CN108311164B - 一种铁改性光催化材料及其制备方法和应用 - Google Patents
一种铁改性光催化材料及其制备方法和应用 Download PDFInfo
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- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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Abstract
本发明公开了一种铁改性光催化材料及其制备方法和应用。所述制备方法是在含有铁盐和硝酸铋的溶液中,加入溴化钾溶液,高温反应后即得所述铁改性光催化材料。采用本发明的制备工艺能够成功制备出带有异质结的光催化剂,能够大大提高光催化效果;铁盐的引入能够增大光催化材料的比表面积,增强其吸附性能;在双氧水存在的条件下,光催化反应过程使得此催化材料表面铁元素在二价铁和三价铁之间形成链式反应,催化降解效果非常优异;操作方法简单易行,原料易得,成本低廉,在实际应用中推广实施的前景良好。
Description
技术领域
本发明属于水处理技术领域,具体涉及一种铁改性光催化材料及其制备方法和应用。
背景技术
随着人类的活动,越来越多的新兴持久性有毒污染物进入水环境中。传统的水处理方法不能满足要求。幸运的是,高级氧化工艺已成功的用于处理含有新兴污染物的水体中。高级氧化工艺采用化学氧化剂(如过氧化氢、过硫酸铵、臭氧)、光化学和声化学技术,生成活性物种(如羟基自由基、超氧自由基、硫酸根自由基)。类芬顿反应产生的羟基自由基是对环境友好的且有较高的氧化还原电位。
羟基自由基的产生是由于二价铁催化分解双氧水,生成三价铁,同时,双氧水还原三价铁再生二价铁,产生了一个链式反应。然而,因为双氧水与三价铁的反应比与二价铁的慢得多,还原三价铁再生二价铁是总反应的限制步骤。为了提高污染物的降解效率,光的照射可以促进三价铁还原为二价铁。
溴氧化铋(BiOBr)作为可见光催化剂,由于其较高的催化活性和稳定性,被广泛关注。BiOBr具有层状正方氟氯铅矿(PbFCl)结构,这是由溴化双板与[Bi2O2]层交错而形成的。然而,BiOBr的带隙约为2.9eV,只能吸收部分可见光。为了克服这一缺点,采用多种方法改进材料,包括各种层次纳米结构的引入和卤素改性。此外,过渡金属的改性能够提高BiOBr的催化活性。最近的研究显示,对BiOBr进行过渡金属(Zn,Sn)改性,可以提高光催化活性,但在其表面的金属氧化物可以迅速降低其光催化活性。双氧水和光的存在可以激活催化活性位点,从而提高催化剂的催化活性。
综上所述,开发一种铁改性光催化材料对于提高双氧水存在下的光催化效率具有重要的意义,且在目前也已十分必要。
发明内容
(一)要解决的技术问题
有鉴于此,本发明的目的是提供一种铁改性光催化材料及其制备方法和应用,以期解决前述现有技术中存在的至少部分技术问题。
(二)技术方案
为了实现上述目的,本发明一方面提供一种铁改性光催化材料的制备方法,其是在含有铁盐和硝酸铋的溶液中,加入溴化钾溶液,高温反应后即得所述铁改性光催化材料。
优选地,所述含有铁盐和硝酸铋的溶液由下述步骤得到:
(1)在氩气保护下,在含冰醋酸的乙二醇溶液中加入硝酸铋,搅拌直到硝酸铋全部溶解,配制成浓度为0.1mol/L的硝酸铋溶液;
(2)在氩气保护下,向步骤(1)得到的硝酸铋溶液中加入铁盐,搅拌直到铁盐全部溶解,即得到所述含有铁盐和硝酸铋的溶液。
其中,步骤(1)中,所述含冰醋酸的乙二醇溶液中,冰醋酸与乙二醇的体积比优选为1:10。
步骤(2)中,所述铁盐优选FeCl2·4H2O,其添加量优选5~40%,更优选20%,所述百分比为所述铁盐的物质的量占所述硝酸铋的物质的量的百分比。
优选地,所述的溴化钾溶液为在氩气保护下,在乙二醇溶液中加入溴化钾,搅拌直到溴化钾全部溶解,配制成浓度为0.1mol/L的溴化钾溶液。
优选地,所述的溴化钾溶液的添加量为100%,所述百分比为所述溴化钾溶液的体积占所述含有铁盐和硝酸铋的溶液的体积的百分比。
优选地,所述高温反应为在氩气保护下,于160摄氏度下进行密封反应,反应时间不少于12小时。
优选地,在所述反应后,还将反应体系自然冷却至室温,离心,然后采用无水乙醇与超纯水分别洗涤多次,冷冻干燥,得到所述铁改性光催化材料。
本发明的另一方面提供一种由前述制备方法制得的铁改性光催化材料。
本发明的又一方面还提供前述铁改性光催化材料在水处理中的应用。
(三)有益效果
相比现有技术,本发明的技术方案取得了下述有益效果:
1)采用本发明的制备工艺能够成功制备出带有异质结的光催化剂,能够大大提高光催化效果;
2)铁盐的引入能够增大光催化材料的比表面积,增强其吸附性能;
3)在双氧水存在的条件下,光催化反应过程使得此催化材料表面铁元素在二价铁和三价铁之间形成链式反应,催化降解效果非常优异;
4)操作方法简单易行,原料易得,成本低廉,在实际应用中推广实施的前景良好。
附图说明
图1显示BiOBr样品和x-FBB样品的XRD图谱(插图:在28°-34°范围内,{110}晶面衍射峰的位置图);
图2显示样品的SEM图谱:(a)BiOBr,(b)0.05-FBB,(c)0.1-FBB,(d)0.2-FBB,(e)0.4-FBB;0.2-FBB的SEM图谱(f),EDS图谱(g)和Mapping图谱(h);
图3a显示BiOBr样品和x-FBB样品的N2吸附-脱附等温线;图3b显示BiOBr样品和x-FBB样品的孔隙大小分布;
图4显示BiOBr样品和x-FBB样品的紫外-可见DRS光谱图;
图5a和图5b显示在可见光类芬顿催化反应中,制备的光催化剂对罗丹明B的降解随光照时间的变化,其中图5a显示RhB的浓度变化(C/C0),图5b显示伪一级动力学反应常数。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白,以下结合具体实施例,并参照附图,对本发明作进一步的详细说明。
为了说明本发明对水中污染物的光降解效果,本发明的研发人员考察了在双氧水存在的条件下,不同铁盐添加量下制备的光催化剂对罗丹明B的降解效果,以期更好地发挥该光催化剂对水中污染物的降解能力。
实施例1
在氩气的保护下,乙二醇中加入体积比为1:10的冰醋酸后,加入硝酸铋,搅拌直到硝酸铋全部溶解,配制成浓度为0.1mol/L的硝酸铋溶液;向上述溶液中加入Fe/Bi摩尔比为0,0.05,0.1,0.2,0.4的FeCl2·4H2O,搅拌直到铁盐全部溶解;所得的溶液中加入体积比为1:1的含有0.1mol/L溴化钾的乙二醇溶液。然后,将混合溶液在160摄氏度下反应不少于12小时。自然冷却至室温后,离心,采用无水乙醇与超纯水分别洗涤多次,冷冻干燥。
所得的样品用x-FBB表示,其中x(0.05,0.1,0.2,0.4)为Fe/Bi摩尔比,分别为0.05,0.1,0.2,0.4;未经过铁改性的样品为BiOBr样品。所有的操作均在氩气保护下完成。
图1为所制备的BiOBr样品和x-FBB样品的XRD图谱。可以看出,BiOBr样本的所有衍射峰均与四方相BiOBr的标准数据(JCPDS card no.09-0393)相匹配。然而,x-FBB样品可以与四方相BiOBr的标准数据(JCPDS card no.09-0393)和菱形相Bi(JCPDS card no.44-1246)相对应。x-FBB样品中,对应的Bi晶相的峰强度随样品中Fe含量的增加而增加。这表明,二价铁可以还原Bi3+至Bi0,从而有助于非晶相转变为结晶相,因此加入二价铁可以强化Bi金属单质的生长。无定形的Bi金属纳米粒子可能存在于BiOBr样品中。图1的插图为{110}晶面的衍射峰位置图。随着Fe/Bi摩尔比的增大,x-FBB样品的衍射峰位置稍转向更高的2θ值,其他峰位置也出现了类似的现象。这是因为,离子半径的差异导致了晶格参数的变化,二价铁离子半径(0.075nm)小于Bi3+的(0.103nm)。同时,掺杂的Fe可能通过取代Bi3+而进入BiOBr晶格中。
采用SEM分析了所制备的BiOBr样品和x-FBB样品的微观结构、形貌和粒度。图2展示了样品的扫描电镜图像。其中,图2a显示,直径约为8μm的BiOBr微球的外表面由小麦状的纳米颗粒所包裹着。图2b-2d显示,x-FBB微球,直径范围从3μm到5μm,看上去是由许多纳米薄片挤在一起所形成的。图2e显示,有一部分掺杂的微球被抑制生成。图2f-2h为0.2-FBB样品的化学元素映射分析,显示了Bi、O、Br和Fe元素在0.2-FBB样品表面分布均匀。这表明,铁离子的加入可以促进纳米片的生成。
图3a显示,通过N2吸附-脱附方法分析了样品的比表面积和孔隙率。等温线属于IV型曲线,在0.5-1.0p/p0间出现了明显的滞后环,属于典型的介孔材料。根据IUPAC建议,上述滞后环可以被归类为H3型循环,是一种由形成裂隙状孔洞的层状颗粒凝结(松散聚集)组成的材料。通过样品的N2吸附-脱附等温线计算其比表面积。如图3b所示,利用布鲁诺尔-埃米特-泰勒比表面积法(BET)测定,样品包含小介孔(3.6nm)和最大孔隙直径约为15nm的大介孔。表1中列出了,样品的孔径、孔隙体积和表面积,可以看出,它们随着Fe/Bi摩尔比的增大而增大。此结果可能归因于,所形成的纳米片状结构叠加后形成一种网状结构而导致的。
表1由吸附等温线和XPS得到的样品物理参数
通过紫外-可见分光光度计测定所得样品的光学特性。图4显示了BiOBr样品和x-FBB样品的紫外-可见DRS光谱。400nm波长附近吸光度的急剧增加说明,此处为纯BiOBr的直接带隙,禁带宽度为2.54eV。通过x-FBB样品的紫外-可见DRS图谱可以看出,这些样品发生了系统的红移,并在可见光及近红外区域的吸收量增加。从样品的颜色逐渐由白变红黄色这一现象,也可简单地得出这个结论。在可见光范围内吸收的加强,可以归因于氧空位和金属Bi的存在。
通过初始浓度为20mg/L的罗丹明的降解速率,来评价BiOBr样品和x-FBB样品的可见光类芬顿催化活性。图5a显示了在可见光类芬顿催化降解过程中,罗丹明B的浓度随光照时间的变化。空白实验显示,罗丹明B在没有催化剂存在的条件下,光降解量极低,几乎可以被忽略。在30分钟的吸附-解吸平衡后,吸附能力最强的催化剂为0.2-FBB,吸附效率为43%。60分钟的光照后,样品BiOBr、0.05-FBB、0.1-FBB、0.2-FBB和0.4-FBB对罗丹明B的降解效率分别为56.5%、46.8%、81.3%、99.0%和95.2%。采用伪一级动力学模型:ln(C/C0)=-kt来描述此催化降解过程,其中k是不同催化剂的表观速率常数,作为基本动力学参数。从图5b看出,样品BiOBr、0.05-FBB、0.1-FBB、0.2-FBB和0.4-FBB的动力学常数分别为0.0114min-1、0.0092min-1、0.0178min-1、0.0449min-1和0.0326min-1。这表明,在H2O2强化光催化反应中,0.2-FBB的催化性能最强。
在类芬顿反应和光催化反应中,样品0.05-FBB、0.1-FBB、0.2-FBB和0.4-FBB的动力学常数分别为0.00165min-1、0.00263min-1、0.00445min-1、0.00172min-1和0.00168min-1、0.00179min-1、0.00269min-1、0.0003min-1,这些远远低于它们在可见光类芬顿反应中的动力学常数。这表明,H2O2可以在可见光下,激活x-FBB样品的催化活性位点。
上述结果说明,本发明的方法制备的铁改性光催化材料能够对水体中的污染物进行高效的催化降解,具有良好的推广应用前景。
以上所述的具体实施例,对本发明的目的、技术方案和有益效果进行了进一步详细说明,应理解的是,以上所述仅为本发明的具体实施例而已,并不用于限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (5)
1.一种铁改性光催化材料的制备方法,其特征在于,其是在含有铁盐和硝酸铋的溶液中,加入溴化钾溶液,高温反应后即得所述铁改性光催化材料,具体包括:
(1)在氩气保护下,在含冰醋酸的乙二醇溶液中加入硝酸铋,搅拌直到硝酸铋全部溶解,配制成浓度为0.1mol/L的硝酸铋溶液,其中冰醋酸与乙二醇的体积比为1:10;
(2)在氩气保护下,向步骤(1)得到的硝酸铋溶液中加入铁盐FeCl2·4H2O,搅拌直到铁盐全部溶解,即得到所述含有铁盐和硝酸铋的溶液,其中,所述铁盐FeCl2·4H2O的添加量为5~40%,所述百分比为所述铁盐的物质的量占所述硝酸铋的物质的量的百分比;
(3)在乙二醇溶液中加入溴化钾,搅拌直到溴化钾全部溶解,所述的溴化钾溶液的浓度为0.1mol/L;
(4)在氩气保护下,于160摄氏度下进行密封反应,反应时间不少于12小时;
(5)将反应体系自然冷却至室温,离心,然后采用无水乙醇与超纯水分别洗涤多次,冷冻干燥,即得到所述铁改性光催化材料;
其中,得到的所述铁改性光催化材料具有异质结,掺杂的铁元素通过取代三阶铋离子进入BiOBr晶格中,用以提高光催化材料的比表面积、吸附性能和光催化效果。
2.根据权利要求1所述的制备方法,其特征在于,步骤(2)中,所述铁盐FeCl2·4H2O的添加量为20%。
3.根据权利要求1所述的制备方法,其特征在于,所述的溴化钾溶液的添加量为100%,所述百分比为所述溴化钾溶液的体积占所述含有铁盐和硝酸铋的溶液的体积的百分比。
4.根据权利要求1~3任一项所述的制备方法制得的铁改性光催化材料,其特征在于,应用在双氧水存在的条件下,光催化反应过程中,所述双氧水使得所述铁改性光催化材料表面铁元素在二价铁和三价铁之间形成链式反应,用以提高催化降解效果。
5.权利要求4所述的铁改性光催化材料在水处理中的应用。
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