CN106552651A - 一种Bi12O17Br2光催化剂的合成及应用方法 - Google Patents
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Abstract
一种Bi12O17Br2光催化剂的合成及应用方法,属于环境化工光催化水处理技术领域。其特征在于:以Bi(NO3)3·5H2O和NaBrO3为原料,以乙二醇和水为溶剂,在室温下利用简单易行经济环保的醇解法,通过控制乙二醇和水的加入量,制得了组成单一、带隙适配和可以充分利用光生电子空穴对的Bi12O17Br2光催化剂粉体。从而加强了此类催化剂对光生电子空穴对的充分利用,提高了对太阳光的利用率。此外此种方法在低温下即可实现,简单易行、经济环保且对有机物的降解表现出了良好的响应能力和光催化降解能力,对环境治理和绿色能源利用具有重要意义。
Description
技术领域
本发明一种Bi12O17Br2光催化剂的合成及应用方法,属于纳米材料技术领域,具体涉及一种可以用于降解液体中有机污染物的光催化剂Bi12O17Br2的制备方法及应用方法。
背景技术
在环境污染和能源危机日益严重的今天,半导体光催化技术因其操作简单、无污染、反应彻底、速率快和所用能源可再生,而被视为是一种具有应用前景的污染物处理和能源转化技术。在过去的几十年里,许多光催化剂已经被广泛应用于有机污染物的降解以及氢能的转换,其中BiOBr作为一种重要的Ⅴ-Ⅵ-Ⅶ型三元化合物半导体光催化材料,为四方PbFCl型晶系结构,空间群和对称性分别为P4/nmm(No.129)和D7 4h。其由于独特的开放式层状结构和间接跃迁模式,在光催化反应过程中表现出了较好的光生载流子转移速率及光生电子-空穴对分离效率,进而拥有了较好的光催化活性,在空气净化和有机废水处理方面展现出了潜在的应用前景,成为了目前国内外学者的研究重点。
在光催化反应过程中,半导体光催化剂受光激发,产生光生电子,并由催化剂的价带跃迁至导带,同时在价带上生成光生空穴,从而在催化剂内部形成高能量的电子-空穴对。其中价带上的空穴具有强氧化能力,可以直接与吸附在催化剂表面的有机物发生反应,或者与吸附在催化剂表面的H2O或OH-反应生成具有强氧化能力的活性物种羟基自由基(HO·),进而将有机物转化为无害的CO2和H2O;而导带上的电子则具有还原能力,可以与溶液中的溶解氧(O2)反应生成超氧自由基(·O2 -),再与有机污染物直接反应或者先经过一系列反应生成羟基自由基(HO·),再与有机物进行降解反应。同时在此过程中溶解氧(O2)可以捕获光生电子,阻止电子空穴复合,提高光催化活性。综合以上反应机理可以看出,光催化效率不仅取决于光生载流子的激发和复合率,而且还取决于光生电子空穴对的还原和氧化能力,而对于BiOBr来说,其价带值(3.19eV)明显高于TiO2(2.91eV)、BiOI(2.42eV)等催化剂以及H2O2(1.77eV)和O3(2.07eV)等传统的氧化剂。这说明BiOBr在反应体系中具有更强的氧化能力,从而可以能够更好、更快和更广的将有机污染物进行氧化降解和矿化。但其导带位置(0.83eV)却远远地低于O2/·O2 -(-0.83eV),使得此类催化剂在光催化过程中不能与催化剂表面的氧分子相结合,形成超氧自由基,从而对有机污染物实现降解,这不仅会造成太阳光的能源浪费,而且多余的电子势必会返回到导带与空穴复合,导致BiOBr催化剂在光催化过程中活性物种数量的下降,因此寻找一种合适的方法对其能带结构进行改性,以使其在保证足够氧化能力的同时,还原能力得到增强成为了目前的研究重点。
近几年的研究表明,通过控制BiOBr催化剂中Br含量的多少,可以有效地对BiOBr的能带结构进行调控(Journal of Materials Chemistry A 2015,3,5592-5598.TheJournal of Physical Chemistry C 2015,119(23),13032-13040.IOP ConferenceSeries:Materials Science and Engineering 2016,137(1),012020.Journal of theTaiwan Institute of Chemical Engineers 2014,45(5),2688-2697.ChemicalEngineering Journal 2016,299,217-226),从而使其能带结构达到最优化,进而拥有最佳的价带导带位置,但就目前的研究来看,此类催化剂的制备过程往往需要高温高压,且方法较复杂,所需时间较长,更重要的是所制的催化剂不纯净,多为混合物,因此如何寻找出一种简单经济环保的制备方法,以得到纯净的、Br含量相对较少和能带结构适配的BixOyBrz系列催化剂,从而实现对光生电子空穴对的充分利用,具有很大的现实意义,同时也是光催化技术领域一项长期而艰巨的任务。
发明内容
本发明一种Bi12O17Br2光催化剂的合成及应用方法,其目的是提供一种简单经济环保的方法,以制备出一种组成单一、带隙结构匹配和可以充分利用光生电子空穴对的光催化剂,从而达到对太阳能的充分有效利用以及降解环境中有机物污染之功效。
本发明一种Bi12O17Br2光催化剂的合成方法,其特征在于是以五水硝酸铋和溴酸钠为原料,通过调节溶剂乙二醇和水的比例,利用简单经济环保的醇解法在常温下制得了组成单一、带隙适配和可以充分利用光生电子空穴对的Bi12O17Br2光催化剂,其具体制备步骤为:
1)称取0.005~0.015mol的五水硝酸铋,将其放置于50~60mL的乙二醇溶剂中,在室温下搅拌1~2h,直至形成澄清溶液,记为溶液A;
2)称取0.005~0.015mol的溴酸钠,将其放置于70~60mL的水溶剂中,在室温下搅拌1~2h,直至形成澄清溶液,记为溶液B;
3)将上述溶液A加入溶液B中,并在室温下继续搅拌反应1~6h,即可得到沉淀;
4)用离心机将步骤3中所得沉淀分别进行分离,并用蒸馏水和无水乙醇分别洗涤2~3次后,在50~70℃下烘干,即得到组成单一、带隙适配、可以充分利用光生电子空穴对、光催化活性好且可用于降解水中微量难降解有机污染物的Bi12O17Br2。
用上述方法合成的一种Bi12O17Br2光催化剂的应用方法,其特征在于所述的原料五水硝酸铋和溴酸钠的加入量摩尔比应为1,所述溶剂乙二醇和水的加入量体积比应为0.7~1,且总量维持在120mL。
用上述方法合成的一种Bi12O17Br2光催化剂的应用方法,其特征在于所述的水中微量难降解有机污染物为间苯二酚或双酚A,反应条件为:常温常压,催化剂用量为0.03g,间苯二酚或双酚A的处理量为50~100mL和10mg·L-1,所用光源为氙灯,功率为500W,照度为120klx,距离反应界面20cm,所发光为波长为200~800nm的模拟太阳光。
本发明一种Bi12O17Br2光催化剂的合成及应用方法优点为:
1.目前所报道的关于此类催化剂的制备大多数采用的都是水热法,需要在高温高压的反应釜中加热至100~400℃下,反应,亦或者采用十六烷基三甲基溴化铵这类高分子物质作为溴源,且反应过程中需要添加尿素作为改性剂,而本发明所用的醇解法在室温下即可进行且反应过程中无高分子物质以及改性剂参与,因此原料易得,所用方法简单易行、经济环保且简单安全,易于实现工业化生产;
2.本发明所制催化剂的组成单一,为纯的Bi12O17Br2光催化剂,同时通过对其带隙位置的表征,发现其价带位置为2.89eV,导带位置为-0.18eV,说明此种催化剂受光激发后产生的电子-空穴对有足够的还原氧化能力与溶液中的溶解氧(O2/O2 ·-—-0.046eV)以及吸附在催化剂表面的H2O(·OH/H2O—2.27eV)或OH-(·OH/OH-—1.99eV)反应生成活性物种超氧自由基和羟基自由基,因此此种催化剂具有非常适宜的带隙结构,从而可以充分利用光生电子空穴对,进而加强了对太阳光的有效利用;
3.本发明所制Bi12O17Br2催化剂无论是对于间苯二酚还是双酚A溶液均可以在35min内使其降解率达到95%以上,且经过五次循环实验后降解率仍保持在94%以上,相比较于传统的BiOBr光催化剂(相同条件下35min之内对于间苯二酚或者双酚A的降解率为42%)表现出了良好的光催化活性,且性能稳定,可重复使用,对环境治理和绿色能源利用具有重要意义。
附图说明
图1为本发明实施方式1所制Bi12O17Br2光催化剂的XRD图谱
图2为本发明实施方式1所制Bi12O17Br2光催化剂的DRS图谱
图3为本发明实施方式1所制Bi12O17Br2光催化剂的Mott-Schottky图谱
图4为本发明实施方式1所制Bi12O17Br2光催化剂的VB-XPS图谱
图5为本发明实施方式1所制Bi12O17Br2光催化剂的能带结构图谱。
具体实施方式
为了使本发明的技术方案更加清楚明白,下面将用实施例具体给予详细说明,但本发明的内容不只局限于所列举的实施方式的范围。
实施方式1
将0.01mol Bi(NO3)3·5H2O加入到60mL乙二醇中在室温下搅拌1.5h,形成澄清溶液A;将0.01mol NaBrO3加入到60mL蒸馏水中在室温下搅拌1.5h,形成澄清溶液B;接着将溶液A加入溶液B中,并在室温下继续搅拌反应2h,即可得到沉淀,并用离心机将所得沉淀进行分离,然后用蒸馏水和无水乙醇分别洗涤3次后,在60℃下烘干,即得到Bi12O17Br2催化剂,记为Bi12O17Br2-A。
所得Bi12O17Br2-A光催化剂用于光催化降解间苯二酚或者双酚A溶液。其反应条件为:常温常压,所用模拟太阳光为氙灯,功率为500W,照度为120klx距离反应界面20cm。催化剂用量为0.03g,水中有机污染物间苯二酚或者双酚A的处理量为100mL和10mg·L-1。降解过程中首先在避光条件下吸附5min,以期达到吸附平衡;然后打开光源,对间苯二酚或者双酚A溶液进行光催化降解实验,每隔5min取样一次,利用紫外-可见分光光度法对溶液中剩余待降解物的浓度进行分析并计算其降解率,结果如表1所示。
实施方式2
将0.005mol Bi(NO3)3·5H2O加入到55mL乙二醇中在室温下搅拌1.5h,形成澄清溶液A;将0.005mol NaBrO3加入到65mL蒸馏水中在室温下搅拌1.5h,形成澄清溶液B;接着将溶液A加入溶液B中,并在室温下继续搅拌反应4h,即可得到沉淀,并用离心机将所得沉淀进行分离,然后用蒸馏水和无水乙醇分别洗涤3次后,在60℃下烘干,即得到Bi12O17Br2催化剂,记为Bi12O17Br2-B。
所得Bi12O17Br2-B光催化剂用于光催化降解间苯二酚或者双酚A溶液。其反应条件为:常温常压,所用模拟太阳光为氙灯,功率为500W,照度为120klx距离反应界面20cm。催化剂用量为0.03g,水中有机污染物间苯二酚或者双酚A的处理量为100mL和10mg·L-1。降解过程中首先在避光条件下吸附5min,以期达到吸附平衡;然后打开光源,对间苯二酚或者双酚A溶液进行光催化降解实验,每隔5min取样一次,利用紫外-可见分光光度法对溶液中剩余待降解物的浓度进行分析并计算其降解率,结果如表1所示。
实施方式3
将0.015mol Bi(NO3)3·5H2O加入到60mL乙二醇中在室温下搅拌1.5h,形成澄清溶液A;将0.015mol NaBrO3加入到60mL蒸馏水中在室温下搅拌1.5h,形成澄清溶液B;接着将溶液A加入溶液B中,并在室温下继续搅拌反应6h,即可得到沉淀,并用离心机将所得沉淀进行分离,然后用蒸馏水和无水乙醇分别洗涤3次后,在60℃下烘干,即得到Bi12O17Br2催化剂,记为Bi12O17Br2-C。
所得Bi12O17Br2-C光催化剂用于光催化降解间苯二酚或者双酚A溶液。其反应条件为:常温常压,所用模拟太阳光为氙灯,功率为500W,照度为120klx距离反应界面20cm。催化剂用量为0.03g,水中有机污染物间苯二酚或者双酚A的处理量为100mL和10mg·L-1。降解过程中首先在避光条件下吸附5min,以期达到吸附平衡;然后打开光源,对间苯二酚或者双酚A溶液进行光催化降解实验,每隔5min取样一次,利用紫外-可见分光光度法对溶液中剩余待降解物的浓度进行分析并计算其降解率,结果如表1所示。
以上实施方式中所用药品试剂均为分析纯
表1所制不同Bi12O17Br2催化剂在可见光下对于间苯二酚或双酚A的降解活性
Claims (2)
1.一种Bi12O17Br2光催化剂的合成方法,其特征在于是以五水硝酸铋和溴酸钠为原料,通过调节溶剂乙二醇和水的比例,利用醇解法在常温下制得了组成单一、带隙适配和可以充分利用光生电子空穴对的Bi12O17Br2光催化剂,其具体制备步骤为:
1)称取0.005~0.015 mol的五水硝酸铋,将其放置于50~60 mL的乙二醇溶剂中,在室温下搅拌1~2 h,直至形成澄清溶液,记为溶液A;
2)称取0.005~0.015 mol的溴酸钠,将其放置于70~60 mL的水溶剂中,在室温下搅拌1~2 h,直至形成澄清溶液,记为溶液B;
3)将上述溶液A加入溶液B中,并在室温下继续搅拌反应1~6 h,即可得到沉淀;
4)用离心机将步骤3中所得沉淀分别进行分离,并用蒸馏水和无水乙醇分别洗涤2~3次后,在50~70 ℃下烘干,即得到组成单一、带隙适配、可以充分利用光生电子空穴对、光催化活性好且可用于降解水中微量难降解有机污染物的Bi12O17Br2。
2.用权利要求1的方法合成的一种Bi12O17Br2光催化剂的应用方法,其特征在于所述的原料五水硝酸铋和溴酸钠的加入量摩尔比应为1,所述溶剂乙二醇和水的加入量体积比应为0.7~1,且总量维持在120 mL;所述的水中微量难降解有机污染物为间苯二酚或双酚A,反应条件为:常温常压,催化剂用量为0.03 g,间苯二酚或双酚A的处理量为50~100 mL和10mg·L-1,所用光源为氙灯,功率为500 W,照度为120 klx,距离反应界面20 cm, 所发光为波长为200~800 nm的模拟太阳光。
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