CN115090311A - 一种钒酸铋/碳酸根自掺杂碳酸氧铋光催化材料的制备方法和应用 - Google Patents
一种钒酸铋/碳酸根自掺杂碳酸氧铋光催化材料的制备方法和应用 Download PDFInfo
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Abstract
本发明提供了一种钒酸铋/碳酸根自掺杂碳酸氧铋光催化材料的制备方法和应用,制备方法包括:(1)将五水合硝酸铋、尿素和柠檬酸钠溶解在去离子水中,搅拌后转移到聚四氟乙烯内衬的水热反应釜中进行水热反应,反应结束后离心分离取沉淀,经洗涤,干燥,研磨得到产物CO3 2‑‑Bi2O2CO3;(2)将CO3 2‑‑Bi2O2CO3溶解于超纯水中,搅拌,加入NH4VO3,搅拌后将溶液转移到聚四氟乙烯内衬的水热反应釜中进行水热反应,反应结束后过滤收集沉淀,经洗涤,干燥,研磨得到产物BiVO4/CO3 2‑‑Bi2O2CO3。用氙灯作为光源,通过滤波片将低波长的光滤去(λ<420nm),用2‑羟基‑1,4‑萘醌、左氧氟沙星的降解率来表征AgI/CO3 2‑‑Bi2O2CO3光催化材料的光催化性能。该材料具有化学稳定性高、光吸收能力较强、制备方法简单、成本低等优点。
Description
技术领域
本发明属于光催化材料制备领域,尤其是可见光催化材料技术领域,具体涉及一种钒酸铋/碳酸根自掺杂碳酸氧铋光催化材料的制备方法和应用。
背景技术
在污水处理中,光催化氧化作为一种新型高级氧化技术,在光化学氧化基础上发展起来,氧化能力强,无二次污染,其可在常温常压下进行,具有环保、节能等特点。
铋基半导体是近年发展起来的新型光催化材料。由于Bi原子的特殊结构,其化合物很容易形成层状结构,产生具有可见光响应能力的铋系化合物。Bi2O2CO3作为一种很有前途的光催化剂,由于其化学稳定性、无毒性和低成本,在光降解有毒离子或化合物的环境净化方面受到了广泛关注。Bi2O2CO3作为一种典型的奥里维里斯(Aurivillius)型氧化物,属于四方晶系,具有[Bi2O2]2+层和[CO3]2+层交替组成的独特层状结构;同时,极化作用产生的内电场有利于光生电子与空穴的分离,从而使其有较高的光催化性能。然而,Bi2O2CO3较大的带隙值(3.1~3.5eV)对可见光的吸收有较大限制。鉴于Bi2O2CO3的内部阴离子基团和适合修饰的层状结构,Bi2O2CO3作为一种可行的衬底,用于探测阴离子基团自掺杂对宽禁带半导体的影响。因此,制备了对可见光吸收性能更好的CO3 2-自掺杂的Bi2O2CO3(CO3 2--Bi2O2CO3)。但改进后CO3 2--Bi2O2CO3在光催化应用中依旧存在电子-空穴对的快速复合的缺点。通过对其形成异质结可以促进太阳能的吸收和利用,加速光生载流子的传输。
钒酸铋(BiVO4)具有相对窄的带隙,禁带宽度大约为2.4eV,在光化学太阳能电池、离子导电性和有机污染物的光降解等方面有着广泛的应用。故认为,将BiVO4与CO3 2--Bi2O2CO3复合制备高效光催化剂是可行的。
发明内容
本发明提供一种钒酸铋/碳酸根自掺杂碳酸氧铋光催化材料的制备方法和应用,光催化剂的制备方法简单、成本低、可见光响应程度提高、光催化性能好,对于2-羟基-1,4-萘醌和左氧氟沙星有较好的去除效果,无二次污染。
具体步骤为:
(1)将五水合硝酸铋、尿素和柠檬酸钠溶解在去离子水中,搅拌,获得均匀的悬浮液;
(2)将步骤(1)所得溶液转移到聚四氟乙烯内衬的水热反应釜中进行水热反应;
(3)将步骤(2)得到的反应液过滤收集沉淀,洗涤,干燥,研磨得到产物CO3 2--Bi2O2CO3;
(4)称取上述步骤所得产物CO3 2--Bi2O2CO3溶解于超纯水中,搅拌;
(5)向步骤(4)所得溶液加入NH4VO3,搅拌;
(6)向步骤(5)所得溶液转移到聚四氟乙烯内衬的水热反应釜中进行水热反应;
(7)将步骤(6)得到的反应液过滤收集沉淀,洗涤,干燥,研磨得到产物BiVO4/CO3 2--Bi2O2CO3。
优选的,所述步骤(1)磁力搅拌时间均为60min。
优选的,所述步骤(2)的水热反应温度为160℃,并在此温度下保持24h。
优选的,所述步骤(3)烘箱干燥温度为60℃,时间为20h;
优选的,所述步骤(4)磁力搅拌时间为30min;
优选的,所述步骤(5)磁力搅拌时间为30min;
优选的,所述步骤(6)水热反应温度为160℃,并在此温度下保持24h;
优选的,所述步骤(7)真空干燥温度为50℃,时间为12h。
本发明方法的优点:
(1)本发明主要采用自掺杂、形成异质结的方法对光催化剂进行改性。形成异质结是提高可见光响应的一种重要方法,可以利用价带、能级的差异,促进光催化剂中电子传递,减少光电子和空穴的复合,从而提高光催化剂对2-羟基-1,4-萘醌和左氧氟沙星的去除效果。
(2)本发明是以Bi2O2CO3为基础,通过自掺杂的方式形成CO3 2--Bi2O2CO3。通过简单的水热法制备了不同复合比例的BiVO4/CO3 2--Bi2O2CO3,制备方法简单易操作,制备的BiVO4/CO3 2--Bi2O2CO3复合光催化材料具有在可见光下有效降解2-羟基-1,4-萘醌、左氧氟沙星的性能。
(3)制备的BiVO4/CO3 2--Bi2O2CO3复合光催化材料具有较好的循环稳定性,避免了进行一次光催化后材料的光催化效率大幅度降低的问题。
(4)运用简单,只需要将制备的BiVO4/CO3 2--Bi2O2CO3复合光催化材料粉末投入到一定浓度的2-羟基-1,4-萘醌或左氧氟沙星中,在可见光下就可以进行降解。
附图说明
图1:BiVO4/CO3 2--Bi2O2CO3光催化材料的XRD谱图;
图2:BiVO4/CO3 2--Bi2O2CO3光催化材料的SEM图;
图3:BiVO4/CO3 2--Bi2O2CO3光催化材料的傅里叶红外光谱图;
图4:BiVO4/CO3 2--Bi2O2CO3光催化材料的紫外-可见漫反射光谱图(a)及禁带宽度图(b);
图5:BiVO4/CO3 2--Bi2O2CO3光催化材料的PL图;
图6:BiVO4/CO3 2--Bi2O2CO3光催化材料的光电流和EIS图;
图7:BiVO4/CO3 2--Bi2O2CO3光催化材料降解左氧氟沙星的C/C0图(a),动力学拟合图(b),降解2-羟基-1,4-萘醌的C/C0图(c)和动力学拟合图(d);
图8:BiVO4/CO3 2--Bi2O2CO3光催化材料降解左氧氟沙星的循环实验图。
具体实施方式
下面结合说明书附图,对本发明做进一步的详细说明,所述是对本发明的解释而不是限定。
实施例1:可见光催化剂的制备及应用实验
一、制备
(一)CO3 2--Bi2O2CO3的制备:
将1mmol五水合硝酸铋、2mmol尿素和0.4412g柠檬酸钠溶解在35mL去离子水中。将混合物磁力搅拌1h,然后将其转移到聚四氟乙烯内衬的水热反应釜中。将水热反应釜加热至160℃,并在此温度下保持24h。之后,过滤产品,用蒸馏水洗涤,并在60℃下干燥20h,研磨后即得CO3 2--Bi2O2CO3粉末,命名为CBOC。
(二)BiVO4/CO3 2--Bi2O2CO3(0.1VCBOC)光催化材料的制备:
称取0.2g CO3 2--Bi2O2CO3溶解于35mL的超纯水,磁力搅拌30min,向烧杯中加入0.0092g的NH4VO3,继续磁力搅拌30min,然后将其转移到聚四氟乙烯内衬的水热反应釜中。将水热反应釜加热至160℃,并在此温度下保持24小时。过滤,洗涤,并在50℃真空干燥箱干燥12小时,研磨后即得淡黄色粉末,命名为0.1VCBOC。
(三)BiVO4/CO3 2--Bi2O2CO3(0.4VCBOC)光催化材料的制备:
称取0.2g CO3 2--Bi2O2CO3溶解于35mL的超纯水,磁力搅拌30min,向烧杯中加入0.0368g的NH4VO3,继续磁力搅拌30min,然后将其转移到聚四氟乙烯内衬的水热反应釜中。将水热反应釜加热至160℃,并在此温度下保持24小时。过滤,洗涤,并在50℃真空干燥箱干燥12小时,研磨后即得淡黄色粉末,命名为0.4VCBOC。
(四)BiVO4/CO3 2--Bi2O2CO3(0.8VCBOC)光催化材料的制备:
称取0.2g CO3 2--Bi2O2CO3溶解于35mL的超纯水,磁力搅拌30min,向烧杯中加入0.0736g的NH4VO3,继续磁力搅拌30min,然后将其转移到聚四氟乙烯内衬的水热反应釜中。将水热反应釜加热至160℃,并在此温度下保持24小时。过滤,洗涤,并在50℃真空干燥箱干燥12小时,研磨后即得淡黄色粉末,命名为0.8VCBOC。
(五)BiVO4/CO3 2--Bi2O2CO3(1VCBOC)光催化材料的制备:
称取0.2g CO3 2--Bi2O2CO3溶解于35mL的超纯水,磁力搅拌30min,向烧杯中加入0.0920g的NH4VO3,继续磁力搅拌30min,然后将其转移到聚四氟乙烯内衬的水热反应釜中。将水热反应釜加热至160℃,并在此温度下保持24小时。过滤,洗涤,并在50℃真空干燥箱干燥12小时,研磨后即得淡黄色粉末,命名为1VCBOC。
二、表征
图1为实施例1中所制备材料的XRD图,随着BiVO4与CO3 2--Bi2O2CO3摩尔比的增加,BiVO4的特征峰强度逐渐增强。
图2为实施例1中所制备材料的SEM图,可以看出随着加入的偏钒酸铵量的增多,原始的CBOC玫瑰花状逐渐解体,最后成为棱形的纳米厚度的微米片状。
图3为实施例1中所制备材料的傅里叶红外图,约3389cm-1处的峰可归因于化学吸附或物理吸附水分子的O–H基团的拉伸和变形振动。548cm-1处的峰被分配给Bi-O。在700-910cm-1的范围内的峰分配给v1(VO4)和v3(VO4)。1351cm-1处显示出密集的峰值可以分配给CO3 2-的v3模式,在1065和844cm-1处出现归因于CO3 2-的v1和v2模式。
图4为实施例1中所制备材料的紫外可见漫反射光谱图,纯CBOC具有微弱的可见光响应,吸收带边缘约为370nm,而在引入BiVO4后,其复合材料对可见光的吸收增强。随着BiVO4量的增多,复合材料对可见光的吸收越来越强。
图5为实施例1中所制备材料的PL图,CBOC的发光强度高于0.8VCBOC,表明0.8VCBOC呈现电荷载流子的低复合率和较高的光子效率。
图6为实施例1中所制备材料的光电流响应和EIS图,与纯BiVO4和CBOC样品相比,0.8VCBOC显示出更大的光电流。这意味着0.8VCBOC样品的电子和空穴复合率低于纯BiVO4和CBOC。0.8VCBOC半径小于BiVO4和CBOC的半径,表明复合样品具有较小的电荷转移阻抗和较高的电荷分离能力。
三、应用实验
使用天平称取50mg光催化材料分别置于装有体积100mL浓度为10mg/L的2-羟基-1,4-萘醌溶液(左氧氟沙星溶液)的烧杯中,在黑暗条件下磁力搅拌30min,使其达到吸附饱和平衡的状态后进行光照反应。光源选用300W的氙灯,并安装紫外滤光片于其上滤掉紫外光(λ>420nm)。在不同的时间段吸取5mL反应液,并过0.22μm的一次性滤膜,通过紫外-可见分光光度计在最大波长(λmax=269nm)下测定2-羟基-1,4-萘醌的浓度,在最大波长(λmax=289nm)测定左氧氟沙星的浓度。
图7为实施例1中所制备材料降解左氧氟沙星的C/C0图(a)和动力学拟合图(b)。纯Bi2O2CO3对左氧氟沙星的降解率为63%,表明纯Bi2O2CO3活性较弱。0.1VCBOC、0.4VCBOC、0.8VCBOC、1VCBOC光催化剂降解效率分别为:9%,72%,78%,75%。顺序为:0.8VCBOC>1VCBOC>0.4V CBOC>0.1VCBOC。反应速率常数k为:CBOC(0.013min-1)、0.1VCBOC(0.0012min-1)、0.4VCBOC(0.015min-1)、0.8VCBOC(0.021min-1)、1VCBOC(0.018min-1)。由图7(c)和(d)可以看出,0.8VCBOC和纯CBOC在90min内对2-羟基-1,4-萘醌分别为83%,42%。与原始的CBOC相比,0.8VCBOC在可见光照射下光催化活性更高。结果表明,BiVO4/CO3 2--Bi2O2CO3异质结可以提升在阳光下对左氧氟沙星的降解能力,而BiVO4过量时会抑制VCBOC对光子的吸收。
图8为实施例1中所制备材料0.8VCBOC降解左氧氟沙星的循环实验图。经过多次离心、清洗、干燥和回收后,0.8VCBOC对左氧氟沙星的降解效率仍保持在78%左右。这表明催化剂的光催化活性在反应前后没有显著变化,该光催化剂对左氧氟沙星的降解是稳定有效的。
Claims (10)
1.一种钒酸铋/碳酸根自掺杂碳酸氧铋光催化材料的制备方法,包括如下步骤:
(1)将五水合硝酸铋、尿素和柠檬酸钠溶解在去离子水中,搅拌,获得均匀的悬浮液;
(2)将步骤(1)所得溶液转移到聚四氟乙烯内衬的水热反应釜中进行水热反应;
(3)将步骤(2)得到的反应液过滤收集沉淀,洗涤,干燥,研磨得到产物CO3 2--Bi2O2CO3;
(4)称取上述步骤所得产物CO3 2--Bi2O2CO3溶解于超纯水中,搅拌;
(5)向步骤(4)所得溶液加入NH4VO3,搅拌;
(6)向步骤(5)所得溶液转移到聚四氟乙烯内衬的水热反应釜中进行水热反应;
(7)将步骤(6)得到的反应液过滤收集沉淀,洗涤,干燥,研磨得到产物BiVO4/CO3 2--Bi2O2CO3。
2.根据权利要求1所述的方法,其特征在于:所述步骤(1)磁力搅拌时间均为60min。
3.根据权利要求1所述的方法,其特征在于:所述步骤(2)的水热反应温度为160℃,并在此温度下保持24h。
4.根据权利要求1所述的方法,其特征在于:(3)烘箱干燥温度为60℃,时间为20h。
5.根据权利要求1所述的方法,其特征在于:所述步骤(4)磁力搅拌时间为30mi。
6.根据权利要求1所述的方法,其特征在于:所述步骤(5)磁力搅拌时间为30min。
7.根据权利要求1所述的方法,其特征在于:所述步骤(6)水热反应温度为160℃,并在此温度下保持24h。
8.根据权利要求1所述的方法,其特征在于:所述步骤(7)真空干燥温度为50℃,时间为12h。
9.根据权利要求1~8所述的方法得到的BiVO4/CO3 2--Bi2O2CO3光催化材料。
10.根据权利要求9所述的方法得到的BiVO4/CO3 2--Bi2O2CO3光催化材料处理2-羟基-1,4-萘醌溶液(左氧氟沙星溶液),其特征在于,包括如下步骤:
向反应器中加入浓度为10mg/L的2-羟基-1,4-萘醌溶液(左氧氟沙星溶液),及所述光催化剂50mg,暗反应30min,再进行光照反应。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016064976A (ja) * | 2014-09-17 | 2016-04-28 | 国立大学法人 東京大学 | 金属(x)ドープバナジン酸ビスマスの製造方法および金属(x)ドープバナジン酸ビスマス |
CN107486153A (zh) * | 2017-09-15 | 2017-12-19 | 河南师范大学 | 一种具有光致脱附性能的新型吸附材料C/Bi2O2CO3的制备方法 |
US20180008953A1 (en) * | 2016-07-08 | 2018-01-11 | Soochow University | Composite with synergistic effect of adsorption and visible light catalytic degradation and preparation method and application thereof |
CN108525689A (zh) * | 2018-04-16 | 2018-09-14 | 陕西科技大学 | 一种水热法合成碳酸氧铋光催化剂的方法 |
CN114210353A (zh) * | 2022-01-18 | 2022-03-22 | 山东农业大学 | 一种碳酸氧铋-硫化铋异质结构光催化材料的制备方法 |
-
2022
- 2022-07-03 CN CN202210779537.7A patent/CN115090311A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016064976A (ja) * | 2014-09-17 | 2016-04-28 | 国立大学法人 東京大学 | 金属(x)ドープバナジン酸ビスマスの製造方法および金属(x)ドープバナジン酸ビスマス |
US20180008953A1 (en) * | 2016-07-08 | 2018-01-11 | Soochow University | Composite with synergistic effect of adsorption and visible light catalytic degradation and preparation method and application thereof |
CN107486153A (zh) * | 2017-09-15 | 2017-12-19 | 河南师范大学 | 一种具有光致脱附性能的新型吸附材料C/Bi2O2CO3的制备方法 |
CN108525689A (zh) * | 2018-04-16 | 2018-09-14 | 陕西科技大学 | 一种水热法合成碳酸氧铋光催化剂的方法 |
CN114210353A (zh) * | 2022-01-18 | 2022-03-22 | 山东农业大学 | 一种碳酸氧铋-硫化铋异质结构光催化材料的制备方法 |
Non-Patent Citations (3)
Title |
---|
HONGWEI HUANG ET AL.: ""Anionic Group Self-Doping as a Promising Strategy: Band-Gap Engineering and Multi-Functional Applications of High-Performance CO32−-Doped Bi2O2CO3"", 《ACS CATAL.》 * |
PUTTASWAMY MADHUSUDAN ET AL.: ""Novel urea assisted hydrothermal synthesis of hierarchical BiVO4/Bi2O2CO3 nanocomposites with enhanced visible-light photocatalytic activity"", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
USMAN SAIDU: ""Synthesis and Characterization of BiVO4nanoparticles and its Photocatalytic Activity on Levofloxacin Antibiotics"", 《CHEMSEARCH JOURNAL》 * |
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