CN111298844A - 一种BiOBr/Fe3O4@UiO-66三元复合光催化材料 - Google Patents
一种BiOBr/Fe3O4@UiO-66三元复合光催化材料 Download PDFInfo
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 27
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 25
- 239000011206 ternary composite Substances 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 14
- 229910001868 water Inorganic materials 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000013207 UiO-66 Substances 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 14
- 229910052797 bismuth Inorganic materials 0.000 description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- 229910017135 Fe—O Inorganic materials 0.000 description 5
- 238000004566 IR spectroscopy Methods 0.000 description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
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- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
本发明提出了一种BiOBr/Fe3O4@UiO‑66三元复合光催化材料，其制备方法如下：1)制备Fe3O4；2)制备Fe3O4@UiO‑66复合材料；3)制备BiOBr/Fe3O4@UIO‑66复合材料；本发明在制备过程中充分利用了Fe3O4的磁性，使Fe3O4@UIO‑66复合材料和BiOBr/Fe3O4@UiO‑66复合材料可以直接通过磁铁加以分离，简化了分离工艺，有效提升了光催化材料的重复使用率。
Description
技术领域
本发明涉及一种BiOBr/Fe3O4@UiO-66三元复合光催化材料，属于催化剂技术领域。
背景技术
近年来，全世界正面临着能源短缺和环境污染的难题，光催化技术是将太阳能直接转化为化学能的最有效的途径之一，光催化技术具有能耗低、操作简便、反应条件温和，在常温常压下就可以进行，在处理环境问题上已成为研究热点。
除了TiO2外，目前研究较多的催化剂有这几大类：(1)无机金属氧化物和硫化物，如CdS、Cu2O、ZnS等；(2)复合氧化物光催化剂，如铋系、钼系、银系等二元或多元复合氧化物，是一大类新型窄带隙光催化材料。
中国铋资源量居世界首位，铋的化学性质与铅相似，所以可以用来代替对环境污染较大的铅。铋系氧化物的中心原子是铋，它的杂化方式是铋的6s轨道和氧的2p轨道进行杂化。这种杂化方式使得氧化物的带隙变窄，增加了对可将光的响应能力；同时拓宽了价带的宽度，增强了空穴的移动速率。近年来，一些研究发现铋的一系列多元复合氧化物均具有良好的光催化活性。
BiOX(X＝I、Br、Cl)是一种三元结构的半导体材料，晶体结构为四方晶系。它的化学稳定性好，禁带宽度大小合适，在可见光范围内的光催化效果也好。卤氧化铋的催化活性与卤素原子的序数有关，原子序数越大，其活性增强效果越好。
但是，目前合成的大多数半导体纳米复合材料虽然具有光催化活性，但是存在分离困难，难以循环利用的缺点，因此，将Fe3O4于光催化半导体相复合，将赋予光催化材料磁性，通过磁性即可分离，大大提高了材料的重复使用率，也将拓展其在生产中的实际应用。
发明内容
本发明针对上述问题，从而提出了一种BiOBr/Fe3O4@UiO-66三元复合光催化材料。
具体的技术方案如下：
一种BiOBr/Fe3O4@UiO-66三元复合光催化材料，其制备方法如下：
1)制备Fe3O4
将2.72g FeCl3·6H2O、0.99g FeCl2·6H2O，溶于80ml水中、剧烈搅拌，然后将溶液加热到70-90℃，同时滴加NH3·H2O至pH＝10，反应在70-90℃下继续反应20-40min，剧烈搅拌；将溶液冷却至室温，然后洗涤，去除未反应的物质，干燥得到黑色粉末即为Fe3O4；
2)制备Fe3O4@UiO-66复合材料
将0.156g ZrCl4、0.132g对苯二甲酸、0.185g Fe3O4溶于50ml DMF中，再加入4mL乙酸，超声搅拌得到均相悬浊液A；将均相悬浊液A转移至水热釜中，在120-140℃下反应11-13h；磁铁收集棕色复合材料，洗涤、干燥后得到的棕色粉末即为Fe3O4@UiO-66复合材料；
3)制备BiOBr/Fe3O4@UiO-66复合材料
将0.1455g Bi(NO3)3·5H2O、0.0357g KBr、0.0915g Fe3O4@UiO-66复合材料、0.0343g十二烷基苯磺酸钠溶于4mL乙二醇中，再加入4ml水，超声搅拌，得到均相悬浊液B；将均相悬浊液B转移至水热釜中，在170-190℃下反应4-6h，自然冷却至室温，磁铁收集黑色复合材料，并洗涤、干燥后得到的黑色粉末即为BiOBr/Fe3O4@UiO-66复合材料。
进一步的，在步骤1)中，Fe2+与Fe3+的摩尔比为2:1。
进一步的，在步骤2)和步骤3)中，将均相悬浊液A和均相悬浊液B分别转移至水热釜的聚四氟乙烯内衬中。
进一步的，在步骤2)和步骤3)中分别使用乙醇和去离子水进行洗涤。
进一步的，在步骤1)、步骤2)和步骤3)中、需洗涤2-4次。
本发明的有益效果为：
1)本发明在制备过程中充分利用了的Fe3O4磁性，使Fe3O4@UiO-66复合材料和BiOBr/Fe3O4@UiO-66复合材料可以直接通过磁铁加以分离，简化了工艺流程。
2)UiO-66作为一个高稳定的金属有机框架，比表面大，孔径规则，作为半导体材料的载体，能够有效的分散活性中心，同时较大的比表面积使其具有一定的吸附能力，因此以UiO-66为载体的光催化材料将具有吸附和光催化的协同效应，增强其催化活性。
附图说明
图1为不同物质的红外吸收光谱图；
图2为不同物质的XRD图；
图3为不同物质对罗丹明B的光催化降解曲线。
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
一种BiOBr/Fe3O4@UiO-66三元复合光催化材料，其制备方法如下：
1)制备Fe3O4
将2.72g FeCl3·6H2O、0.99g FeCl2·6H2O，溶于80mL水中、在1000rpm的速度下搅拌，然后将溶液以5℃/min的速度加热到80℃，同时滴加NH3·H2O至pH＝10，反应80℃，在1000rpm的速度下搅拌继续反应30min。将溶液冷却至室温，然后去离子水洗涤2-3次，去除未反应的物质，将湿颗粒在70℃下干燥过夜；得到的黑色粉末即为Fe3O4；
2)制备Fe3O4@UiO-66复合材料
将0.156g ZrCl4、0.132g对苯二甲酸、0.185g Fe3O4溶于50Ml DMF中，再加入4mL乙酸，超声搅拌30min得到均相悬浊液A；将均相悬浊液A转移至水热釜的聚四氟乙烯内衬中，在130℃下反应12h；磁铁收集棕色复合材料，并用乙醇、去离子水洗涤3次，在60℃下干燥12h后，得到的棕色粉末即为Fe3O4@UiO-66复合材料；
3)制备BiOBr/Fe3O4@UiO-66复合材料
将0.1455g Bi(NO3)3·5H2O、0.0357g KBr、0.0915g Fe3O4@UiO-66复合材料、0.0343g十二烷基苯磺酸钠溶于4mL乙二醇中，再加入4ml水，超声搅拌，得到均相悬浊液B；将均相悬浊液B转移至水热釜的聚四氟乙烯内衬中，在180℃下反应5h，自然冷却至室温，磁铁收集黑色复合材料，并用乙醇、去离子水洗涤3次，在60℃下干燥12h后，得到的黑色粉末即为BiOBr/Fe3O4@UiO-66复合材料。
在本实施例中，步骤3)使用的BiOBr在三元复合材料的质量分数为50％。
实施例二
基于实施例一的制备方法，在本实施例中，步骤3)使用的BiOBr在三元复合材料的质量分数为25％。
实施例三
基于实施例一的制备方法，在本实施例中，步骤3)使用的BiOBr在三元复合材料的质量分数为75％。
实施例四
利用红外光谱对UiO-66进行分析和鉴定，结果如图1所示；由图1可知，3434cm-1处有一个较宽的峰，UiO-66中羟基的吸收峰正好与之对应，说明合成UiO-66孔洞中含有大量的水。1651cm-1可以归于羧基中C＝O的振动吸收；1407cm-1处的峰与UiO-66中对苯二甲酸的羧基的吸收峰相对应；
UIO-66的制备方法为：称取0.233g ZrCl4、0.16613g对苯二甲酸、3.6mL乙酸溶于50mL DMF中，搅拌30min得到均相悬浊液；将悬浊液倒入水热釜的聚四氟乙烯内衬中，120℃下反应24h，自然冷却至室温，离心，去离子水洗涤，然后80℃下干燥12h；最后得到白色粉末即为UiO-66。
实施例五
利用红外光谱对BiOBr进行分析和鉴定，结果如图1所示；
由图1可知，3416cm-1处有一个宽峰，水的羟基的吸收峰正好与之对应，说明合成样品还残留水分；504cm-1处的峰与BiOBr中Bi-O键伸缩振动产生的吸收峰相对应。
BiOBr的制备方法为：称取1.455g Bi(NO3)3·5H2O、0.357g KBr溶于40ml乙二醇中，在室温下剧烈搅拌1h。将溶液倒入水热釜的聚四氟乙烯内衬中，160℃下反应12h，自然冷却至室温，离心，去离子水洗涤，然后80℃下干燥12h。最后得到白色粉末即为BiOBr。
实施例六
利用红外光谱对Fe3O4进行分析和鉴定，结果如图1所示；
由图1可知，3400cm-1处有一个宽峰，水的羟基正好与之对应，说明合成样品还残留水分；580cm-1处的峰与Fe3O4中Fe-O键伸缩振动产生的吸收峰相对应。
实施例七
利用红外光谱对质量分数为50％的Fe3O4@UiO-66复合材料进行分析和鉴定，结果如图1所示；
如图1可知，Fe3O4@UiO-66红外谱图上1651cm-1和1407cm-1处分别有两个特征吸收峰与UiO-66的特征吸收峰相对应，说明二元材料中存在UiO-66；Fe3O4中Fe-O键伸缩振动产生的吸收峰应该在580cm-1的位置上，但是图中显示的峰值对应位置为559cm-1，这是由于Fe3O4@UiO-66复合材料制备过程中有醋酸的参加使Fe-O键所处环境发生变化导致的。
实施例八
利用红外光谱对BiOBr/Fe3O4@UiO-66复合材料进行分析和鉴定，其中Fe3O4@UiO-66的质量分数为25％、50％和75％，结果如图1所示；
由图1可知，Fe3O4@UiO-66红外谱图上1651cm-1和1407cm-1处分别有两个特征吸收峰与UiO-66的特征吸收峰相对应，说明三元材料中存在UiO-66，581cm-1处的峰与Fe3O4中Fe-O键伸缩振动产生的吸收峰相对应，504cm-1处的峰与BiOBr中Bi-O键伸缩振动产生的吸收峰相对应。
实施例九
利用XRD对BiOBr、UiO-66、Fe3O4、Fe3O4@UiO-66和三元复合材料进行结构鉴定，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。
实施例十
用合成的样品对罗丹明B进行光催化降解有机污染物，根据所测得的吸光度值绘制对应的降解曲线。
合成的样品包括BiOBr、Fe3O4、Fe3O4@UiO-66(FU)复合材料、25％BiOBr/75％FU、50％BiOBr/50％FU、75％BiOBr/25％FU的复合材料。
图3为不同物质对罗丹明B的光催化降解曲线；
由图3可知，75％BiOBr/25％FU在相同条件下对罗丹明B的光催化降解效率最好，其次是50％BiOBr/50％FU，说明在材料复合后光催化性能显著提升。其中，BiOBr作为主要的催化材料，其质量分数越大，降解处理的效果越好。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围内。
Claims (5)
1.一种BiOBr/Fe3O4@UIO-66三元复合光催化材料，其特征为，其制备方法如下：
1)制备Fe3O4
将2.72g FeCl3·6H2O、0.99g FeCl2·6H2O，溶于80mL水中搅拌，然后将溶液加热到70-90℃，同时滴加NH3·H2O至pH＝10，反应在70-90℃下继续反应30min，剧烈搅拌。将溶液冷却至室温，洗涤并干燥，得到黑色粉末即为Fe3O4；
2)制备Fe3O4@UiO-66复合材料
将0.156g ZrCl4、0.132g对苯二甲酸、0.185g Fe3O4溶于50mL DMF中，再加入4mL乙酸，超声搅拌得到均相悬浊液A；将均相悬浊液A转移至水热釜中，在120-140℃下反应11-13h；磁铁收集棕色复合材料，洗涤、干燥后得到的棕色粉末即为理论质量比为1:1的Fe3O4@UiO-66复合材料；
3)制备BiOBr/Fe3O4@UIO-66复合材料
将0.1455g Bi(NO3)3·5H2O、0.0357g KBr、0.0915g Fe3O4@UiO-66复合材料、0.0343g十二烷基苯磺酸钠溶于4mL乙二醇中，再加入4mL乙酸，超声搅拌，得到均相悬浊液B；将均相悬浊液B转移至水热釜中，在170-190℃下反应4-6h，自然冷却至室温，磁铁收集黑色复合材料，并洗涤、干燥后得到的黑色粉末即为BiOBr/Fe3O4@UiO-66复合材料。
2.如权利要求1所述的一种BiOBr/Fe3O4@UiO-66三元复合光催化材料，其特征为，在步骤1)中，Fe2+与Fe3+的摩尔比为2:1。
3.如权利要求1或2所述的一种BiOBr/Fe3O4@UiO-66三元复合光催化材料，其特征为，在步骤2)和步骤3)中，将均相悬浊液A和均相悬浊液B分别转移至水热釜的聚四氟乙烯内衬中。
4.如权利要求3所述的一种BiOBr/Fe3O4@UiO-66三元复合光催化材料，其特征为，在步骤2)和步骤3)中分别使用乙醇和去离子水进行洗涤。
5.如权利要求4所述的一种BiOBr/Fe3O4@UiO-66三元复合光催化材料，其特征为，在步骤1)、步骤2)和步骤3)中、需洗涤2-4次。
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