CN111229323B - 一种BiO(OH)xI1-x/AgI@UiO-66异质结复合材料 - Google Patents
一种BiO(OH)xI1-x/AgI@UiO-66异质结复合材料 Download PDFInfo
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 18
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- 239000001509 sodium citrate Substances 0.000 claims abstract description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 7
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Abstract
本发明提出了一种BiO(OH)xI1‑x/AgI@UiO‑66异质结复合材料;其制备方法如下:1)制备UiO‑66材料;2)采用原位水热合成法制备BiOI@UiO‑66二元复合材料;3)使用BiOI@UiO‑66二元复合材料、硝酸银和柠檬酸钠水溶液制备BiO(OH)xI1‑x/AgI@UiO‑66异质结复合材料;本发明具有可见光吸收能力更强,电子‑空穴分离加快的特点。
Description
技术领域
本发明涉及一种BiO(OH)xI1-x/AgI@UiO-66异质结复合材料,属于催化剂技术领域。
背景技术
科学技术和工业的发展促进了社会进步,同时带来了能源短缺和环境污染等威胁世界的问题。基于太阳能化学转化和储存的新能源和新技术的研究和开发已成为许多发达国家的发展重点。光催化的机理是在光的照射下,半导体光催化材料受到激发产生光生电子-空穴对,与材料表面吸附或者所处环境中的物质发生氧化还原反应降解污染物,因此在环境污染治理方面具有应用前景,尤其在废水中持久性污染物的处理方面表现突出。
发明内容
本发明针对上述问题,从而提出了一种BiO(OH)xI1-x/AgI@UiO-66异质结复合材料。
具体的技术方案如下:
一种BiO(OH)xI1-x/AgI@UiO-66异质结复合材料,其制备方法如下:
1)制备UiO-66;
2)采用原位水热合成法制备BiOI@UiO-66二元复合材料;
3)使用BiOI@UiO-66二元复合材料、硝酸银和柠檬酸钠水溶液制备得到BiO(OH)xI1-x/AgI@UiO-66异质结复合材料。
进一步的,步骤1)的UiO-66的制备方法为:
①将1mmol,0.233g四氯化锆和1mmol,0.16613g对苯二甲酸溶于50mL的N,N-二甲基甲酰胺中,缓慢滴加3.6mL的乙酸,室温下搅拌30min得到悬浊液;
②将悬浊液转移至聚四氟乙烯内衬的不锈钢高压釜中,密封并放入鼓风干燥箱中120℃反应24h;
③高压反应釜自然冷却至室温;
④产品高速离心分离,去离子水洗涤2到3次,样品放入80℃的烘箱下真空干燥12h,制备得到UiO-66材料。
进一步的,步骤2)中的BiOI@UiO-66二元复合材料的制备方法为:
①将UiO-66加入到10mL的乙二醇溶液中,室温下搅拌30min,形成悬浮液A;
②0.4851g Bi(NO3)3·5H2O和0.20775g KI加入到25mL的乙二醇中,室温下搅拌30min,形成悬浊液B;
③将悬浊液B缓慢加入到悬浮液A中,搅拌2h,转移至50mL的聚四氟乙烯内衬的不锈钢高压釜中,密封并放入鼓风干燥箱中120℃反应12h;
④高压反应釜在室温下自然冷却,高速离心分离,用去离子水洗涤2到3次并进行离心处理,样品放入80℃的烘箱下真空干燥12h,制备得到BiOI@UiO-66二元复合材料。
进一步的,步骤2)①中的UiO-66的添加量为制备的BiOI@UiO-66二元复合材料总质量的25%、50%或75%。
进一步的,步骤3)中的BiO(OH)xI1-x/AgI@UiO-66异质结复合材料的制备方法为:
①BiOI@UiO-66二元复合材料和硝酸银,溶于100mL水中,避光超声30min;
②溶液加热至沸腾时加入1%的柠檬酸钠水溶液5mL,溶液继续回流1h;
③溶液冷却后,高速离心分离,用去离子水洗涤2到3次,样品放入80℃的烘箱下真空干燥12h,制备BiO(OH)xI1-x/AgI@UiO-66异质结复合材料。
进一步的,通过BiOI@UiO-66二元复合材料和硝酸银的添加比例的调整,控制BiO(OH)xI1-x/AgI@UiO-66异质结复合材料的成分差异。
本发明的有益效果为:
1)BiOX具有较高的光催化活性主要有以下两方面原因:一方面,当价带上的电子被激发到导带轨道上时,会产生光生电子-空穴对,BiOX(X=Cl,Br,I)具有独特层状结构,拥有足够的空间来极化相应的原子和轨道,这一诱导偶极矩能够促进电子-空穴对的分离,极大地提高了光催化活性;此外,BiOX(X=Cl,Br,I)是间接跃迁带隙半导体,被激发的电子需穿过一定的k层方能到达价带,尽可能地减少了激发电子和空穴的再复合。独特的开放式结构和间接跃迁模式的共同作用促进了光生电子-空穴对的有效分离,快速传递了光生载流子,使得BiOX具有优良的光催化性能;
2)BiOX与AgNO3反应,生成AgI并与BiOX通过Ag-I-Bi交联键相连,形成了较强的界面作用,同时提升了电子-空穴的转移速率,增强了光催化性能。
3)UiO-66性能稳定,孔洞规则,比表面高,是一个优异的多孔载体,通过UiO-66与BiOX复合,可以高度分散BiOX活性粒子,从而也间接的分散BiO(OH)xI1-x/AgI异质结。
附图说明
图1为BiOI、UiO-66及二元、异质结复合材料的红外光谱图;
图2为BiOI、UiO-66及二元复合材料的XRD图;
图3为材料1、5、6的XRD图;
图4为BiOI、UiO-66及二元复合材料、材料1、5、6对玫瑰红的光降解图。
具体实施方式
为使本发明的技术方案更加清晰明确,下面结合附图对本发明进行进一步描述,任何对本发明技术方案的技术特征进行等价替换和常规推理得出的方案均落入本发明保护范围。
实施例一
具体的技术方案如下:
一种BiO(OH)xI1-x/AgI@UiO-66异质结复合材料,其制备方法如下:
1)制备UiO-66;
2)采用原位水热合成法制备BiOI@UiO-66二元复合材料;
3)使用BiOI@UiO-66二元复合材料、硝酸银和柠檬酸钠水溶液制备得到BiO(OH)xI1-x/AgI@UiO-66异质结复合材料。
进一步的,步骤1)的UiO-66的制备方法为:
①将1mmol,0.233g的四氯化锆和1mmol 0.16613g对苯二甲酸溶于50mL的N,N-二甲基甲酰胺中,缓慢滴加3.6mL的乙酸,室温下搅拌30min得到悬浊液;
②将悬浊液转移至聚四氟乙烯内衬的不锈钢高压釜中,密封并放入鼓风干燥箱中120反应24h;
③高压反应釜自然冷却至室温;
④产品高速离心分离,并用去离子水洗涤2到3次,最后将洗涤后到样品放入80℃的烘箱下真空干燥12h,制备UiO-66材料。
进一步的,步骤2)中的BiOI@UiO-66二元复合材料的制备方法为:
①将UiO-66加入到10mL的乙二醇溶液中,室温下搅拌30min,形成悬浮液A;
②0.4851g Bi(NO3)3·5H2O和0.20775g KI加入到25mL乙二醇,室温下搅拌30min,形成悬浊液B;
③将悬浊液B缓慢加入到悬浮液A中搅拌2h,转移至50mL的聚四氟乙烯内衬的不锈钢高压釜中,密封并放入鼓风干燥箱中120℃反应12h;
④高压反应釜在室温下自然冷却,高速离心分离,并用去离子水洗涤2到3次,样品放入80℃的烘箱下真空干燥12h,制备得到BiOI@UiO-66二元复合材料。
进一步的,步骤3)中的BiO(OH)xI1-x/AgI@UiO-66异质结复合材料的制备方法为:
①BiOI@UiO-66二元复合材料和硝酸银,溶于100mL水中,避光超声30min;
②溶液加热至沸腾时,加入1%的柠檬酸钠水溶液5mL,溶液继续回流1h;
③溶液冷却到室温,高速离心分离,用去离子水洗涤2到3次,样品放入80℃烘箱下真空干燥12h,制备BiO(OH)xI1-x/AgI@UiO-66异质结复合材料。
实施例二
根据实施例一的制备方法,用于制备异质结复合材料的BiOI@UiO-66二元复合材料中UiO-66的质量分数为A,制备得到的BiO(OH)xI1-x/AgI@UiO-66时,Ag+的质量分数为B;根据调整UiO-66的添加量,以及BiOI@UiO-66二元复合材料和硝酸银的添加比例,共制备得到六种异质结复合材料,具体成分比例如下:
序号 | 材料成分 | A(%) |
1 | BiOI@25%UiO-66 | 25 |
2 | BiOI@50%UiO-66 | 50 |
3 | BiOI@75%UiO-66 | 75 |
实施例三
利用红外光谱对UiO-66进行分析和鉴定,结果如图1可知,3435cm-1处的较宽峰对应UiO-66的-OH吸收峰,说明材料中含有大量的水,这是由于UiO-66是多孔材料吸收了水的原因。1657cm-1可以归于羧基碳氧双键C=O的振动吸收;1407cm-1是由COO-的伸缩振动所引起的吸收峰,这是源于UiO-66中对苯二甲酸上的羧基。
实施例四
利用红外光谱对BiOI进行分析和鉴定,结果如图1可知,Bi-O键的A2u型振动峰位于500cm-1处,762cm-1处的吸收峰对应于Bi-O键的非对称拉伸振动。1615cm-1处较强的吸收峰对应BiOI表面水分子O-H键的弯曲振动。
实施例五
利用红外光谱对BiOI@UiO-66进行分析和鉴定,结果如图1可知,BiOI@UiO-66有UiO-66和BiOI的特征峰,二元复合纳米材料中UiO-66、BiOI的特征峰明显,但是有些特征峰的强度有所减弱,且UiO-66的羟基峰的强度有所减弱,且UiO-66的羟基峰稍有变化合并为1393cm-1,可能是复合纳米材料的制备过程中酸掺杂造成UiO-66的羟基所处的环境有变化导致的。
实施例六
利用红外光谱对材料1、材料5和材料6为例进行分析和鉴定,结果如图1可知,但是异质结复合材料保持二元的特征峰。其中UiO-66、BiOI的特征峰明显。
实施例七
利用XRD对BiOI、UiO-66、BiOI@UiO-66和复合材料(材料1、材料5和材料6)进行结构鉴定,结果如图2所示。单体BiOI、UiO-66的XRD理论与实际谱图较好吻合,且纯度较高。BiOI@UiO-66谱图中可以发现BiOI、UiO-66相应的2θ角,其中UiO-66由于含量较低,峰的强度较弱。AgNO3与BiOI@UiO-66反应后的异质结复合材料与BiOI@UiO-66谱图中的2θ角基本一致。而BiOI在29.16°和31.83°的两个2θ角对称偏移至28.38°和32.23°。这主要是BiOI与AgNO3反应,形成了BiO(OH)xI1-x/AgI复合物的缘故。
实施例八
基于实施例二中的三种二元复合材料、三种异质结复合材料(材料1、5、6),在可见光条件下进行光催化实验,通过降解罗丹明B溶液(10mg/L)来评估样品的光催化活性。
在100mL容量瓶中配制10mg/L罗丹明B溶液并且用电子分析天平准确称取20mg合成材料;
向光催化反应器中加入100mL罗丹明B溶液和20mg合成材料,进行搅拌分散,暗反应30min,确保光催化剂与有机污染物能达到吸附-解吸平衡;
30min暗反应后,搅拌条件下,使用250W氙灯进行光催化反应。设定反应时间为1小时,反应过程中,每隔5min,使用取样管从反应器上端吸取约5mL反应液,经高速离心去除沉淀,留取上层清液;
最后,利用紫外分光光度计(UV-vis)检测上层清液的吸光度(554nm,对应罗丹明B的最强吸收峰),并记录上层清液的吸光度,计算出该复合材料对罗丹明B溶液的处理效率。
作为对比,光降解反应材料为BiOI、三种二元复合材料、三种异质结复合材料(材料1、5、6),光降解效果见图4;材料5、6的光催化性能最佳,说明复合后的异质结光催化材料的可见光吸收能力更强,电子-空穴分离加快。
Claims (1)
1.一种BiO(OH)xI1-x/AgI@UiO-66异质结复合材料,其特征在于,其制备方法如下:
1)制备UiO-66;
2)采用原位水热合成法制备BiOI@UiO-66二元复合材料;
3)使用BiOI@UiO-66二元复合材料、硝酸银和柠檬酸钠水溶液制备得到BiO(OH)xI1-x/AgI@UiO-66异质结复合材料,
步骤1)的UiO-66的制备方法为:
①将1mmol的0.233g四氯化锆和1mmol,0.16613g对苯二甲酸溶于50mL的N,N-二甲基甲酰胺中,缓慢滴加3.6mL的乙酸,室温下搅拌30min得到均相悬浊液;
②将悬浊液转移至聚四氟乙烯内衬的不锈钢高压釜中,密封并放入鼓风干燥箱中120℃反应24h;
③高压反应釜自然冷却至室温;
④产品高速离心分离,并用去离子水洗涤2到3次,最后放入80℃真空干燥12h,制备得到UiO-66材料,
步骤2)中BiOI@UiO-66二元复合材料的制备方法为:
①将UiO-66加入到10mL的乙二醇溶液中,室温下搅拌30min,形成悬浮液A;
②0.4851gBi(NO3)3·5H2O和0.20775g碘化钾加入到25mL的乙二醇中,室温下搅拌30min,形成悬浊液B;
③将悬浊液B缓慢加入到悬浮液A中,搅拌2h后转移至50mL聚四氟乙烯内衬的不锈钢高压釜中,密封并放入鼓风干燥箱中120℃反应12h;
④高压反应釜自然冷却,高速离心分离,并用去离子水洗涤2到3次,放入80℃的烘箱下真空干燥12h,得到BiOI@UiO-66二元复合材料,
步骤3)中的BiO(OH)xI1-x/AgI@UiO-66异质结复合材料的制备方法为:
①BiOI@UiO-66二元复合材料和硝酸银溶于100mL水中,避光超声30min得到悬浊液;
②悬浊液加热,待沸腾时加入1%的柠檬酸钠水溶液5mL后回流1h;
③反应结束后,溶液自然冷却,高速离心分离并用去离子水洗涤2到3次,放入80℃的烘箱下真空干燥12h,得到BiO(OH)xI1-x/AgI@UiO-66异质结复合材料。
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