CN109675591B - 一种Fe(II)和或Cu(II)改性光催化材料的制备方法及其应用 - Google Patents
一种Fe(II)和或Cu(II)改性光催化材料的制备方法及其应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 49
- 238000006731 degradation reaction Methods 0.000 claims abstract description 28
- 230000015556 catabolic process Effects 0.000 claims abstract description 26
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 claims description 45
- 229960000623 carbamazepine Drugs 0.000 claims description 45
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
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- 238000006243 chemical reaction Methods 0.000 claims description 17
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 14
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 13
- 229910052797 bismuth Inorganic materials 0.000 claims description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 10
- 150000001879 copper Chemical class 0.000 claims description 9
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 8
- 229960002089 ferrous chloride Drugs 0.000 claims description 7
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical group Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 10
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- 238000005516 engineering process Methods 0.000 abstract description 8
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种Fe(II)和或Cu(II)改性光催化材料的制备方法及其应用,本发明将二价铁和二价铜掺杂进入BiOBr光催化材料中,构建双重氧化体系(光催化和类芬顿技术),可通过金属的表面等离子共振效应,极大地提高光催化效率,并能增大催化材料的比表面积,增强其吸附性能;该制备方法简单、操作方便、原料易得、生产加工成本低,制备的Fe(II)和或Cu(II)改性光催化材料可以强化激素、化妆品、农药等难降解有机污染物在降解方面的应用。
Description
技术领域
本发明涉及光催化材料领域,尤其涉及一种Fe(II)和或Cu(II)改性光催化材料的制备方法及其应用。
背景技术
随着全球化工行业的迅速发展,污染物排放增多,环境污染已受到严重威胁。在众多的污染治理技术中,光催化技术以其环境友好型以及可实现深度治理的特点,受到了科研工作者的关注。
光催化材料是指通过该材料、在光的作用下发生的光化学反应所需的一类半导体催化剂材料。通常,光催化过程中产生的空穴(h+)、羟基自由基(·OH)和超氧自由基(·O2-)有强氧化能力,能够与污染物发生氧化还原反应,实现污染物分子的完全降解,并最终分解为CO2、H2O和无毒的无机物等。
可见光光催化技术因具有反应条件温和、能耗低、操作简便以及可利用太阳光作为反应光源等特点,在环境污染治理和能源开发方面发挥着越来越重要的作用。可见光催化技术的关键在于新型可见光催化剂的制备及其改性,传统的可见光催化剂存在效率低且回收利用相对较难等缺点,如何提高可见光催化剂的效率,实现其可持续循环利用成为国内外光催化领域的研究热点。
世界上能作为光催化材料的有很多,包括二氧化钛、氧化锌、氧化锡、二氧化锆、硫化镉等多种氧化物硫化物半导体,其中二氧化钛(Titanium Dioxide)因其氧化能力强,化学性质稳定无毒,成为世界上最当红的纳米光触媒材料。二氧化钛半导体材料是研究最早最传统的光催化材料,但是,二氧化钛半导体材料存在许多缺陷,所以,能充分利用太阳能的新型铋系光催化材料备受研究者的关注,在处理环境污染方面具有潜在应用价值。
铋系光催化材料,由于具有良好的紫外光和可见光光催化活性、独特的层状结构以及高的光稳定性,越来越受到人们的关注。而卤氧化铋BiOX(X=Cl、Br、I)也是一种高效的光催化剂,其中的BiOBr因其较窄的禁带宽度,特殊的电子结构、优良的光电性能以及可见光催化能力较强等备受青睐。虽然BiOBr具有良好光催化活性,但为充分实现其在实际应用中的价值,必须进一步提高BiOBr的光催化活性。
发明内容
针对上述技术中存在的不足之处,本发明的目的是提供一种Fe(II)和或Cu(II)改性光催化材料的制备方法及其应用,该方法将二价铁和二价铜掺杂进入BiOBr光催化材料中,构建双重氧化体系(光催化和类芬顿技术),可通过金属的表面等离子共振效应,极大地提高光催化效率,并能增大催化材料的比表面积,增强其吸附性能。
本发明的另一个目的是提供一种Fe(II)和或Cu(II)改性光催化材料的制备方法及其应用,该制备方法简单、操作方便、原料易得、生产加工成本低,用于降解水中的新兴污染物,在实际工作中能得到广泛的应用。
为实现上述目的,本发明是这样实现的:
一种Fe(II)和或Cu(II)改性光催化材料的制备方法,其包括以溴化物、五水合硝酸铋、亚铁盐和或铜盐为原料,以乙二醇为溶剂,采用水热共沉淀法制备Fe(II)和或Cu(II)改性光催化材料。
进一步,其包括以下步骤:
S1、将亚铁盐、铜盐与五水合硝酸铋加入含体积分数为10%冰醋酸的乙二醇中,搅拌至充分溶解,配制成溶液;
S2、向步骤S1中制得的溶液添加溴化钾溶液;
S3、将步骤S2中制得溶液加热并使其在高温下反应,其中反应温度为150-180℃,反应时间为10-15h;
S4、反应结束后,将反应产物冷却、冷冻并干燥,得到所需的Fe(II)和或Cu(II)改性光催化剂。
进一步,在步骤S1中,亚铁盐、铜盐与五水合硝酸铋的加入量之间的摩尔比为Fe(II):Cu(II):Bi(Ⅲ)=0.25:0:1~0:0.25:1,其中每1mol铋元素对应加入20-100ml含体积分数为10%冰醋酸的乙二醇。乙二醇只是作为溶剂使用,铜、铁元素的总加入量是铋元素加入量的0.25倍,优选为Fe(II):Cu(II):Bi(Ⅲ)=0.24:0.01:1~0.20:0.05:1。
进一步,在步骤S2中,溴化钾溶液中的溶剂为乙二醇,且每1mol铋元素对应加入1mol溴元素。溴化钾的加入量只与铋元素的加入量有关,当铋元素的加入量为定值时,所述溴化钾的加入量也是定值,且溴元素的加入量可以稍微过量,有利于反应的完成。具体的,所述溴化钾溶液可用其他溴化物溶液代替,但其效果没有溴化钾的效果好,其中,溴化钾在乙二醇中的含量优选为0.1mol/L。
进一步,在步骤S1中,亚铁盐为氯化亚铁,铜盐为硝酸铜或氯化铜。
进一步,步骤S1-S4均在氩气、氮气或氦气保护下完成。
本发明制备的Fe(II)和或Cu(II)改性光催化材料可以在可见光催化处理水中污染物领域中应用。
进一步,本发明制备的Fe(II)和或Cu(II)改性光催化材料可以强化激素、化妆品、农药等难降解有机污染物在降解方面的应用。
进一步,所述Fe(II)和或Cu(II)改性光催化材料与双氧水配合使用,其中双氧水浓度为1mmol/L,pH为3-7。
进一步,所述Fe(II)和或Cu(II)改性光催化材料呈球状,粒径为2-4μm,比表面积为10-20g/m2,孔径为8-12nm,孔容量为0.025-0.060cm3/g,能带间隙为2.60-2.90eV。
本发明的优势在于,本发明将二价铁和二价铜掺杂进入BiOBr光催化材料中,构建双重氧化体系(光催化和类芬顿技术),可通过金属的表面等离子共振效应,极大地提高光催化效率,并能增大催化材料的比表面积,增强其吸附性能;该制备方法简单、操作方便、原料易得、生产加工成本低,制备的Fe(II)和或Cu(II)改性光催化材料可以强化激素、化妆品、农药等难降解有机污染物在降解方面的应用。
附图说明
图1为本发明的制备方法示意图。
图2为实施例一~实施例六所制备的产品的XRD图谱。
图3为不同光催化剂对卡马西平(CBZ)的降解随光照时间的变化曲线图。
图4为不同CBZ浓度时,0.02-FCB对卡马西平(CBZ)的降解随光照时间的变化曲线图。
图5为图4中不同CBZ浓度时0.02-FCB对卡马西平(CBZ)降解的二级动力学反应常数的曲线图。
图6为在不同双氧水浓度条件下,0.02-FCB对卡马西平(CBZ)的降解随光照时间的变化曲线图。
图7为图6中在不同双氧水浓度条件下,0.02-FCB对卡马西平(CBZ)的降解的二级动力学反应速率常数的曲线图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
实施例一:
在氩气的保护下,将含0.24mol Fe(II)的氯化亚铁、含0.01mol Cu(II)的氯化铜和含1mol Bi(Ⅲ)的五水合硝酸铋(Fe(II):Cu(II):Bi(Ⅲ)=0.24:0.01:1),溶于50ml含体积分数为10%冰醋酸的乙二醇中,搅拌至充分溶解,配制成溶液;并向上述溶液中加入含有0.1mol/L溴化钾的乙二醇溶液,其中溴元素的加入量为1mol;将上述溶液置于160℃下反应12h后冷冻并干燥。
制得的样品用x-FCB表示,其中x为Cu(II)与Bi(Ⅲ)进料的摩尔比,F代表铁元素,C代表铜元素,B代表铋元素。在本实施例中x为0.01,即本实施例制得的产品表示为0.01-FCB。
实施例二:将进料量改为含0.23mol Fe(II)的氯化亚铁、含0.02mol Cu(II)的氯化铜和含1mol Bi(Ⅲ)的五水合硝酸铋(Fe(II):Cu(II):Bi(Ⅲ)=0.23:0.02:1),其余步骤与实施例一相同;本实施例制得的产品表示为0.02-FCB。
实施例三:将进料量改为含0.20mol Fe(II)的氯化亚铁、含0.05mol Cu(II)的氯化铜和含1mol Bi(Ⅲ)的五水合硝酸铋(Fe(II):Cu(II):Bi(Ⅲ)=0.20:0.05:1),其余步骤与实施例一相同;本实施例制得的产品表示为0.05-FCB。
实施例四:将进料量改为含0.15mol Fe(II)的氯化亚铁、含0.1mol Cu(II)的氯化铜和含1mol Bi(Ⅲ)的五水合硝酸铋(Fe(II):Cu(II):Bi(Ⅲ)=0.15:0.1:1),其余步骤与实施例一相同;本实施例制得的产品表示为0.1-FCB。
实施例五:将进料量改为不添加氯化亚铁、添加含0.01mol Cu(II)的氯化铜和含1mol Bi(Ⅲ)的五水合硝酸铋(Fe(II):Cu(II):Bi(Ⅲ)=0:0.01:1),其余步骤与实施例一相同;本实施例作为实施例一的对比试验,由此制得的经过Cu(II)改性的光催化材料,本实施例制得的产品表示为CB。
实施例六:将进料量改为不添加氯化铜,添加含0.24mol Fe(II)的氯化亚铁和含1mol Bi(Ⅲ)的五水合硝酸铋(即Fe(II):Cu(II):Bi(Ⅲ)=0.24:0:1),其余步骤与实施例一相同;本实施例作为实施例一的对比试验,由此制得的经过Fe(II)改性的光催化材料,本实施例制得的产品表示为FB。
实施例七:将进料量改为不添加氯化亚铁、添加含0.25mol Cu(II)的氯化铜和含1mol Bi(Ⅲ)的五水合硝酸铋(即Fe(II):Cu(II):Bi(Ⅲ)=0:0.01:1),其余步骤与实施例一相同;由此制得的经过Cu(II)改性的光催化材料,本实施例制得的产品表示为0.25-CB。
实施例八:将进料量改为不添加氯化铜,添加含0.25mol Fe(II)的氯化亚铁和含1mol Bi(Ⅲ)的五水合硝酸铋(Fe(II):Cu(II):Bi(Ⅲ)=0.24:0:1),其余步骤与实施例一相同;本由此制得的经过Fe(II)改性的光催化材料,本实施例制得的产品表示为0.25-FB。
参照图2,由实施例一~实施例六所制备的x-FCB产品的XRD图谱可以看出,随着Fe(II)和Cu(II)加入后,BiOBr的晶面对应峰强度有很大影响。与BiOBr晶相相比,改性后光催化剂的晶面{110}位置向高2θ值移动,表明Fe(II)或Cu(II)与BiOBr中Bi发生同晶置换导致晶格参数发生变化,利于活性物种形成。当Fe(II)含量增多和Cu(II)含量降低时,27°左右的峰强度突然增加且不断增强,反之减少,甚至消失。经过pdf卡片比对,该特征峰属于斜方六面体结构Bi晶相(JCPDS-ICDD CardNo.00-044-1246),说明Fe(II)存在利于单质Bi的生成,而Cu(II)则相反。
本发明结合具体实施例一~实施例六,测试了在双氧水存在的条件下,不同亚铁盐和铜盐添加量下制备的Fe(II)和或Cu(II)改性光催化材料对卡马西平(CBZ)的降解效果,进一步说明本发明的光催化材料对水中污染物的降解能力。
参照图3,图3为不同光催化剂对卡马西平(CBZ)的降解随光照时间的变化曲线图,图3显示了在可见光-类芬顿催化降解过程中,CBZ的浓度随光照时间的变化。实验条件为:光催化材料浓度:0.5g/L;CBZ浓度:1.5mg/L;双氧水浓度:1mmol;将光催化材料和卡马西平(CBZ)在pH为中性的条件下进行反应,先在黑暗条件下反应30min,使催化材料对污染物的吸附达到饱和,然后加入双氧水,使溶液中双氧水初始浓度为1mmol/L,在>400nm波长的条件下进行反应。
表1为一级、二级动力学反应常数及拟合度
通过对初始浓度为1.5mg/L的卡马西平(CBZ)的降解,来评价x-FCB产品、CB产品和FB产品的可见光-类芬顿催化活性。通过图3和表1可知,在30分钟的吸附-解吸平衡后,吸附效率不足5%。10分钟的光照后,CBZ在0.01-FCB、0.02-FCB、0.05-FCB催化剂存在的条件下,光降解量最大,几乎完全降解。采用一级、二级动力学模型:C=C0e-kt和C=C0/(1+C0kt)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。从拟合度可以看出,单独铁或铜改性催化剂对CBZ降解反应适合于一级动力学反应模型;而二者共同存在时CBZ降解反应适合于二级动力学反应模型。
参照图4-5,图4展示了不同CBZ浓度时0.02-FCB对卡马西平(CBZ)的降解随光照时间的变化曲线图,图5为不同CBZ浓度时0.02-FCB对卡马西平(CBZ)降解的二级动力学反应常数的曲线图。实验条件为:0.02-FCB浓度:0.5g/L;双氧水浓度:1mmol/L;CBZ:1~10mg/L。通过实验可以看出,随着CBZ浓度升高,0.02-FCB催化材料的性能减弱,反应的动力学常数从2.4L·min-1·mg-1降低到0.14L·min-1·mg-1。因此确定在可见光-类芬顿反应中,最佳处理浓度不得超过5mg/L。
图6展示了在不同双氧水浓度条件下,0.02-FCB对卡马西平(CBZ)的降解随光照时间的变化曲线图,图7为在不同双氧水浓度条件下,0.02-FCB对卡马西平(CBZ)的降解的二级动力学反应速率常数的曲线图。实验条件为:0.02-FCB浓度:0.5g/L,CBZ浓度:1.5mg/L,双氧水浓度:0.5~10mmol/L。通过实验可以看出,在双氧水浓度为1~10mmol/L的条件下,0.02-FCB催化材料的性能最强,反应的动力学常数为2.4L·min-1·mg-1,因此确定在可见光-类芬顿反应中,双氧水的最优浓度为1mmol/L。
上述试验结果说明,本利用方法制备的Fe(II)和或Cu(II)改性光催化材料,亚铁盐、铜盐与五水合硝酸铋的加入量之间的摩尔比为优选为Fe(II):Cu(II):Bi(Ⅲ)=0.24:0.01:1~0.20:0.05:1。Fe(II)和或Cu(II)改性光催化材料在双氧水浓度为1mmol/L,CBZ浓度不超过5mg/L的条件下,可见光-类芬顿催化降解的效果最优,能够对水体中的污染物进行高效的催化降解,推广应用前景良好。
本发明的优势在于,本发明将二价铁和二价铜掺杂进入BiOBr光催化材料中,构建双重氧化体系(光催化和类芬顿技术),可通过金属的表面等离子共振效应,极大地提高光催化效率,并能增大催化材料的比表面积,增强其吸附性能;该制备方法简单、操作方便、原料易得、生产加工成本低,制备的Fe(II)和或Cu(II)改性光催化材料可以强化激素、化妆品、农药等难降解有机污染物在降解方面的应用。
以上只是本发明优选的实施例,但是本发明并非局限于此,任何本领域的技术人员能思之的变化都应落入本发明的保护范围。
Claims (6)
1.一种Fe(II)和Cu(II)改性光催化材料在可见光-类芬顿催化降解卡马西平中的应用,其特征在于所述Fe(II)和Cu(II)改性光催化材料的制备方法包括以下步骤:
S1、将亚铁盐、铜盐与五水合硝酸铋加入含体积分数为10%冰醋酸的乙二醇中,搅拌至充分溶解,配制成溶液;亚铁盐、铜盐与五水合硝酸铋的加入量之间的摩尔比为Fe(II):Cu(II):Bi(III)=0.24:0.01:1~0.23:0.02:1,其中每1mol铋元素对应加入20-100mL含体积分数为10%冰醋酸的乙二醇;
S2、向步骤S1中制得的溶液添加溴化钾溶液;
S3、将步骤S2中制得溶液加热并使其在高温下反应,其中反应温度为150-180℃,反应时间为10-15h;
S4、反应结束后,将反应产物冷却、冷冻并干燥,得到所需的Fe(II)和Cu(II)改性光催化材料。
2.根据权利要求1所述的一种Fe(II)和Cu(II)改性光催化材料在可见光-类芬顿催化降解卡马西平中的应用,其特征在于在步骤S2中,溴化钾溶液中的溶剂为乙二醇,且每1mol铋元素对应加入1mol溴元素。
3.根据权利要求1所述的一种Fe(II)和Cu(II)改性光催化材料在可见光-类芬顿催化降解卡马西平中的应用,其特征在于在步骤S1中,亚铁盐为氯化亚铁,铜盐为硝酸铜或氯化铜。
4.根据权利要求1所述的一种Fe(II)和Cu(II)改性光催化材料在可见光-类芬顿催化降解卡马西平中的应用,其特征在于,步骤S1-S4均在氩气、氮气或氦气保护下完成。
5.根据权利要求1-4任一项所述的Fe(II)和Cu(II)改性光催化材料在可见光-类芬顿催化降解卡马西平中的应用,其特征在于制得的Fe(II)和Cu(II)改性光催化材料呈球状,粒径为2-4μm,比表面积为10-20m2 /g ,孔径为8-12nm,孔容量为0.025-0.060cm3/g,能带间隙为2.60-2.90eV。
6.根据权利要求1所述的一种Fe(II)和Cu(II)改性光催化材料在可见光-类芬顿催化降解卡马西平中的应用,其特征在于所述Fe(II)和Cu(II)改性光催化材料与双氧水配合使用,其中双氧水浓度为1mmol/L,pH为3-7。
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