CN113101947B - 一种硫化银-还原氧化石墨烯-二氧化钛复合材料及其制备方法和应用 - Google Patents
一种硫化银-还原氧化石墨烯-二氧化钛复合材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种硫化银‑还原氧化石墨烯‑二氧化钛复合材料及其制备方法和应用。本发明的硫化银‑还原氧化石墨烯‑二氧化钛复合材料的组成包括二氧化钛薄膜以及修饰在二氧化钛薄膜表面的片状还原氧化石墨烯和硫化银颗粒,其制备方法包括以下步骤:1)通过阳极氧化法制备修饰有还原氧化石墨烯的二氧化钛氧化膜;2)将硫化银颗粒沉积到修饰有还原氧化石墨烯的二氧化钛氧化膜表面,即得硫化银‑还原氧化石墨烯‑二氧化钛复合材料。本发明的硫化银‑还原氧化石墨烯‑二氧化钛复合材料具有光催化活性高、化学稳定性高、生物相容性优良、成本低、安全无毒等优点,用于光催化降解罗丹明B的降解率高。
Description
技术领域
本发明涉及光催化技术领域,具体涉及一种硫化银-还原氧化石墨烯-二氧化钛复合材料及其制备方法和应用。
背景技术
随着轻纺工业的快速发展,纺织领域有大量的含染料废水产生,造成的环境污染问题也越来越严重,亟待解决。光电催化降解是一种高效、节能的含染料废水处理技术,具有很好的实际应用前景。
光催化剂是光电催化降解技术的关键,在众多的光催化剂中,二氧化钛作为一种较为活跃的光催化剂被广泛应用在空气净化、水分解、光电催化等领域。然而,由于二氧化钛存在禁带较宽、光生电子-空穴易复合、对有机物的吸附能力差等缺点,其催化降解的实际应用效果不佳。
目前,解决上述问题的方法主要包括以下几种:1)铂、钯、铑、银、钌等贵金属的沉积; 2)Cds、Ag2S、PbSe等窄能隙半导体的敏化;3)RGO、多壁碳纳米管等的修饰。然而,这几种方法均存在明显的缺点,例如:贵金属资源十分有限,且价格十分昂贵,注定了贵金属沉积的方法无法大规模推广应用;研究人员开发了一种MWCNT-Ag2S-TiO2纳米颗粒,其采用的是以碳纳米管为修饰材料的碳掺杂方法,但由于碳掺杂材料无法与二氧化钛表面接触紧密,最终会导致二氧化钛的活性位点减少,光催化活性较差;研究人员还开发了一种Ag2S-TiO2纳米颗粒复合光催化剂,但由于TiO2纳米颗粒无法提供足够的表面积去与Ag2S复合,光催化降解效果会下降,不利于TiO2光催化性能的提高。
发明内容
本发明的目的在于提供一种硫化银-还原氧化石墨烯-二氧化钛复合材料及其制备方法和应用。
本发明所采取的技术方案是:
一种硫化银-还原氧化石墨烯-二氧化钛复合材料,其组成包括二氧化钛薄膜以及修饰在二氧化钛薄膜表面的片状还原氧化石墨烯和硫化银颗粒。
上述硫化银-还原氧化石墨烯-二氧化钛复合材料的制备方法包括以下步骤:
1)将葡萄糖酸钠和还原氧化石墨烯加水配制成电解液,再设置两块钛片分别作为阳极和阴极,进行阳极氧化,得到修饰有还原氧化石墨烯的二氧化钛氧化膜;
2)将修饰有还原氧化石墨烯的二氧化钛氧化膜浸入可溶性银盐溶液中进行电沉积,再浸入硫脲溶液中进行电沉积,再浸入乙醇溶液中进行电沉积,再取出干燥,完成一次硫化银沉积,重复操作沉积多次,即得硫化银-还原氧化石墨烯-二氧化钛复合材料。
优选的,步骤1)所述钛片预先进行过碱洗(除油)、酸洗(除氧化膜)和水洗。
优选的,步骤1)所述阳极氧化在电压90V~110V下进行,阳极氧化时间为8min~12min。
优选的,步骤2)所述可溶性银盐、硫脲的摩尔比为1:0.8~1:1.2。
优选的,步骤2)所述可溶性银盐为硝酸银、乙酸银中的至少一种。
优选的,步骤2)所述电沉积在电位-0.2V~0.8V下进行,时间为50s~400s。
优选的,步骤2)所述硫化银沉积的次数为10次~16次。
本发明的有益效果是:本发明的硫化银-还原氧化石墨烯-二氧化钛复合材料具有光催化活性高、化学稳定性高、生物相容性优良、成本低、安全无毒等优点,用于光催化降解罗丹明B的降解率高。
具体来说:
本发明的硫化银-还原氧化石墨烯-二氧化钛复合材料的组成包括二氧化钛(TiO2)薄膜以及修饰在二氧化钛薄膜表面的片状还原氧化石墨烯(RGO)和硫化银(Ag2S)颗粒,还原氧化石墨烯的导电性好、表面积大,有助于提高TiO2薄膜的光催化性能,且Ag2S是窄禁带半导体,具有协同效应和单一性,能够增加复合材料对可见光的吸收,最终,制备的复合材料对罗丹明B的降解率超过90%。
附图说明
图1为TiO2薄膜、RGO-TiO2薄膜和Ag2S-RGO-TiO2薄膜的扫描电镜图。
图2为TiO2薄膜、RGO-TiO2薄膜和Ag2S-RGO-TiO2薄膜的X射线衍射图。
图3为TiO2薄膜、RGO-TiO2薄膜和Ag2S-RGO-TiO2薄膜的拉曼光谱图。
图4为TiO2薄膜、RGO-TiO2薄膜和Ag2S-RGO-TiO2薄膜的紫外-可见漫反射吸收光谱图。
图5为不同沉积电位制备的Ag2S-RGO-TiO2薄膜的光电流响应图。
图6为不同沉积圈数制备的Ag2S-RGO-TiO2薄膜的光电流响应图。
图7为不同沉积时间制备的Ag2S-RGO-TiO2薄膜的光电流响应图。
图8为Ag2S-RGO-TiO2薄膜光电催化降解罗丹明B的效果测试图。
具体实施方式
下面结合具体实施例对本发明作进一步的解释和说明。
实施例:
一种硫化银-还原氧化石墨烯-二氧化钛复合材料,其制备方法包括以下步骤:
1)将钛片的边缘用400#砂纸打磨光滑,再依次用600#、1000#和2000#砂纸打磨钛片表面至颜色呈灰白,再在抛光布上铺一层铝粉将钛片抛光,再用去离子水洗净,再将钛片放入去离子水中,超声清洗5min,用氮气吹干,再将0.2g的NaOH和0.46g的Na2CO3溶解在20mL的去离子水中配制成碱液,再加热至100℃后将钛片放入碱液中,超声清洗5min,再用去离子水清洗,再用氮气吹干,再取质量分数40%的HF溶液、质量分数30%的H2O2溶液和去离子水按照质量比1:6:3配制20mL的酸液,再将钛片浸入酸洗中清洗30s,再用去离子水清洗,用氮气吹干,再将钛片浸入乙醇中超声清洗5min,再用去离子水清洗,用氮气吹干,再配制葡萄糖酸钠浓度20g/L、还原氧化石墨烯浓度20g/L的混合溶液作为电解液,将洗净的钛片夹在直流电源的阳极,阴极采用面积大于阳极钛片两倍的钛片,在100V的电压下进行10min阳极氧化,得到修饰有还原氧化石墨烯的二氧化钛氧化膜(RGO-TiO2薄膜);
2)将修饰有还原氧化石墨烯的二氧化钛氧化膜浸入浓度0.025mol/L的AgNO3溶液中,设置沉积电位0.4V,沉积时间200s,再浸入浓度0.025mol/L的硫脲溶液中,设置沉积电位 0.4V,沉积时间200s,再浸入乙醇溶液(乙醇、去离子水的体积比为4:1)中,设置沉积电位 0.4V,沉积时间200s,再取出干燥,完成一次硫化银沉积,重复操作沉积12次,即得硫化银 -还原氧化石墨烯-二氧化钛复合材料(Ag2S-RGO-TiO2薄膜)。
性能测试:
1)TiO2薄膜(参照实施例制备,但未在电解液中添加RGO)、RGO-TiO2薄膜和 Ag2S-RGO-TiO2薄膜的扫描电镜(SEM)图如图1所示,X射线衍射(XRD)图如图2所示,拉曼光谱(Raman)图如图3所示,紫外-可见漫反射吸收光谱(UV-Vis)图如图4所示。
由图1可知:图中的A为TiO2薄膜,从A中可以看到有“花瓣状”颗粒的出现,即氧化钛晶粒;图中的B为RGO-TiO2薄膜,从B可以看出RGO的形貌为片状结构,反映了其层状微结构,可以清晰地观察到RGO较大的层间空间和较薄层的边缘;图中的C为 Ag2S-RGO-TiO2薄膜,从C可以看出薄膜形貌良好,几乎没有团聚倾向;结合图中的B和C 可知Ag2S颗粒在石墨烯上分布均匀;结合图中的A和C可知Ag2S颗粒和RGO成功地修饰到TiO2薄膜表面。
由图2可知:RGO-TiO2薄膜和TiO2薄膜的XRD图无明显区别,观察不到还原氧化石墨烯的特征峰,原因可能在于常规粉末的X射线衍射计检测不到石墨烯二维的薄膜结构或者石墨烯含量太少;修饰Ag2S后,Ag2S-RGO-TiO2薄膜的XRD图中出现了与卡片(JCPDS 14-0072) 相一致的特征峰34°、36.8°和38°,说明Ag2S的成功修饰。
由图3可知:RGO-TiO2薄膜和TiO2薄膜都有特征峰148cm-1、396cm-1、516cm-1和636cm-1,这些峰对应锐钛矿TiO2的Eg(1)、B1g(1)、B1g(2)或A1g、Eg(2)模式,另外,对比RGO-TiO2薄膜和 TiO2薄膜的Raman图可以看出在1350cm-1和1589cm-1处表现出拉曼位移,对应于D和G波段,表明RGO成功修饰到TiO2薄膜表面。
由图4可知:TiO2薄膜有三个主要的吸收峰,在400nm左右的峰为TiO2的特征峰,经过修饰后,在RGO-TiO2薄膜和Ag2S-RGO-TiO2薄膜中,三个主要吸收峰的位置都发生了明显的红移,修饰Ag2S和RGO后的TiO2薄膜在可见光区域吸光度增加,表明RGO-TiO2薄膜和Ag2S-RGO-TiO2薄膜的禁带宽度比TiO2薄膜窄,以上结果表明沉积Ag2S量子点和修饰 RGO可以显著提高TiO2薄膜的可见光吸收性能,原因在于:RGO的加入导致了碳掺杂,促进了复合材料对可见光的吸收,而Ag2S是窄禁带半导体,能够增加复合材料对可见光的吸收。
2)调整硫化银沉积过程中的沉积电位,得到的不同沉积电位制备的Ag2S-RGO-TiO2薄膜的光电流响应图如图5所示(图中的标号a~h分别对应TiO2薄膜、RGO-TiO2薄膜以及在-0.2V、0V、0.2V、0.4V、0.6V和0.8V沉积电位下制备的Ag2S-RGO-TiO2薄膜),调整硫化银沉积过程中的沉积圈数,得到的不同沉积圈数制备的Ag2S-RGO-TiO2薄膜的光电流响应图如图6所示(图中的标号a~g分别对应TiO2薄膜、RGO-TiO2薄膜以及在4圈、8圈、12圈、 14圈和16圈沉积圈数下制备的Ag2S-RGO-TiO2薄膜),调整硫化银沉积过程中的沉积时间,得到的不同沉积时间制备的Ag2S-RGO-TiO2薄膜的光电流响应图如图7所示(图中的标号a~ g分别对应TiO2薄膜、RGO-TiO2薄膜以及在50s、100s、200s、300s和400s沉积时间下制备的Ag2S-RGO-TiO2薄膜)。
由图5可知:随着RGO-TiO2薄膜上Ag2S沉积电位的逐渐增加,光电流也逐渐增大,在0.4V沉积电位时光电流达到最大,相比TiO2薄膜的光电流增加了83%,当Ag2S沉积电位继续增加时,光电流并没有再继续增大,相反,光电流下降了,是因为随着Ag2S沉积电位的增加会容易使得Ag2S颗粒团聚在一起导致颗粒变大,影响了电子转移效率。
由图6和图7可知:随着RGO-TiO2薄膜上Ag2S沉积圈数和沉积时间的逐渐增加,光电流也逐渐增大,在沉积圈数12圈和沉积时间200s时光电流达到最大,相比TiO2薄膜的光电流分别增加了85%和82%,当Ag2S沉积圈数和沉积时间继续增加时,光电流反而下降了,这可能是因为随着Ag2S沉积圈数和沉积时间的增加,Ag2S含量也会随着增加,Ag2S颗粒的含量影响了RGO-TiO2薄膜自身的光吸收能力,因此,最佳的Ag2S沉积条件为:沉积电位0.4V,沉积圈数12圈,沉积时间200s。
综合图5~7可知:TiO2薄膜、RGO-TiO2薄膜和Ag2S-RGO-TiO2薄膜的光电流大小为:Ag2S-RGO-TiO2薄膜>RGO-TiO2薄膜>TiO2薄膜;RGO-TiO2薄膜与TiO2薄膜相比,光电流增加了38%,可能的原因是RGO具有更好的导电性和更大的表面积,存在含氧官能团,这使得它们成为合成RGO-TiO2纳米复合材料的理想载体,而窄禁带半导体Ag2S的修饰更促进了 RGO-TiO2薄膜中的光生电子和空穴的分离。
3)光电催化降解罗丹明B:将500W氙灯作为光源,模拟太阳光,在氙灯前加一个能滤过波长小于420nm的滤波片模拟可见光,用20mL的石英玻璃杯作为反应器,光催化剂垂直放入石英杯中,光源也垂直照射在光催化剂的表面,光催化剂的光照有效面积为1cm2,降解时,每隔20min取一个点,用紫外-可见分光光度计在其特征峰处测定吸光度,得到的 Ag2S-RGO-TiO2薄膜光电催化降解罗丹明B的效果测试图如图8所示(图中的a代表不同沉积电位得到的Ag2S-RGO-TiO2薄膜的紫外-可见吸收光谱图,b代表不同沉积圈数得到的 Ag2S-RGO-TiO2薄膜的紫外-可见吸收光谱图,c代表不同沉积时间得到的Ag2S-RGO-TiO2薄膜的紫外-可见吸收光谱图,d代表TiO2薄膜、RGO-TiO2薄膜和Ag2S-RGO-TiO2薄膜光电催化降解罗丹明B的效果图)。
由图8可知:修饰上Ag2S的Ag2S-RGO-TiO2薄膜的光电催化降解效率都要远高于TiO2薄膜,其中,Ag2S沉积电位0.4V、沉积圈数12圈、沉积时间200s的条件下制备的 Ag2S-RGO-TiO2薄膜降解罗丹明B的性能最优;当Ag2S沉积12圈,沉积200s后,降解效果并没有提高,这可能是由于大量的Ag2S颗粒沉积团聚到RGO-TiO2薄膜的表面,影响了 RGO-TiO2薄膜自身的光吸收;罗丹明B的降解效率随光照时间的延长而增加,且最优Ag2S 沉积条件下所制备的Ag2S-RGO-TiO2薄膜的降解能力最高,可以在140min后达到92.3%的降解率,比TiO2薄膜的降解效率(13%)提高了7倍;TiO2薄膜、RGO-TiO2薄膜和Ag2S-RGO-TiO2薄膜的光电催化降解罗丹明B的效率大小为:Ag2S-RGO-TiO2薄膜>RGO-TiO2薄膜>TiO2薄膜,其中,RGO-TiO2薄膜的降解率大于TiO2薄膜的原因可能是复合材料的多级结构和修饰上的RGO增加了光催化材料对罗丹明B的吸附能力,其次是修饰上的RGO降低了光生电子和空穴的复合,在修饰Ag2S后的降解率明显增加的原因可能是RGO-TiO2薄膜与窄禁带半导体Ag2S纳米颗粒复合后增加了复合材料对太阳光的吸收和有效降低了电子和空穴的复合率。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (6)
1.一种硫化银-还原氧化石墨烯-二氧化钛复合材料的制备方法,其特征在于,包括以下步骤:
1)将葡萄糖酸钠和还原氧化石墨烯加水配制成电解液,再设置两块钛片分别作为阳极和阴极,进行阳极氧化,得到修饰有还原氧化石墨烯的二氧化钛氧化膜;
2)将修饰有还原氧化石墨烯的二氧化钛氧化膜浸入可溶性银盐溶液中进行电沉积,再浸入硫脲溶液中进行电沉积,再浸入乙醇溶液中进行电沉积,再取出干燥,完成一次硫化银沉积,重复操作沉积多次,即得硫化银-还原氧化石墨烯-二氧化钛复合材料;
所述硫化银-还原氧化石墨烯-二氧化钛复合材料的组成包括二氧化钛薄膜以及修饰在二氧化钛薄膜表面的片状还原氧化石墨烯和硫化银颗粒;
步骤2)所述可溶性银盐、硫脲的摩尔比为1:0.8~1:1.2。
2.根据权利要求1所述的硫化银-还原氧化石墨烯-二氧化钛复合材料的制备方法,其特征在于:步骤1)所述钛片预先进行过碱洗、酸洗和水洗。
3.根据权利要求1或2所述的硫化银-还原氧化石墨烯-二氧化钛复合材料的制备方法,其特征在于:步骤1)所述阳极氧化在电压90V~110V下进行,阳极氧化时间为8min~12min。
4.根据权利要求1所述的硫化银-还原氧化石墨烯-二氧化钛复合材料的制备方法,其特征在于:步骤2)所述可溶性银盐为硝酸银、乙酸银中的至少一种。
5.根据权利要求1所述的硫化银-还原氧化石墨烯-二氧化钛复合材料的制备方法,其特征在于:步骤2)所述电沉积在电位-0.2V~0.8V下进行,时间为50s~400s。
6.根据权利要求1所述的硫化银-还原氧化石墨烯-二氧化钛复合材料的制备方法,其特征在于:步骤2)所述硫化银沉积的次数为10次~16次。
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Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102218332A (zh) * | 2011-04-18 | 2011-10-19 | 哈尔滨工业大学 | 一种负载硫化铟锌银固溶体的掺硫二氧化钛纳米管薄膜、其制备方法及其应用 |
CN102309973A (zh) * | 2011-06-01 | 2012-01-11 | 湖南大学 | 一种复合光电催化剂及制备和应用 |
CN104525221A (zh) * | 2014-12-22 | 2015-04-22 | 清华大学 | 一种可见光响应的二氧化钛/硫化银复合薄膜制备的方法 |
CN105664974A (zh) * | 2016-02-29 | 2016-06-15 | 山东科技大学 | 一种硫化银/二氧化钛纳米带光催化剂及其制备方法 |
CN105983410A (zh) * | 2015-02-16 | 2016-10-05 | 北京纳米能源与系统研究所 | 异质复合型光催化剂及其制备方法 |
CN106245091A (zh) * | 2016-07-26 | 2016-12-21 | 斌源材料科技(上海)有限公司 | 二氧化钛复合材料及其制备方法和应用 |
WO2017192057A1 (en) * | 2016-05-05 | 2017-11-09 | Phu Dytrych Sp. Z O. O. | Modified porous coatings and a modular device for air treatment containing modified porous coatings. |
CN108855236A (zh) * | 2018-07-17 | 2018-11-23 | 成都市水泷头化工科技有限公司 | 一种用于污水处理的可回收耐高温光催化薄膜及制备方法 |
CN108993470A (zh) * | 2018-08-02 | 2018-12-14 | 福州大学 | 一种二氧化钛/石墨烯/氧化锌双阵列结构光催化材料的制备及应用 |
CN109589958A (zh) * | 2018-12-17 | 2019-04-09 | 上海绿晟环保科技有限公司 | 一种负载型石墨烯/TiO2光催化膜的制备方法 |
CN109794234A (zh) * | 2019-03-04 | 2019-05-24 | 合肥工业大学 | 一种石墨烯量子点修饰氧化锰/氧化钛纳米管阵列材料及其制备方法和应用 |
CN110512264A (zh) * | 2019-08-28 | 2019-11-29 | 青岛农业大学 | 一种光电极的制备方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103495427B (zh) * | 2013-10-17 | 2015-11-18 | 大连理工大学 | 利用低温等离子体制备负载型金属硫化物催化剂的方法 |
-
2021
- 2021-03-22 CN CN202110301947.6A patent/CN113101947B/zh not_active Expired - Fee Related
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102218332A (zh) * | 2011-04-18 | 2011-10-19 | 哈尔滨工业大学 | 一种负载硫化铟锌银固溶体的掺硫二氧化钛纳米管薄膜、其制备方法及其应用 |
CN102309973A (zh) * | 2011-06-01 | 2012-01-11 | 湖南大学 | 一种复合光电催化剂及制备和应用 |
CN104525221A (zh) * | 2014-12-22 | 2015-04-22 | 清华大学 | 一种可见光响应的二氧化钛/硫化银复合薄膜制备的方法 |
CN105983410A (zh) * | 2015-02-16 | 2016-10-05 | 北京纳米能源与系统研究所 | 异质复合型光催化剂及其制备方法 |
CN105664974A (zh) * | 2016-02-29 | 2016-06-15 | 山东科技大学 | 一种硫化银/二氧化钛纳米带光催化剂及其制备方法 |
WO2017192057A1 (en) * | 2016-05-05 | 2017-11-09 | Phu Dytrych Sp. Z O. O. | Modified porous coatings and a modular device for air treatment containing modified porous coatings. |
CN106245091A (zh) * | 2016-07-26 | 2016-12-21 | 斌源材料科技(上海)有限公司 | 二氧化钛复合材料及其制备方法和应用 |
CN108855236A (zh) * | 2018-07-17 | 2018-11-23 | 成都市水泷头化工科技有限公司 | 一种用于污水处理的可回收耐高温光催化薄膜及制备方法 |
CN108993470A (zh) * | 2018-08-02 | 2018-12-14 | 福州大学 | 一种二氧化钛/石墨烯/氧化锌双阵列结构光催化材料的制备及应用 |
CN109589958A (zh) * | 2018-12-17 | 2019-04-09 | 上海绿晟环保科技有限公司 | 一种负载型石墨烯/TiO2光催化膜的制备方法 |
CN109794234A (zh) * | 2019-03-04 | 2019-05-24 | 合肥工业大学 | 一种石墨烯量子点修饰氧化锰/氧化钛纳米管阵列材料及其制备方法和应用 |
CN110512264A (zh) * | 2019-08-28 | 2019-11-29 | 青岛农业大学 | 一种光电极的制备方法 |
Non-Patent Citations (4)
Title |
---|
Enhanced visible light photocatalytic activity of Ag2S-graphene/TiO2 nanocomposites made by sonochemical synthesis;Meng, ZD et al.;《Chinese Journal Of Catalysis》;20130831;1527-1533 * |
Pt/石墨烯/TiO2薄膜电极制备及其光电催化性能研究;钟建丹;《中国优秀硕士学位论文全文数据库》;20170415;B014-313 * |
Silver sulfide nanoparticles sensitized titanium dioxide nanotube arrays synthesized by in situ sulfurization for photocatalytic hydrogen production;Liu, X et al.;《Journal Of Colloid And Interface Science 》;20140101;17-23 * |
TiO2纳米管限域Co3O4催化剂的光解水制氢性能;李新军等;《华南理工大学学报(自然科学版)》;20161115;12-18 * |
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