CN113578343A - 一种rGO/Fe3O4@Ru-TiO2磁性光催化剂及其制备方法和应用 - Google Patents
一种rGO/Fe3O4@Ru-TiO2磁性光催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种rGO/Fe3O4@Ru‑TiO2磁性光催化剂及其制备方法和应用,以Fe3O4为磁性核,钛酸四丁酯和RuCl3·3H2O为前驱体,十二烷基磺酸钠和氨水为助剂,丙酮为溶剂,通过液相沉积法合成Ru掺杂TiO2的Fe3O4@Ru‑TiO2磁性复合材料;再将合成的磁性复合材料与少层片状氧化石墨烯在乙醇/乙二醇的混合溶剂中通过溶剂热法进行负载复合,最终制备出rGO/Fe3O4@Ru‑TiO2磁性光催化剂。该制备方法简单易行,而且制备条件容易控制,所制备的rGO/Fe3O4@Ru‑TiO2磁性光催化剂对亚甲基蓝有较好的可见光光催化降解活性,具有一定的应用前景。
Description
技术领域
本发明属于化工催化技术领域,具体涉及一种rGO/Fe3O4@Ru-TiO2磁性光催化剂及其制备方法和应用。
背景技术
近几十年来,随着全球工业化和高度现代化农业的发展,大量温室气体和有毒、有害、难降解的有机污染物被排放到自然环境中,致使全球出现不同程度的水资源污染和短缺问题,这些都严重威胁着人类的生存环境和身体健康,而有机染料是其中的主要物质,由于这些有机污染物在环境中很难自然降解,因此就需要人们研究出有效的方法和技术去净化处理被污染的水体。亚甲基蓝(MB,C16H18ClN3S)是一种常用的染料,广泛的应用于染整业、农牧渔业等,是由三个共轭的稠环组成,结构较稳定,一般难以自然降解或生物降解,但由于其应用广泛,已成为废水中有机污染物的重要来源。
TiO2纳米材料作为一种高效的光催化剂已经得到广泛的应用,但也存在一定的缺点和不足:(1)较宽的带隙能(Eg)只能对太阳光的紫外线部分(约占太阳光的5%)产生吸收,光吸收范围较窄;(2)光照射激发产生的电子空穴对能在几个纳秒的时间内复合;(3)分离、回收困难也是其应用受限制的主要原因。因此,降低TiO2的带隙能、减少e-/h+的复合率、增加其比表面积、合成出方便、快速分离回收的TiO2基磁性光催化剂越来越受到广大科研工作者的关注。研究发现,以金属或非金属元素进行掺杂改性,或复合负载其它材料等对TiO2的行貌结构、晶体缺陷、比表面积、光生载流子的动力学和稳定性、光吸收性能以及快速分离回收等方面进行优化改进,可以提高和改善光催化剂的活性和稳定性。
发明内容
针对现有技术的不足,本发明提供一种rGO/Fe3O4@Ru-TiO2磁性光催化剂及其制备方法和应用,方法简单易行,而且制备条件易于控制,所制备的rGO/Fe3O4@Ru-TiO2磁性光催化剂具有较好的光催化降解活性,具有一定的应用前景。
本发明是通过以下技术方案实现的:
一种rGO/Fe3O4@Ru-TiO2磁性光催化剂的制备方法,包括以下步骤:
步骤1)向钛酸四丁酯溶液中加入RuCl3·3H2O乙醇溶液,记为溶液A;
步骤2)将Fe3O4磁性纳米微球、十二烷基磺酸钠、丙酮和氨水混合,超声分散10min确保十二烷基磺酸钠能全部溶解在溶液中,记为溶液B;
步骤3)搅拌步骤2)制得的溶液B,室温下将步骤1)制得的溶液A滴加到溶液B中,待溶液A滴加完毕,继续搅拌,然后对混合液中的灰黑色固体进行磁分离和洗涤,真空干燥,得到产物C;
步骤4)将步骤3)制得的产物C进行煅烧处理,制得Ru掺杂TiO2的磁性Fe3O4@Ru-TiO2复合材料;
步骤5)将步骤4)制得的磁性Fe3O4@Ru-TiO2复合材料在稀硝酸溶液中超声5min后,再用去离子水将复合材料洗涤至中性,最后用乙醇洗涤,分离的固体备用;
步骤6)将经步骤5)处理的复合材料与少层片状氧化石墨烯在乙醇/乙二醇的混合溶剂中通过溶剂热法进行负载复合,制得所述rGO/Fe3O4@Ru-TiO2磁性光催化剂。
优选地,步骤1)所述钛酸四丁酯溶液为钛酸四丁酯的乙醇溶液,体积浓度为2%,添加量为40mL;所述RuCl3·3H2O乙醇溶液的质量浓度为1g/L,添加量为0.734mL。
优选地,步骤2)所述Fe3O4磁性纳米微球的添加量为100mg;所述十二烷基磺酸钠的添加量为0.2g;所述氨水的添加量为2mL;所述丙酮的添加量为150mL。
优选地,步骤3)所述继续搅拌的时间为3h;所述真空干燥的温度为60℃,时间为24h。
优选地,步骤4)所述煅烧处理为:在氮气保护下500℃煅烧3h。
优选地,步骤5)所述磁性Fe3O4@Ru-TiO2复合材料的添加量为100mg;所述稀硝酸的浓度为0.1M,添加量为30mL。
优选地,步骤6)所述少层片状氧化石墨烯的添加量为0~20mg;所述乙醇/乙二醇的混合溶剂中乙醇和乙二醇的体积比为1:1,所述混合溶剂的添加量为60mL。
优选地,步骤6)所述溶剂热法的反应条件如下:反应温度为180℃,反应时间为10h,所得产物于60℃真空干燥24h。
一种rGO/Fe3O4@Ru-TiO2磁性光催化剂,由上述的制备方法制得。
一种rGO/Fe3O4@Ru-TiO2磁性光催化剂在降解亚甲基蓝中的应用。
本发明的有益效果如下:
本发明先采用液相沉积法制备出Fe3O4@Ru-TiO2磁性复合材料,再通过将氧化石墨烯负载在Fe3O4@Ru-TiO2上得到rGO/Fe3O4@Ru-TiO2磁性光催化剂材料。通过降低催化剂的带隙能,抑制电子空穴复合率和实现可磁性回收,而且由于rGO层与染料MB分子之间形成π-π共轭键,大大增加了催化剂对染料的吸附量,从而提高了催化剂对MB的光催化降解率。该制备方法简单易行,而且制备条件容易控制,所制备的磁性复合材料rGO/Fe3O4@Ru-TiO2光催化剂对亚甲基蓝有较好的可见光光催化降解活性,具有一定的应用前景。
附图说明
图1为实施例1制得的rGO/Fe3O4@Ru-TiO2的TEM图,图中:(a)为GFRT0;(b)为GFRT1;(c)为GFRT2;(d)为GFRT3;(e)为GFRT4;(f)为GFRT5;
图2为实施例1制得的rGO/Fe3O4@Ru-TiO2的XRD图,图中:(a)为GFRT0;(b)为GFRT1;(c)为GFRT2;(d)为GFRT3;(e)为GFRT4;(f)为GFRT5;
图3为实施例1制得的rGO/Fe3O4@Ru-TiO2磁性光催化剂(GFRT0~GFRT5)对亚甲基蓝在可见光照射下光催化降解的曲线图;
图4为实施例1制得的rGO/Fe3O4@Ru-TiO2磁性光催化剂(GFRT0~GFRT5)对亚甲基蓝在可见光照射下光催化降解的拟合动力学关系图。
具体实施方式
为了更好地理解本发明,下面结合附图与实施例进一步阐明本发明的内容,但本发明内容不仅仅局限于以下实施例。
实施例1
一种rGO/Fe3O4@Ru-TiO2磁性光催化剂,以Fe3O4为磁性核,钛酸四丁酯和RuCl3·3H2O为前驱体,十二烷基磺酸钠为助剂,在室温下通过简单的液相沉积法合成Ru掺杂TiO2的磁性Fe3O4@Ru-TiO2复合纳米材料;再称取100mg的磁性Fe3O4@Ru-TiO2纳米材料分别与0mg、1mg、5mg、10mg、15mg、20mg少层片状氧化石墨烯复合负载,制备出将Fe3O4@Ru-TiO2复合纳米材料负载在还原石墨烯上的rGO/Fe3O4@Ru-TiO2磁性光催化剂。
一种rGO/Fe3O4@Ru-TiO2磁性光催化剂的制备方法,具体步骤如下:
1、Fe3O4@Ru-TiO2磁性光催化剂的合成:
(1)量取40mL无水乙醇和0.8mL的钛酸四丁酯(TBOT),再在溶液中加入0.734mL的RuCl3·3H2O乙醇溶液(1g/L),记为溶液A。
(2)准确称量Fe3O4磁性纳米微球100mg、十二烷基磺酸钠(SDS)0.2g、丙酮150mL以及氨水2mL,超声分散10min确保SDS能全部溶解在溶液中,记为溶液B。
(3)在机械搅拌装置中搅拌B溶液,室温下将溶液A滴加入到溶液B,待溶液A滴加完毕,搅拌3h,反应结束后,对反应液中的灰黑色固体进行磁分离和洗涤,产品在真空干燥箱中60℃干燥24h,得到产物C。
(4)干燥后的产物C使用氮气保护在管式炉中,设定500℃的煅烧温度和3h的煅烧时间进行煅烧,最后得到Ru掺杂TiO2的磁性Fe3O4@Ru-TiO2复合材料。
2、rGO/Fe3O4@Ru-TiO2磁性光催化剂合成:
(5)准确称取100mg的Fe3O4@Ru-TiO2复合材料在30mL的稀硝酸溶液(0.1M)中超声5min后,再用去离子水将复合材料洗涤至中性,最后用乙醇洗涤,分离的固体备用。
(6)分别称取0mg、1mg、5mg、10mg、15mg、20mg的少层片状氧化石墨烯(GO),分别加入6个量取有60mL乙醇/乙二醇(v/v=1/1)的混合溶液中,超声0.5h;再将经过硝酸酸化的复合材料加入到上述分散有GO的乙醇/乙二醇(v/v=1/1)的混合悬浮液中,超声5min,将悬浮液转移至体积为100mL聚四氟乙烯的不锈钢反应釜中,放入烘箱,设定温度为180℃、时间为10h,反应结束后待反应釜自然冷却到室温,对反应釜中的黑色固体用去离子水进行洗涤,在外磁场下磁分离,产物在真空干燥箱中60℃干燥24h,可得到黑色磁性复合材料rGO/Fe3O4@Ru-TiO2。不同GO负载量的光催化剂分别命名为GFRT0、GFRT1、GFRT2、GFRT3、GFRT4、GFRT5。
如图1所示,合成了氧化石墨烯:Fe3O4@Ru-TiO2=(0~20mg):100mg的磁性光催化剂材料rGO/Fe3O4@Ru-TiO2。由图1中可以看到,图1(a)为未使用氧化石墨烯,磁性核Fe3O4表面周围负载有Ru-TiO2层;当使用不同质量的氧化石墨烯进行还原负载合成的Fe3O4@Ru-TiO2时,如图1(a)~图1(f),Fe3O4@Ru-TiO2成功的负载在rGO上,提高氧化石墨烯的用量比例,其表面负载的Fe3O4@Ru-TiO2纳米颗粒随之减少,分散性增强,这将能促进催化剂尽可能的暴露出更多的活性位点,同时也能增加对有机污染的吸附,这都将有利于提高复合催化剂的光催化活性。
如图2所示,GFRT0~GFRT5的XRD谱图曲线分别为图2(a)~图2(f)。图2中分别出现Fe3O4和锐钛型TiO2的特征峰。2θ°分别为30.2°、35.5°、43.0°、57.1°和62.6°处的特征峰分别对应于面心立方晶型Fe3O4的(220)、(311)、(400)、(511)和(440)晶面;2θ°分别为25.34°、37.87°、48.05°和53.99°的特征峰分别对应于锐钛型TiO2的(101)、(004)、(200)、(105)、(211)以及(204)的晶面,但与标准卡(JCPDS card no.21-1272)对比,2θ°数值发生了微小的变化,这表明Ru掺杂进入TiO2晶格中,但对TiO2的晶型没有明显的改变。但从图2中未发现有关Ru的特征峰,这可能是由于Ru的掺杂量非常小,Ru均匀掺杂在TiO2的晶格中,且没有在TiO2表面形成Ru的其它化合物等。同时也未发现rGO的特征峰,可能是由于Fe3O4@Ru-TiO2的峰强度较大,掩蔽了rGO的特征峰。
实施例2光催化剂催化性能评估
光源采用300W氙灯(北京泊菲莱公司,PLS-SXE300+/UV),配有可见光(λ>420nm)滤波片,量取150mL的5×10-5M的MB染料溶液,称取实施例1中制备的光催化剂50mg在染料溶液中超声分散,分散液避光30min静置,使催化剂和染料之间达到吸附-脱附平衡,然后进行机械搅拌,并开灯对染液进行光催化降解,每隔20min取2mL的染液检测UV-vis光谱,降解80min。
由图3可知,催化剂样品GFRT0~GFRT5均能对MB有较好的光催化降解活性,当石墨烯负载量的增加时,催化剂对染料MB的光催化降解性能明显加强。其中,没有负载石墨烯的GFRT0催化剂即为Fe3O4@Ru-TiO2复合材料,光催化降解80min后,MB降解率仅达到44.4%;而经过负载石墨烯后的GFRT1~GFRT3催化剂光降解80min,对MB的降解率有了较大幅度的提高,分别达到48.6%、64.9%和84.5%;进一步增加rGO的负载量,光催化降解20min后,制备的GFRT4以及GFRT5对MB的降解率已经分别能达到78.6%以及86.7%;当降解80min后MB降解率分别已经达到97.4%和97.6%,可以看出rGO的负载量由15%增加到20%时,MB的降解率略微提高。当rGO的负载量为15%时已具有较佳的光催化降解MB性能。值得注意的是,染料溶液与催化剂的避光30min吸附-脱附平衡过程中,负载有rGO的催化剂对MB均有吸附作用,当rGO的负载量较少(0%、1%、5%)时,催化剂对MB的吸附作用并不十分明显,通过吸附最大使染料的浓度下降了15.5%;随着rGO的负载量提高到10%,催化剂对MB的吸附作用随之增强,达到29.3%;进一步增加rGO的负载量到15%和20%时,吸附作用明显增加,分别达到51.7%和71.8%。由此可见,rGO的负载量对催化剂的光催化活性的提高有很大的影响。主要原因可能是锐钛型TiO2掺杂Ru后降低了其带隙能,提高催化剂光吸收能力,其次,rGO的具有的大比表面积和表面具有大量的功能性活性基团或者通过π-π共轭键强烈吸附染料分子,并且催化剂负载rGO后的能起到有效抑制电子空穴的复合,拓宽光吸收范围,增强光降解催化活性。
图4为可见光降解MB的一级动力学拟合关系图,由图4中线性拟合的结果可以得出,复合材料样品GFRT0~GFRT5的k值分别为7.51×10-3、8.71×10-3、1.43×10-2、2.57×10-2、4.93×10-2和5.28×10-2min-1。由此可见,随着对磁性复合材料GFRT组成中的rGO负载量的提高,降解反应速率常数k也随之提高,相比而言,当rGO负载量为15%时,合成的磁性复合材料光催化剂已到达较佳光催化降解性能。
通过对比研究,实施例1中以15mg GO制备的rGO/Fe3O4@Ru-TiO2磁性光催化剂对亚甲基蓝具有较佳的降解活性和动力学常数,分别为97.4%和4.93×10-2min-1。
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,所应理解的是,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 (10)
1.一种rGO/Fe3O4@Ru-TiO2磁性光催化剂的制备方法,其特征在于,包括以下步骤:
步骤1)向钛酸四丁酯溶液中加入RuCl3·3H2O乙醇溶液,记为溶液A;
步骤2)将Fe3O4磁性纳米微球、十二烷基磺酸钠、丙酮和氨水混合,超声分散10min确保十二烷基磺酸钠能全部溶解在溶液中,记为溶液B;
步骤3)搅拌步骤2)制得的溶液B,室温下将步骤1)制得的溶液A滴加到溶液B中,待溶液A滴加完毕,继续搅拌,然后对混合液中的灰黑色固体进行磁分离和洗涤,真空干燥,得到产物C;
步骤4)将步骤3)制得的产物C进行煅烧处理,制得Ru掺杂TiO2的磁性Fe3O4@Ru-TiO2复合材料;
步骤5)将步骤4)制得的磁性Fe3O4@Ru-TiO2复合材料在稀硝酸溶液中超声5min后,再用去离子水将复合材料洗涤至中性,最后用乙醇洗涤,分离的固体备用;
步骤6)将经步骤5)处理的复合材料与少层片状氧化石墨烯在乙醇/乙二醇的混合溶剂中通过溶剂热法进行负载复合,制得所述rGO/Fe3O4@Ru-TiO2磁性光催化剂。
2.根据权利要求1所述的一种rGO/Fe3O4@Ru-TiO2磁性光催化剂的制备方法,其特征在于,步骤1)所述钛酸四丁酯溶液为钛酸四丁酯的乙醇溶液,体积浓度为2%,添加量为40mL;所述RuCl3·3H2O乙醇溶液的质量浓度为1g/L,添加量为0.734mL。
3.根据权利要求1所述的一种rGO/Fe3O4@Ru-TiO2磁性光催化剂的制备方法,其特征在于,步骤2)所述Fe3O4磁性纳米微球的添加量为100mg;所述十二烷基磺酸钠的添加量为0.2g;所述氨水的添加量为2mL;所述丙酮的添加量为150mL。
4.根据权利要求1所述的一种rGO/Fe3O4@Ru-TiO2磁性光催化剂的制备方法,其特征在于,步骤3)所述继续搅拌的时间为3h;所述真空干燥的温度为60℃,时间为24h。
5.根据权利要求1所述的一种rGO/Fe3O4@Ru-TiO2磁性光催化剂的制备方法,其特征在于,步骤4)所述煅烧处理为:在氮气保护下500℃煅烧3h。
6.根据权利要求1所述的一种rGO/Fe3O4@Ru-TiO2磁性光催化剂的制备方法,其特征在于,步骤5)所述磁性Fe3O4@Ru-TiO2复合材料的添加量为100mg;所述稀硝酸的浓度为0.1M,添加量为30mL。
7.根据权利要求1所述的一种rGO/Fe3O4@Ru-TiO2磁性光催化剂的制备方法,其特征在于,步骤6)所述少层片状氧化石墨烯的添加量为0~20mg;所述乙醇/乙二醇的混合溶剂中乙醇和乙二醇的体积比为1:1,所述混合溶剂的添加量为60mL。
8.根据权利要求1所述的一种rGO/Fe3O4@Ru-TiO2磁性光催化剂的制备方法,其特征在于,步骤6)所述溶剂热法的反应条件如下:反应温度为180℃,反应时间为10h,所得产物于60℃真空干燥24h。
9.一种rGO/Fe3O4@Ru-TiO2磁性光催化剂,其特征在于,由权利要求1-8任一项所述的制备方法制得。
10.权利要求9所述的一种rGO/Fe3O4@Ru-TiO2磁性光催化剂在降解亚甲基蓝中的应用。
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