CN112774699B - 一种氯氧化铋碳基复合材料的原位合成方法及其应用 - Google Patents
一种氯氧化铋碳基复合材料的原位合成方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种氯氧化铋碳基复合材料的原位合成方法,包括如下步骤:(1)将铋源溶于醇溶液后加入碳材料超声分散,得分散液A;(2)将维生素B1盐酸盐溶于水中,随后在搅拌下滴加至分散液A中,反应后洗涤、干燥即得氯氧化铋碳基复合材料。本发明的制备过程避免使用酸、碱以及表面活性剂,通过简单的液相合成方法即能得到均一的花瓣状结构的氯氧化铋碳基复合材料,在可见光条件下,可高效催化染料和易挥发有机污染物(VOCs)降解,且复合材料多次循环使用后活性几乎不变。
Description
技术领域
本发明属于氯氧化铋制备技术领域,具体涉及一种氯氧化铋碳基复合材料的原位合成方法及其在可见光催化染料和易挥发有机物降解方面的应用。
背景技术
可见光催化技术可通过半导体光催化材料直接将太阳能转化为化学能或者电能,并能够对环境中有毒有害有机污染物实现完全矿化降解,该技术是一项低成本的绿色共性技术,在环境治理、太阳能转化和自洁净等方向极具应用前景。而可见光催化技术的关键是高效和稳定半导体催化剂的研制。BiOCl材料具有层状结构和较小的带隙宽度(<2.62eV),能带易调控,表现出良好的光催化活性和稳定性,是光催化领域研究的热点之一。研究者通常将BiOCl与其它材料复合,以提高其可见光催化性能。
目前合成BiOCl复合材料,一般是先通过水解法、水(溶剂)热法、醇热法、溶胶凝胶法、软模板法、低温化学气相法、高温固相法、反相微乳液法等制备BiOCl,再与其它材料复合,合成过程较复杂,且一般需要加入酸或者碱以及表面活性剂。
水解法是利用水或溶剂解离出氢离子和氢氧根离子与盐解离出的离子反应生成弱电解质分子,并通过改变反应条件如酸碱性等使BiOCl颗粒沉淀出来,通常使用盐酸调节溶液pH,采用Bi(NO3)3、BiCl3和Bi2O3等为铋源得到,虽然该方法制备的BiOCl操作简单,反应时间短,但需要使用酸,且分散性很差,很难形成均匀微纳米BiOCl材料。
溶剂热法是指在密闭容器中如高压反应釜,在改变反应温度和压力条件下,提高反应的溶解性和反应活性,促进化学反应进行,并可使得常温常压下很难发生反应的物质进行反应,该方法制备的BiOCl形貌可控,产物粒径较均匀,但此方法需要使用设备要求高,产品产量较低,由于局限于密闭容器的容量大小,不适宜大范围实际应用。
醇热法通常是在乙醇、乙二醇等醇溶剂中添加硝酸铋或者氯化铋,经过后续超声或水热技术、冷却、洗涤、研磨等工序,得到BiOCl样品,该方法虽无需表面活性剂,易于控制形貌、分散性好等优点,但操作过程复杂,设备成本较高。
溶胶-凝胶法操作过程一般是在有机溶液中将铋金属醇盐均匀搅拌使之溶解形成前驱体,并发生水解、缩合化合物反应,在溶液中形成一种分散稳定的透明溶胶体系,然后使其在失去流动性的溶剂下反应,溶胶经胶粒间缓慢聚合物,进一步形成三维网络结构的凝胶,再经干燥、烧结固化从而制备出纳米结构材料,该方法制备产品纯度较高,产物粒径分布均匀,但制备步骤多,合成过程复杂,成本较高。
发明内容
为了解决现有BiOCl复合材料合成过程中存在的问题,本发明的目的是在于提供一种条件温和、工艺简单、绿色环保的氯氧化铋碳基复合材料的原位合成方法,该工艺过程避免使用酸、碱以及表面活性剂,通过简单的液相合成方法即能得到均一的花瓣状结构的氯氧化铋碳基复合材料。
本发明的另一目的在于提供了上述氯氧化铋碳基复合材料的应用,在可见光条件下,可高效催化染料和易挥发有机污染物(VOCs)降解,且复合材料多次循环使用后活性几乎不变。
为了实现上述技术目的,本发明采用如下技术方案:
一种氯氧化铋碳基复合材料的原位合成方法,包括如下步骤:
(1)将铋源溶于醇溶液后加入碳材料超声分散,得分散液A;
(2)将维生素B1盐酸盐溶于水中,随后在搅拌下滴加至分散液A中,反应后洗涤、干燥即得氯氧化铋碳基复合材料。
优选的,步骤(1)中,所述铋源选自五水硝酸铋和氯化铋中的一种,铋源的浓度为10~40g/L。
优选的,步骤(1)中,所述醇溶液为醇和水的混合液,醇和水的体积比为0.5-4:1;所述醇选自甲醇、乙醇、异丙醇、乙二醇和丙三醇中的一种。
优选的,步骤(1)中,所述碳材料选自石墨烯、氧化石墨烯、碳纳米管和碳三氮四中的一种,铋源与碳材料的质量比为10-100:1。
优选的,步骤(2)中,所述维生素B1盐酸盐和铋源的摩尔比为0.5-5:1。
优选的,步骤(2)中,所述维生素B1盐酸盐的浓度为0.05-0.5mol/L。
优选的,步骤(2)中,反应温度为室温,反应时间为1~6h。
本发明还提供了上述制得的氯氧化铋碳基复合材料的应用,将其作为可见光下染料或VOCs降解的光催化剂,具体步骤为:室温下,将氯氧化铋碳基复合材料加入到染料浓度为15~150mg/L的水中或VOCs浓度为10~100mg/L的气体中,反应0.1~12h即可。
优选的,所述染料选自甲基橙、罗丹明B和亚甲基蓝中的一种或几种,所述氯氧化铋碳基复合材料与染料的质量比为1:0.01~0.5。
优选的,所述VOCs选自甲醛、甲苯、苯和二甲苯中的一种或几种,所述氯氧化铋碳基复合材料与VOCs的质量比为1:0.005~0.1。
与现有技术相比,本发明的技术效果为:
1、本发明中维生素B1盐酸盐既作为氯源,又作为表面活性剂,有利于形成均一结构且避免使用酸、碱以及表面活性剂,条件温和、工艺简单、绿色环保。
2、本发明采用原位制备的技术,在生成氯氧化铋前加入碳材料,有利于抑制碳基材料的团聚,形成均一的花瓣状结构的复合材料。
3、本发明中采用碳基材料与氯氧化铋复合,不仅有利于提高材料的吸光率,还可调控材料的结构和催化性能,有利于精准构筑高效的可见光光催化剂。
4、本发明制备的氯氧化铋碳基复合材料具有纳米尺寸和多孔结构,可在可见光下高效降解水中的染料或空气中的VOCs,且可多次循环利用。
附图说明
图1为实施例1制得的材料的XRD谱图;
图2为实施例1制得的材料的SEM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,下面结合附图和具体实施例对本发明作进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。
实施例1
室温下,称取1.2g五水硝酸铋溶于60mL乙二醇溶液,随后加入30mg的氧化石墨烯超声分散,得分散液A;将1.6g维生素B1盐酸盐溶于20mL水中,随后在搅拌下缓慢滴加至分散液A中,置于室温下搅拌2h后洗涤干燥即得所述BiOCl@GO复合材料。如图1和图2所示,氧化石墨烯的加入,并没有改变BiOCl的结构,且BiOCl@GO复合材料为均一的花瓣状形貌。
实施例2
室温下,称取1.2g五水硝酸铋溶于30mL甲醇溶液,随后加入12mg的碳纳米管超声分散,得分散液A;将3.7g维生素B1盐酸盐溶于50mL水中,随后在搅拌下缓慢滴加至分散液A中,置于室温下搅拌1h后洗涤干燥即得所述BiOCl@CNTs复合材料。
实施例3
室温下,称取1.2g五水硝酸铋溶于120mL丙三醇溶液,随后加入120mg的C3N4超声分散,得分散液A;将0.74g维生素B1盐酸盐溶于50mL水中,随后在搅拌下缓慢滴加至分散液A中,置于室温下搅拌6h后洗涤干燥即得所述BiOCl@C3N4复合材料。
对比例1
室温下,称取1.2g五水硝酸铋溶于60mL乙二醇溶液,得分散液A;将1.6g维生素B1盐酸盐溶于20mL水中,随后在搅拌下缓慢滴加至分散液A中,置于室温下反应2h后洗涤干燥即得所述BiOCl。
对比例2
室温下,称取1.2g五水硝酸铋溶于60mL乙二醇溶液,得分散液A;将1.6g维生素B1盐酸盐溶于20mL水中,随后在搅拌下缓慢滴加至分散液A中,置于室温下反应2h后洗涤干燥即得所述氯氧化铋;称取30mg氧化石墨烯超声分散在60mL水中,加入上述制得的氯氧化铋搅拌2h,洗涤干燥得到BiOCl@GO复合材料。
对比例3
称取1.2g五水硝酸铋和0.1g赖氨酸溶于5mL盐酸中(浓度为36.5%),然后加入20mL去离子水,并迅速搅拌,同时有白色沉淀生成,用5wt.%的氨水溶液调节pH值为9,继续搅拌10min,将所得沉淀洗涤干燥制备得到BiOCl。
(1)染料降解:
室温下,分别将30mg实施例1-3和对比例1-3制备的材料加入到30mL浓度为45mg/L罗丹明B水溶液中避光超声分散15min,暗反应30min,打开300W氙灯光源,反应30min后过滤除去催化剂,检测残留浓度,计算降解率如表1所示:
表1 罗丹明B降解率数据表
表2 实施例1的BiOCl@GO光催化初始浓度为45mg/L罗丹明B降解循环使用性能
循环1次 | 循环2次 | 循环3次 | 循环4次 | 循环5次 | |
降解率(%) | 99.1 | 99.0 | 98.7 | 98.8 | 98.5 |
注:单次使用完成后,经过滤、洗涤、干燥重复使用。
(2)VOCs降解:
室温下,分别将100mg实施例1-3和对比例1-3制备的材料加入到250mL浓度为30mg/L的甲醛气体中,打开300W氙灯光源,反应6h后,用气体取样器取样检测残留浓度,计算降解率如表3所示:
表3 甲醛降解率数据表
表4 实施例1的BiOCl@GO光催化初始浓度为30mg/L甲醛气体降解循环使用性能
循环1次 | 循环2次 | 循环3次 | 循环4次 | 循环5次 | |
降解率(%) | 98.5 | 98.3 | 98.3 | 98.2 | 98.0 |
注:单次使用完成后,直接重复使用。
Claims (8)
1.一种氯氧化铋碳基复合材料的原位合成方法,其特征在于,包括如下步骤:
(1)将铋源溶于醇溶液后加入碳材料超声分散,得分散液A;所述醇溶液为醇和水的混合液,醇和水的体积比为0.5-4:1;所述醇选自甲醇、乙醇、异丙醇、乙二醇和丙三醇中的一种;
(2)将维生素B1盐酸盐溶于水中,随后在搅拌下滴加至分散液A中,室温反应1-6h后洗涤、干燥即得氯氧化铋碳基复合材料。
2.根据权利要求1所述的一种氯氧化铋碳基复合材料的原位合成方法,其特征在于:步骤(1)中,所述铋源选自五水硝酸铋和氯化铋中的一种,铋源的浓度为10-40 g/L。
3.根据权利要求1所述的一种氯氧化铋碳基复合材料的原位合成方法,其特征在于:步骤(1)中,所述碳材料选自石墨烯、氧化石墨烯、碳纳米管和碳三氮四中的一种,铋源与碳材料的质量比为10-100:1。
4.根据权利要求1所述的一种氯氧化铋碳基复合材料的原位合成方法,其特征在于:步骤(2)中,所述维生素B1盐酸盐和铋源的摩尔比为0.5-5:1。
5.根据权利要求1所述的一种氯氧化铋碳基复合材料的原位合成方法,其特征在于:步骤(2)中,所述维生素B1盐酸盐的浓度为0.05-0.5 mol/L。
6.权利要求1-5任一项所述的原位合成方法得到的氯氧化铋碳基复合材料的应用,其特征在于:将其作为可见光下染料或VOCs降解的光催化剂;
具体步骤为:室温下,将氯氧化铋碳基复合材料加入到染料浓度为15-150 mg/L的水中或VOCs浓度为10-100 mg/L的气体中,反应0.1-12 h即可。
7.根据权利要求6所述的氯氧化铋碳基复合材料的应用,其特征在于:所述染料选自甲基橙、罗丹明B和亚甲基蓝中的一种或几种,所述氯氧化铋碳基复合材料与染料的质量比为1:0.01-0.5。
8.根据权利要求6所述的氯氧化铋碳基复合材料的应用,其特征在于:所述VOCs选自甲醛、甲苯、苯和二甲苯中的一种或几种,所述氯氧化铋碳基复合材料与VOCs的质量比为1:0.005-0.1。
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