铋的能带结构吻合良好。因此,通过将钨酸钴与钼酸铋结合构建异质结,可以促进载流子的分离以提高光催化效率。
发明内容
针对现有技术中存在的问题,本发明提供一种钼酸铋和钨酸钴异质结光催化材料的制备方法及应用,该光催化材料可用于光催化降解水体中的抗生素,该异质结光催化材料能促进光生电子-空穴的分离,具有优异的光催化降解抗生素的性能。
为了解决上述技术问题,本发明采用如下的技术方案:一种钼酸铋和钨酸钴异质结光催化材料的制备方法,首先将摩尔比为2:1的Bi(NO3)3·5H2O和Na2MoO4·2H2O均匀分散于25mL乙二醇中,同时将20~50mg的CoWO4加入20mL乙醇中,搅拌0.5h后,将得到的CoWO4乙醇溶液加入乙二醇溶液中,搅拌均匀后得到混合溶液,将混合溶液转移至聚四氟乙烯内衬的高压釜中,水热反应12h,冷却后用乙醇和水洗涤,分离、烘干后,即可得到Bi2MoO6/CoWO4异质结光催化材料。
上述方法中,所述CoWO4的制备方法为:将KNO3、NaNO3、Na2WO4·2H2O和CoCl2·6H2O的混合物研磨30分钟后放入坩埚中,然后以5℃/min的升温速率,在马弗炉中煅烧6h,最终得到纳米材料,用去离子水洗涤3~5次,在70℃下真空干燥。
上述方法中,所述KNO3、NaNO3、Na2WO4·2H2O和CoCl2·6H2O的摩尔比为30:30:1:1。
上述方法中,所述煅烧温度为500℃。
上述方法中,所述混合溶液的搅拌时间为0.5h。
同时,本发明还提供了上述钼酸铋和钨酸钴异质结光催化材料在降解典型氟喹诺酮类抗生素中的应用。
上述应用中,所述典型氟喹诺酮类抗生素为溶解于水中的诺氟沙星。
与现有技术相比,本发明的优点在于:
1.本发明采用水热法制备出Bi2MoO6/CoWO4光催化材料,制备简单,操作方便。
2.本发明Bi2MoO6/CoWO4光催化材料应用于光催化降解水中的诺氟沙星时,在可见光的照射下(300W氙灯),光照60min后诺氟沙星的降解率超过97%,在光催化降解抗生素领域具有潜在的应用前景。
3.本发明的光催化材料具有良好的光催化性能,经过四次次循环后,诺氟沙星的光降解效率仍高达90.0%,表明光催化材料具有良好的稳定性和可回收性,可有效降解水体中抗生素。
4.本发明的异质结光催化材料在可见光激发下,由于Bi2MoO6的导带电子与CoWO4的空穴之间存在强烈的静电吸引力,Bi2MoO6导带中的光生电子与CoWO4价带中的光生空穴重新结合,将电子保留在CoWO4的导带中,空穴保留在Bi2MoO6的价带中。这样,Bi2MoO6价带上的空穴可将OH-氧化生成·OH,CoWO4导带上的电子可被溶解氧俘获形成·O2 -。因此,异质结材料与单组分材料相比,产生了更多的活性物质,有效地提高了材料对诺氟沙星的光催化降解性能。
附图说明
图1为实施例1材料Bi2MoO6、CoWO4和Bi2MoO6/CoWO4的XRD图;
图2为实施例1材料Bi2MoO6、CoWO4和Bi2MoO6/CoWO4的FTIR衍射图谱;
图3为实施例1材料Bi2MoO6/CoWO4(BMC-30)的SEM图像;
图4为实施例2材料Bi2MoO6、CoWO4和Bi2MoO6/CoWO4对诺氟沙星的光催化降解图;
图5为实施例3不同剂量Bi2MoO6/CoWO4(BMC-30)对诺氟沙星溶液光催化去除率图;
图6为实施例4材料Bi2MoO6/CoWO4(BMC-30)对不同浓度诺氟沙星溶液光催化去除率图;
图7为实施例5材料Bi2MoO6/CoWO4(BMC-30)对不同pH值诺氟沙星溶液光催化去除率图;
图8为实施例6中的光催化材料Bi2MoO6/CoWO4(BMC-30)循环降解诺氟沙星溶液时对应的循环次数-降解效率图;
图9为实施例7中的光催化材料Bi2MoO6/CoWO4(BMC-30)在不同实际水体中对诺氟沙星光催化降解效果图。
具体实施方式
为了使本发明目的、技术方案和优点更加清楚,下面结合实施例对本发明作进一步的详细说明。
实施例1
将摩尔比为2:1的Bi(NO3)3·5H2O(0.97g)和Na2MoO4·2H2O(0.242g)均匀分散于25mL乙二醇中,同时将20~50mg的CoWO4加入20mL乙醇中,搅拌0.5h后,将得到的CoWO4乙醇溶液加入乙二醇溶液中,搅拌均匀后得到混合溶液,将混合溶液转移至聚四氟乙烯内衬的高压釜中,水热反应12h,冷却后用乙醇和水洗涤,分离、烘干后,即可得到钼酸铋/钨酸钴异质结光催化材料。制备的异质结光催化材料命名为BMC-x(x=20,30,40,50),其中x代表加入的CoWO4的量。
CoWO4纳米材料的制备方法如下:
将摩尔比为30:30:1:1的KNO3、NaNO3、Na2WO4·2H2O和CoCl2·6H2O的混合物研磨30分钟后放入坩埚中,然后以5℃/min的升温速率,在马弗炉中500℃下煅烧6h,最终得到CoWO4纳米材料,用去离子水多次洗涤,70℃下真空干燥12h。
图1~3为对以上步骤所得材料进行表征的结果。XRD图谱如附图1所示;FTIR衍射图谱如附图2所示;SEM图像如附图3所示。
实施例2
通过在装有循环水的石英反应器中对诺氟沙星的降解,评估所制备的异质结光催化材料在可见光下的光催化能力。使用300W氙灯和420nm紫外光截止滤光片(>420nm)提供可见光照射。将20mg光催化剂分散到包含50mL诺氟沙星溶液(10mg/L)的石英光反应器中。在黑暗中吸附搅拌30min使催化剂与污染物达到吸附平衡。光照时,每隔10min时间取2.5mL的悬浮液,然后用注射器过滤膜(0.22μm)过滤以去除催化剂颗粒,用高效液相色谱仪测定诺氟沙星的降解率。
图4为本发明实施例1中制得的异质结光催化材料在可见光下对诺氟沙星的光催化降解效果曲线图。从图中可见,光照60min后,单独使用Bi2MoO6、CoWO4对诺氟沙星的光催化降解率分别为77.2%和18.7%,而Bi2MoO6/CoWO4异质结光催化材料(BMC-30)的光降解效率达到97.1%。表明异质结光催化材料与单组分材料相比,有效地提高了对诺氟沙星的光催化降解性能,是一种高效的光催化材料。
实施例3
通过在装有循环水的石英反应器中,评估不同剂量Bi2MoO6/CoWO4异质结光催化材料(BMC-30)在可见光下对诺氟沙星的光催化降解。使用300W氙灯和420nm紫外光截止滤光片(>420nm)提供可见光照射。将不同剂量(200,300,400,500mg/L)光催化剂分散到包含50mL诺氟沙星溶液(10mg/L)的石英光反应器中。在黑暗中吸附搅拌30min使催化剂与污染物达到吸附平衡。光照时,每隔10min取2.5mL的悬浮液,然后用注射器过滤膜(0.22μm)过滤以去除催化剂颗粒,用高效液相色谱仪测定诺氟沙星的降解率。
图5为不同剂量本发明实施例1中制得的Bi2MoO6/CoWO4(BMC-30)在可见光下对诺氟沙星(10mg/L)的光催化降解效果曲线图。由图5可以看出,随着BMC-30剂量从200mg/L增加到500mg/L,黑暗中对诺氟沙星的吸附率从22.4%上升到58.7%,这是由于BMC-30可用吸附位点数量的增加。样品剂量为200mg/L~400mg/L时,诺氟沙星的光降解增强(57.5%~97.1%),这是由于更多的光催化材料提供了更多的活性位点和自由基。而当BMC-30的用量达到500mg/L时,NOR的光降解速率略有下降。这种现象可能是由于过量的投加量导致光催化剂团聚,导致催化剂可用活性位点减少的原因。故本发明所制备的光催化材料在剂量为400mg/L时具有最优的光催化降解效果。
实施例4
通过在装有循环水的石英反应器中,评估不同抗生素浓度对诺氟沙星光催化降解的影响。使用300W氙灯和420nm紫外光截止滤光片(>420nm)提供可见光照射。将20mg异质结光催化材料(BMC-30)分散到包含50mL诺氟沙星溶液的石英光反应器中。在黑暗中吸附搅拌30min使催化剂与污染物达到吸附平衡。光照时,每隔10min取2.5mL的悬浮液,然后用注射器过滤膜(0.22μm)过滤以去除催化剂颗粒,用高效液相色谱仪测定诺氟沙星的降解率。
图6为本发明实施例1中制得的Bi2MoO6/CoWO4异质结光催化材料(BMC-30)在可见光下对不同浓度诺氟沙星溶液的光催化降解效果曲线图。从图中可见,随着诺氟沙星浓度从7.5mg/L增加到20mg/L,光降解率从98.3%下降到56.3%。这是由于过量的诺氟沙星分子会争夺光催化剂表面的吸附位点和反应位点,导致光催化效率下降。故本发明所制备的异质结光催化材料在诺氟沙星浓度低于10mg/L时具有良好的光催化降解效果。
实施例5
通过在装有循环水的石英反应器中,评估不同pH值对诺氟沙星光催化降解的影响。使用300W氙灯和420nm紫外光截止滤光片(>420nm)提供可见光照射。将20mg异质结光催化材料(BMC-30)分散到包含50mL诺氟沙星溶液(10mg/L)的石英光反应器中。在黑暗中吸附搅拌30min使催化剂与污染物达到吸附平衡。光照时,每隔10min取2.5mL的悬浮液,然后用注射器过滤膜(0.22μm)过滤以去除催化剂颗粒,用高效液相色谱仪测定诺氟沙星的降解率。
图7为本发明实施例1中制得的Bi2MoO6/CoWO4异质结光催化材料(BMC-30)在可见光下对不同pH值诺氟沙星溶液的光催化降解效果曲线图。从图中可见,当pH值从5增加到9时,降解率保持在80%以上,这表明所制备材料在实际污水处理工艺中具有很强的可用性。当pH=3或11时,吸附和光降解效率降低。原因可能是较低的初始pH值(pH=3)可以加速·OH向H2O的转变。此外,当pH值较高时,过量的OH-可以与活性物种(h+)结合。此外,已有研究报道,诺氟沙星(阴离子)主要存在于pH值超过8.75的溶液中。当pH值极高(pH=11)时,多余的OH-容易与诺氟沙星争夺光催化剂表面有限的活性位点,导致降解性能较差。故本发明所制备的光催化材料在pH为5~9时具有良好的光催化降解效果。
实施例6
催化剂的长期可重复使用性和稳定性是实际水处理工艺的关键因素。在本发明中,使用BMC-30纳米复合材料进行了四个循环的诺氟沙星光催化降解。每次循环完成后,将收集的催化剂离心、洗涤多次,在70℃下干燥12h。如图8所示,经过4次循环后,诺氟沙星的光降解效率仍高达90.0%,表明BMC-30具有良好的稳定性和可回收性。
实施例7
通过在装有循环水的石英反应器中,评估BMC-30在不同环境水体中(湖水、河水、自来水和超纯水)对诺氟沙星的光催化降解。使用300W氙灯和420nm紫外光截止滤光片(>420nm)提供可见光照射。将20mg异质结光催化材料(BMC-30)分散到包含50mL诺氟沙星溶液(10mg/L)的石英光反应器中。在黑暗中吸附搅拌30min使催化剂与污染物达到吸附平衡。光照时,每隔10min取2.5mL的悬浮液,然后用注射器过滤膜(0.22μm)过滤以去除催化剂颗粒,用高效液相色谱仪测定诺氟沙星的降解率。
如图9所示,与超纯水相比,诺氟沙星在环境水体中的光降解效率有所下降。这主要是由于BMC-30的活性位点被悬浮物和有机物占据,从而降低了材料对诺氟沙星的吸附和光降解。上述结果表明所制备材料在实际水体中对诺氟沙星仍然具有较好的光催化降解效率,证明了BMC-30在废水中具有良好的应用前景。
实施例8
通过在装有循环水的石英反应器中,评估BMC-30在实际医疗废水中对氟喹诺酮类抗生素的光催化降解。使用300W氙灯和420nm紫外光截止滤光片(>420nm)提供可见光照射。将20mg光催化剂(BMC-30)分散到包含50mL医疗废水的石英光反应器中。在黑暗中吸附搅拌30min使催化剂与污染物达到吸附平衡。光照60min后,取2.5mL的悬浮液,然后用注射器过滤膜(0.22μm)过滤以去除催化剂颗粒及固体物质。用高效液相色谱-质谱仪测定抗生素的降解率。
本发明使用BMC-30对医疗废水中的另一种典型氟喹诺酮类抗生素氧氟沙星进行光催化降解,所制备材料对实际医疗废水中氧氟沙星的光催化降解情况如表1:
表1、BMC-30对医疗废水中氧氟沙星的降解性能
由表1可知,BMC-30对医疗废水中氧氟沙星的去除率达到74.2%,证明所制备材料对实际废水中氟喹诺酮类抗生素具有良好的降解效果。
上述实施例仅仅是为清楚地说明所作的举例,而并非对实施方式的限定。凡属于本发明思路下的技术方案均属于本发明的保护范围。
Claims (7)
1.一种钼酸铋和钨酸钴异质结光催化材料的制备方法,其特征在于:首先将摩尔比为2:1的Bi(NO3)3·5H2O和Na2MoO4·2H2O均匀分散于25mL乙二醇中,同时将20~50mg的CoWO4加入20mL乙醇中,搅拌0.5h后,将得到的CoWO4乙醇溶液加入乙二醇溶液中,搅拌均匀后得到混合溶液,然后将混合溶液转移至聚四氟乙烯内衬的高压釜中,水热反应12h,冷却后用乙醇和水洗涤,分离、烘干后,即可得到Bi2MoO6/CoWO4异质结光催化材料。
2.根据权利要求1所述的钼酸铋和钨酸钴异质结光催化材料的制备方法及应用,其特征在于:所述CoWO4的制备方法为:将KNO3、NaNO3、Na2WO4·2H2O和CoCl2·6H2O的混合物研磨30分钟后放入坩埚中,然后以5℃/min的升温速率,在马弗炉中煅烧6h,最终得到纳米材料,用去离子水洗涤3~5次,在70℃下真空干燥。
3.根据权利要求2所述的钼酸铋和钨酸钴异质结光催化材料的制备方法及应用,其特征在于:所述KNO3、NaNO3、Na2WO4·2H2O和CoCl2·6H2O的摩尔比为30:30:1:1。
4.根据权利要求2所述的钼酸铋和钨酸钴异质结光催化材料的制备方法及应用,其特征在于:所述煅烧温度为500℃。
5.根据权利要求1所述的钼酸铋和钨酸钴异质结光催化材料的制备方法及应用,其特征在于:所述混合溶液的搅拌时间为0.5h。
6.权利要求1~6任意一项所述钼酸铋和钨酸钴异质结光催化材料在降解典型氟喹诺酮类抗生素中的应用。
7.根据权利要求6所述的应用,其特征在于:所述典型氟喹诺酮类抗生素为溶解于水中的诺氟沙星。
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