CN108160121B - 一种复合可见光光催化剂Ag2CO3/TiO2/UIO-66-(COOH)2及有机物降解应用 - Google Patents
一种复合可见光光催化剂Ag2CO3/TiO2/UIO-66-(COOH)2及有机物降解应用 Download PDFInfo
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- CN108160121B CN108160121B CN201810121773.3A CN201810121773A CN108160121B CN 108160121 B CN108160121 B CN 108160121B CN 201810121773 A CN201810121773 A CN 201810121773A CN 108160121 B CN108160121 B CN 108160121B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 46
- WIKQEUJFZPCFNJ-UHFFFAOYSA-N carbonic acid;silver Chemical compound [Ag].[Ag].OC(O)=O WIKQEUJFZPCFNJ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 title claims description 35
- KQTXIZHBFFWWFW-UHFFFAOYSA-L silver(I) carbonate Inorganic materials [Ag]OC(=O)O[Ag] KQTXIZHBFFWWFW-UHFFFAOYSA-L 0.000 title claims description 29
- 238000006731 degradation reaction Methods 0.000 title abstract description 6
- 230000015556 catabolic process Effects 0.000 title abstract description 5
- 239000005416 organic matter Substances 0.000 title description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 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 claims abstract description 7
- 230000000593 degrading effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 38
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 34
- 238000010041 electrostatic spinning Methods 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 22
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- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 20
- 239000003446 ligand Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 16
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- 229910001961 silver nitrate Inorganic materials 0.000 claims description 10
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910007926 ZrCl Inorganic materials 0.000 claims description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
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- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 6
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
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- 229910052751 metal Inorganic materials 0.000 description 8
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 238000011068 loading method Methods 0.000 description 6
- 229910001958 silver carbonate Inorganic materials 0.000 description 6
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 5
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000013384 organic framework Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
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- 239000000741 silica gel Substances 0.000 description 2
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- 239000011734 sodium Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
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- 229910052797 bismuth Inorganic materials 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 239000013256 coordination polymer Substances 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical compound [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
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- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
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- 239000013598 vector Substances 0.000 description 1
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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Abstract
本发明涉及一种复合可见光光催化剂,具体的说是一种改性的Ag2CO3/TiO2/UIO‑66‑(COOH)2可见光光催化剂及其在有机物罗丹明、甲醛中的降解应用。本发明的负载型光催化剂,应用广泛,制作简单,成本较低,稳定性好,可以在短时间内有效降解罗丹明、甲醛有机物,提高了可见光催化剂的降解效率。
Description
技术领域
本发明涉及一种复合可见光光催化剂,具体的说是一种改性的Ag2CO3/TiO2/ UIO-66-(COOH)2可见光光催化剂及其应用。
背景技术
环境污染和能源危机已逐渐危及人类的生存。光催化技术被认为是解决能源和环境问题最有效、最具有前景的方法。TiO2具有高效、无毒、化学性质稳定等优点,是目前研究最广泛的光催化剂。通过掺杂改性,或与窄带半导体复合等方法能改善TiO2对可见光的响应,但其可见光活性仍然很低,距离实际应用还有很大距离。因此有必要开发具有高可见光活性的新型光催化剂。
Ag2CO3具有很强的可见光光催化活性,在环境污染治理和清洁能源转换等领域的应用前景十分广阔。然而,在光催化降解过程中,Ag2CO3易被光腐蚀, Ag2CO3的银离子易被光生电子还原为银,导致催化剂活性逐渐下降,严重制约了其实际应用。因此,提高Ag2CO3的光稳定性是一个重要的研究方向。
虽然纳米TiO2的光催化活性高,但是它在溶液中易团聚,而且难以分离和回收,容易造成二次污染,并且光催化剂易失活,重复利用率低,所以严重制约了其光催化技术的推广使用。为了解决这些问题,研究者通过使纳米TiO2颗粒负载在结构和性质都很稳定的载体上来实现或者进行金属元素掺杂,比如银,非金属离子掺杂,比如N,C;稀土元素Re掺杂,或者将二氧化钛与其他可见光响应物质进行复合,比如TdS,ZnO等,以提高二氧化钛的可见光响应性能,增加光催化剂能级。
负载之后的纳米TiO2光催化剂,在很大程度上增加了TiO2光催化剂的比表面积,并且对抑制晶粒的团聚和晶相的转变也有一定的积极作用。而且由于载体本身为活性吸附材料,在暗处多孔载体能首先吸附有机污染物,达成吸附解离平衡,然后在光照下,有机污染物可以与TiO2发生更高效的光催化作用,进而提高了的TiO2光催化活性。另外,纳米TiO2在载体上的高度分散,也可以提高其对光的利用率。
现在国内外应用较广泛的载体有硅胶、氧化铝、玻璃纤维、石墨烯、活性炭以及一些天然矿物如硅藻土、沸石等。因沸石丰富的孔结构和高稳定性,使其成为用于催化剂最广泛的载体之一。但是沸石也有很多不足,比如对微孔材料来说,它的吸附能力有限,特别是在溶液中,大分子溶剂进不到孔内。因此,我们需要一种孔径可调,而且可调范围较广的一种载体,然而MOF这种多孔材料就很满足现在研究的需要。目前,仅有SBA-15分子筛作为纳米TiO2光催化剂的载体的研究,引起了国内外学者的广泛关注和兴趣。
TiO2光催化剂的固载方法可以分为两大类,一是物理负载法,二是化学负载法。物理负载法不涉及化学反应,因而实验操作比化学负载法简单,但是化学负载法合成的TiO2负载型光催化剂的水热稳定性较高,化学性质更稳定。
当前,合成负载型TiO2/载体的化学方法主要有直接合成法和后合成法两种。先合成载体材料然后再通过浸渍法、沉积法或者移植法将TiO2分散到硅胶、氧化铝、玻璃纤维、石墨烯、活性炭或分子筛,合成TiO2/载体。此方法的优点是 TiO2/载体的水热稳定性高,缺点是TiO2的分散性较差,而且TiO2的量不太好控制。但是一般情况下还是使用后合成法的较多,而且可以通过修饰载体的方法,弥补TiO2的分散性较差的缺点。
近几年,过渡金属或重金属对负载型二氧化钛掺杂修饰的研究,越来越受到重视,而且掺杂后的负载型二氧化钛的光催化效果有了很大的提高,而且应用范围也很广泛。有学者为了将负载型二氧化钛光催化剂具有良好的稳定性,用Au 元素对TiO2/SBA-15进行掺杂,合成出来的Au/TiO2/SBA-15,也有采用金属 Cu和Bi进行掺杂改性合成M/TiO2/SBA-15光催化剂,但是仍然存在二氧化钛分散性能一般,催化剂不能长期稳定的问题。
发明内容
MOFs金属有机骨架是近年发展十分迅速的配位聚合物,具有三维的孔结构,一般以金属离子为连接点,有机配体支撑成空间3D延伸,是继沸石和碳纳米管之外的又一类重要的新型多孔材料,具有高空隙率、低密度、大比表面积、孔道规则、孔径可调等性能,UiO-66是具有高稳定性的刚性MOFs材料,MOFs 的稳定性主要由无机金属单元的稳定性,以及金属与配体间结合力的强弱来决定。大多数MOFs的一个关键不足之处在于热稳定性不高,一般来说,MOFs 的热稳定性在350-400℃。UiO-66是一种具有超高稳定性的MOF,化学式为Zr6O4(OH)4(CO2)12,它的骨架坍塌温度高于500℃,它的稳定性来源来高度对称的无机金属单元Zr6O4(OH)4,以及该Zr6八面体核与配体中羧基氧O的强相互作用。一个Zr6八面体核与12个对苯二甲酸配体配位,形成四面体、和八面体两种类型的孔笼,每个八面体笼的八个面上,均与一个四面体笼相连,此连接方式在三维空间不断延伸,从而形成具有孔径的MOFs。另外,化学稳定性试验表明,UiO-66具有良好的抗水性、抗酸性。
为了克服现有技术的不足,本发明首先通过将载体UiO-66-(Zr)进行羧酸改性,形成UiO-66-(COOH)2,使载体UiO-66的比表面积增大,增加二氧化钛的分散点,从而利于控制分散性能和TiO2负载量。
为了使UiO-66能更好的与二氧化钛结合,而且使附着在UiO-66上的二氧化钛,这种替换能保持UiO-66的结构基本不变,而且使其水热稳定性提高了,酸附着点增多使得钛能均匀分散。
本申请通过对二氧化钛的金属盐掺杂,将同样具有可见光活性的AgCO3与 TiO2复合,简单有效的将二者的协同光催化性能发挥,形成优势互补,而且,为了使活性组分形成良好的分散,增加光催化剂的稳定性和提高使用寿命,将具有超高稳定性的金属有机骨架UiO-66(Zr)首先进行酸性改性,提高载体的羧酸负载点,从而提高催化剂的活性组分分布点,使得催化剂在使用寿命与光催化活性同时优化,目前还没有类似报道制备合成光催化剂结构为Ag2CO3/TiO2/ UIO-66-(COOH)2。
本发明的复合可见光催化剂的制备方法如下:
(1)按重量计,将5-10份聚乙烯吡咯烷酮、80~100份无水乙醇、50~100份钛酸丁酯混合后,在40~90℃的温度条件下恒温反应2~8小时,得到静电纺丝溶液,采用静电纺丝工艺对静电纺丝溶液进行静电纺丝,得到TiO2纳米纤维;
(2)将得到的TiO2纳米纤维在80~100℃下干燥处理1-4小时,再以1℃/分钟的升温速率加热到500~1000℃,恒温4~8小时后,得到纳米TiO2。
(3)将制备得到的纳米TiO2超声分散于水中,调节溶液ph值,加入硝酸银AgNO3溶液,搅拌均匀,然后加入Na2CO3,生成沉淀,取固体洗涤,100-150 ℃干燥得到Ag2CO3/TiO2。
(4)晶化反应合成UIO-66-(COOH)2:在反应釜中将ZrCl4、冰乙酸溶解在溶剂DMF中,超声分散10min-2h,然后将配体1,2,4,5-苯四羧酸投入上述溶液中,搅拌,在100-150℃下晶化反应10-24小时,反应完成后降温冷却,离心过滤,洗涤,干燥。各组分摩尔比ZrCl4∶配体∶模板剂冰乙酸=1∶1-2∶20-30。
(5)采用浸渍法将Ag2CO3/TiO2负载于UIO-66-(COOH)2多孔材料,得到 Ag2CO3/TiO2/UIO-66-(COOH)2复合光催化剂。
复合可见光光催化剂中Ag2CO3∶TiO2∶UIO-66-(COOH)2的质量比为1-20∶ 30-50∶20-40。
优选的,步骤(3)中硝酸银的浓度为0.2-1mol/L,加入量为10-20mL/L;碳酸钠的浓度为0.5-2mol/L,优选0.5-1mol/L。
优选的,步骤(5)的浸渍是将步骤(3)中的Ag2CO3/TiO2分散与水中,加入UIO-66-(COOH)2载体材料进行浸渍反应1-30小时,静置2-5小时,洗涤,干燥,干燥温度优选70-100℃。
本发明首先通过静电纺丝法制备得到均匀的二氧化钛纳米纤维,然后干燥,研磨形成纳米二氧化钛微球颗粒,具有良好的晶型稳定性,具有较大的长径比和较小的直径,均匀的孔结构,然后在进一步与Ag2CO3进行复合光催化剂的制备,由于碳酸银具有高温分解的性质,因此,在二者复合过程中,需要控制反应温度和干燥条件,不能超过200℃,而且,本发明采用了简单的离子沉淀法,通过控制体系的ph和碳酸钠与硝酸银的加入浓度,可以有效形成碳酸银产物,而二者相互促进电子-空穴的分离,有利于快速产生光电子,在此基础上,将Ag2CO3/TiO2浸渍于羧酸改性的UiO-66,金属有机骨架多孔材料中由于嵌入Zr的孔笼结构,形成多个八面体、四面体的三维结构,可以形成Ag2CO3、TiO2嵌入或者负载于载体表明,在特定的三维结构中加速光电离子的传递和产生,提高光催化效率。
而且,传统的UiO-66改性经常是采用-NH2、-CH3等,本发明采用配体1,2,4,5- 苯四羧酸替换其他配体,具体配体是1,2,4,5-苯四羧酸(即H4BETA),即1,2,4,5- 苯四甲酸。采用简单的水热溶剂法制备出多孔材料,具有良好的稳定性,耐高温性和孔结构性能。
进一步的,本发明还进行了更加深入的研究,增加了B掺杂的步骤,具体步骤:(1)按重量计,将5-10份聚乙烯吡咯烷酮、80~100份无水乙醇、50~100 份钛酸丁酯混合后,进一步加入2-5mol/L硼酸,在40~90℃的温度条件下恒温反应2~8小时,得到含硼的二氧化钛静电纺丝溶液,采用静电纺丝工艺对静电纺丝溶液进行静电纺丝,得到含B-TiO2纳米纤维;
(2)将得到的含B-TiO2纳米纤维在80~100℃下干燥处理小时,再以1℃/分钟的升温速率加热到500~1000℃,恒温4~8小时后,得到纳米B均匀掺杂TiO2 (B-TiO2)。
(3)将制备得到的纳米B-TiO2超声分散于水中,调节溶液ph值,加入硝酸银 AgNO3溶液和,搅拌均匀,然后加入Na2CO3,生成沉淀,取固体洗涤,100-150 ℃干燥得到硼掺杂的Ag2CO3/TiO2。
(4)晶化反应合成UIO-66-(COOH)2:在反应釜中将ZrCl4、冰乙酸溶解在溶剂DMF中,超声分散10min-2h,然后将配体1,2,4,5-苯四羧酸投入上述溶液中,搅拌,在100-150℃下晶化反应10-24小时,反应完成后降温冷却,离心过滤,洗涤,干燥。
(5)采用浸渍法将B掺杂的Ag2CO3/TiO2负载于UIO-66-(COOH)2多孔材料,将含有硼的Ag2CO3/TiO2分散与水中,加入UIO-66-(COOH)2载体材料进行浸渍反应1-30小时,静置2-5小时,洗涤,100℃干燥得到硼掺杂的Ag2CO3/TiO2/ UIO-66-(COOH)2复合光催化剂。其中B掺杂量,以催化剂基础计算1-10wt%。
上述技术方案中利用了金属盐碳酸银、非金属B离子同时掺杂,可以形成协同作用,形成强空穴-电子,从而进一步提高光催化活性。
本发明将制备的复合光催化剂应用于有机物罗丹明和甲醛的降解过程中,在密闭的玻璃箱中盛入3μL有机物培养皿和涂覆有光催化剂,箱内有机物气体浓度为1.8mg/m3,30W日光灯连续照射,考察罗丹明、甲醛的降解率。
具体实施方式
下面结合具体实施方式对本发明作进一步详细的说明。
实施例1
(1)按重量计,将5份聚乙烯吡咯烷酮、100份无水乙醇、50份钛酸丁酯混合后,在50的温度条件下恒温反应3小时,得到静电纺丝溶液,采用静电纺丝工艺对静电纺丝溶液进行静电纺丝,得到TiO2纳米纤维;
(2)将得到的TiO2纳米纤维在100℃下干燥处理1小时,再以1℃/分钟的升温速率加热到500℃,恒温4小时后,得到纳米TiO2。对所得产品进行X射线粉末衍射(XRD)测试,形成锐钛矿型纳米二氧化钛。
(3)将制备得到的纳米TiO2超声分散于水中,调节溶液ph值(7-10),加入硝酸银1mol/L AgNO3溶液10mL/L,搅拌均匀,然后加入1mol/L Na2CO3,生成沉淀,取固体洗涤,100℃干燥得到Ag2CO3/TiO2。
(4)晶化反应合成UIO-66-(COOH)2:在反应釜中将ZrCl4、冰乙酸溶解在溶剂DMF中,超声分散10min-2h,然后将配体1,2,4,5-苯四羧酸投入上述溶液中,搅拌,在100-150℃下晶化反应10-24小时,反应完成后降温冷却,离心过滤,洗涤,干燥。其中各组分摩尔比ZrCl4∶配体∶模板剂冰乙酸=1∶1∶20。
(5)采用浸渍法将Ag2CO3/TiO2负载于UIO-66-(COOH)2多孔材料,将步骤(3) 中的Ag2CO3/TiO2分散与水中,加入UIO-66-(COOH)2载体材料进行浸渍反应 1-30小时,静置2-5小时,洗涤,100℃干燥,得到Ag2CO3/TiO2/UIO-66-(COOH)2复合光催化剂。Ag2CO3∶TiO2∶UIO-66-(COOH)2的质量比为15∶45∶40。
实施例2
(1)按重量计,将10份聚乙烯吡咯烷酮、100份无水乙醇、100份钛酸丁酯混合后,在60℃的温度条件下恒温反应6小时,得到静电纺丝溶液,采用静电纺丝工艺对静电纺丝溶液进行静电纺丝,得到TiO2纳米纤维;
(2)将得到的TiO2纳米纤维在100℃下干燥处理2小时,再以1℃/分钟的升温速率加热到900℃,恒温68小时后,得到纳米TiO2。
(3)将制备得到的纳米TiO2超声分散于水中,调节溶液ph值(9-10),加入 0.5mol/L硝酸银AgNO3溶液20nl,搅拌均匀,然后加入1mol/L的Na2CO3,生成沉淀,取固体洗涤,100-150℃干燥得到Ag2CO3/TiO2。
(4)晶化反应合成UIO-66-(COOH)2:在反应釜中将ZrCl4、冰乙酸溶解在溶剂DMF中,超声分散10min-2h,然后将配体1,2,4,5-苯四羧酸投入上述溶液中,搅拌,在100-150℃下晶化反应10-24小时,反应完成后降温冷却,离心过滤,洗涤,干燥。其中各组分摩尔比ZrCl4∶配体∶模板剂冰乙酸=1∶1∶30。
(5)采用浸渍法将Ag2CO3/TiO2负载于UIO-66-(COOH)2多孔材料,将 Ag2CO3/TiO2分散与水中,加入UIO-66-(COOH)2载体材料进行浸渍反应1-30小时,静置2-5小时,洗涤,100℃干燥得到Ag2CO3/TiO2/UIO-66-(COOH)2复合光催化剂。Ag2CO3∶TiO2∶UIO-66-(COOH)2的质量比为20∶40∶40。
实施例3
(1)按重量计,将10份聚乙烯吡咯烷酮、80份无水乙醇、80份钛酸丁酯混合后,在80℃的温度条件下恒温反应2小时,得到静电纺丝溶液,采用静电纺丝工艺对静电纺丝溶液进行静电纺丝,得到TiO2纳米纤维;
(2)将得到的TiO2纳米纤维在80℃下干燥处理3小时,再以1℃/分钟的升温速率加热到9000℃,恒温4小时后,得到纳米TiO2。
(3)将制备得到的纳米TiO2超声分散于水中,调节溶液ph值,加入硝酸银 1mol/LAgNO3溶液20mL/L,搅拌均匀,然后加入1mol/L Na2CO3,生成沉淀,取固体洗涤,100-150℃干燥得到Ag2CO3/TiO2。
(4)晶化反应合成UIO-66-(COOH)2:在反应釜中将ZrCl4、冰乙酸溶解在溶剂DMF中,超声分散10min-2h,然后将配体1,2,4,5-苯四羧酸投入上述溶液中,搅拌,在100-150℃下晶化反应15小时,反应完成后降温冷却,离心过滤,洗涤,干燥。其中各组分摩尔比ZrCl4∶配体∶模板剂冰乙酸=1∶1∶20。
(5)将步骤(3)中的Ag2CO3/TiO2分散与水中,加入UIO-66-(COOH)2载体材料进行浸渍反应10小时,静置2小时,洗涤,100℃干燥,得到Ag2CO3/TiO2/ UIO-66-(COOh)2复合光催化剂。复合可见光光催化剂中Ag2CO3∶TiO2∶ UIO-66-(COOH)2的质量比为20∶45∶35。
实施例4
(1)按重量计,将8份聚乙烯吡咯烷酮、100份无水乙醇、100份钛酸丁酯混合后,进一步加入5mol/L硼酸,在60℃的温度条件下恒温反应5小时,得到含硼的二氧化钛静电纺丝溶液,采用静电纺丝工艺对静电纺丝溶液进行静电纺丝,得到含 B-TiO2纳米纤维;
(2)将得到的含B-TiO2纳米纤维在80~100℃下干燥处理4小时,再以1℃/分钟的升温速率加热到600℃,恒温4~8小时后,得到纳米B均匀掺杂TiO2(B-TiO2)。
(3)将制备得到的纳米B-TiO2超声分散于水中,调节溶液ph值,加入1mol/L硝酸银AgNO3溶液和,搅拌均匀,然后加入1mol/L Na2CO3,生成沉淀,取固体洗涤,100-150℃干燥得到硼掺杂的Ag2CO3/TiO2。
(4)晶化反应合成UIO-66-(COOH)2:在反应釜中将ZrCl4、冰乙酸溶解在溶剂DMF中,超声分散10min-2h,然后将配体1,2,4,5-苯四羧酸投入上述溶液中,搅拌,在100-150℃下晶化反应10-24小时,反应完成后降温冷却,离心过滤,洗涤,干燥。其中各组分摩尔比ZrCl4∶配体∶模板剂冰乙酸=1∶2∶30。
(5)采用浸渍法将B掺杂的Ag2CO3/TiO2负载于UIO-66-(COOH)2多孔材料,将含有硼的Ag2CO3/TiO2分散与水中,加入UIO-66-(COOH)2载体材料进行浸渍反应1-30小时,静置2-5小时,洗涤,100℃干燥得到硼掺杂的Ag2CO3/TiO2/ UIO-66-(COOH)2复合光催化剂。其中B掺杂量,以催化剂基础计算10wt%,复合光催化剂中Ag2CO3∶TiO2∶UIO-66-(COOH)2的质量比为20∶40∶40。
对比例1
不采用载体,仅制备Ag2CO3/TiO2复合光催化剂,其他实验参数同实施例1。
对比例2
采用载体氧化铝,浸渍Ag2CO3/TiO2其他实验参数同实施例1,得到 Ag2CO3/TiO2/Al2O3负载型复合光催化剂。
对比例3
采用载体SBA-15分子筛,浸渍Ag2CO3/TiO2其他实验参数同实施例1,得到 Ag2CO3/TiO2/SBA-15负载型复合光催化剂。
对比例4
采用未经过羧酸改性的UiO-66(Zr)载体,负载渍Ag2CO3/TiO2其他实验参数同实施例1,得到Ag2CO3/TiO2/UiO-66负载型复合光催化剂。
应用例
将实施例与对比例所制备的复合可见光光催化剂用于降解有机物罗丹明、甲醛等有机物。在密闭的玻璃箱中盛入3μL有机物培养皿和涂覆有光催化剂,箱内有机物气体浓度为1.8mg/m3,30W日光灯连续照射,罗丹明、甲醛的降解率如下表 1。
有上述结果可以看出,本发明的负载型可见光复合催化剂在催化剂用量小,光照时间短的情况下(小于30min),仍然具有罗丹明、甲醛有机物吸附率在98%以上的优异效果,可以看出对于纳米二氧化碳进行碳酸银的复合与载体改性大大提高了光降解有机物的效率,具有重要的意义。而且催化剂制备过程简单,有望进行工业试验与推广。
以上所述,仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本领域的技术人员在本发明所揭露的技术范围内,可不经过创造性劳动想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应该以权利要求书所限定的保护范围为准。
Claims (3)
1.一种复合可见光光催化剂,其特征在于,所述光催化剂结构为Ag2CO3/TiO2/UIO-66-(COOH)2,具体制备方法如下:
(1)按重量计,将5份聚乙烯吡咯烷酮、100份无水乙醇、50份钛酸丁酯混合后,在50℃的温度条件下恒温反应3小时,得到静电纺丝溶液,采用静电纺丝工艺对静电纺丝溶液进行静电纺丝,得到TiO2纳米纤维;
(2)将得到的TiO2纳米纤维在100℃下干燥处理1小时,再以1℃/分钟的升温速率加热到500℃,恒温4小时后,得到纳米TiO2,对所得产品进行X射线粉末衍射(XRD)测试,形成锐钛矿型纳米二氧化钛;
(3)将制备得到的纳米TiO2超声分散于水中,调节溶液pH 值7-10,加入硝酸银1mol/LAgNO3溶液10mL,搅拌均匀,然后加入1mol/L Na2CO3,生成沉淀,取固体洗涤,100℃干燥得到Ag2CO3/TiO2;
(4)晶化反应合成UIO-66-(COOH)2:在反应釜中将ZrCl4、冰乙酸溶解在溶剂DMF中,超声分散10min-2h,然后将配体1,2,4,5-苯四羧酸投入上述溶液中,搅拌,在100-150℃下晶化反应10-24小时,反应完成后降温冷却,离心过滤,洗涤,干燥,其中各组分摩尔比ZrCl4∶配体∶模板剂冰乙酸=1∶1∶20;
(5)采用浸渍法将Ag2CO3/TiO2负载于UIO-66-(COOH)2多孔材料,将步骤(3)中的Ag2CO3/TiO2分散于水中,加入UIO-66-(COOH)2载体材料进行浸渍反应1-30小时,静置2-5小时,洗涤,100℃干燥,得到Ag2CO3/TiO2/UIO-66-(COOH)2复合光催化剂,Ag2CO3∶TiO2∶UIO-66-(COOH)2的质量比为15∶45∶40。
2.如权利要求1所述的复合可见光光催化剂在降解有机物罗丹明、甲醛中的应用。
3.如权利要求2所述的应用,其特征在于:在密闭的玻璃箱中盛入3μL有机物培养皿和涂覆有5g光催化剂,箱内有机物气体浓度为1.8mg/m3,30W日光灯连续照射。
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Effective date of registration: 20221111 Address after: No. 99, Gangcheng Road, Dongying Port Economic Development Zone, Dongying City, Shandong Province 257237 Patentee after: Donggang Zhike Industrial Park Co.,Ltd. Address before: 325025 719 Sha Cheng street, Sha town, Wenzhou economic and Technological Development Zone, Wenzhou, Zhejiang Patentee before: Xiang Jinglai |
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