CN102151577A - A kind of Ag3PO4/Mg-Al LDO visible light composite photocatalyst and its preparation and application - Google Patents
A kind of Ag3PO4/Mg-Al LDO visible light composite photocatalyst and its preparation and application Download PDFInfo
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- 229910003023 Mg-Al Inorganic materials 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910000161 silver phosphate Inorganic materials 0.000 title 1
- 238000003756 stirring Methods 0.000 claims abstract description 22
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 11
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 10
- 239000010452 phosphate Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 8
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002105 nanoparticle Substances 0.000 claims abstract description 6
- 239000002351 wastewater Substances 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 230000015556 catabolic process Effects 0.000 claims abstract description 4
- 238000006731 degradation reaction Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 3
- 231100000719 pollutant Toxicity 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000003513 alkali Substances 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- IJJPOUUNTYKRHG-UHFFFAOYSA-N dialuminum hexanitrate Chemical compound [Al+3].[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O IJJPOUUNTYKRHG-UHFFFAOYSA-N 0.000 claims 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000003463 adsorbent Substances 0.000 abstract description 3
- 150000001450 anions Chemical class 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 15
- WXLFIFHRGFOVCD-UHFFFAOYSA-L azophloxine Chemical compound [Na+].[Na+].OC1=C2C(NC(=O)C)=CC(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=C1N=NC1=CC=CC=C1 WXLFIFHRGFOVCD-UHFFFAOYSA-L 0.000 description 14
- 235000012739 red 2G Nutrition 0.000 description 14
- 230000001699 photocatalysis Effects 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
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- 238000002329 infrared spectrum Methods 0.000 description 4
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- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000000985 reflectance spectrum Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- DGLRDKLJZLEJCY-UHFFFAOYSA-L disodium hydrogenphosphate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].OP([O-])([O-])=O DGLRDKLJZLEJCY-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- CLMDNNLJBONLSV-UHFFFAOYSA-N magnesium;dinitrate;dihydrate Chemical compound O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O CLMDNNLJBONLSV-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 1
- 229940063656 aluminum chloride Drugs 0.000 description 1
- 229940009861 aluminum chloride hexahydrate Drugs 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
- 229910052599 brucite Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 229960002337 magnesium chloride Drugs 0.000 description 1
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
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- KPZYAGQLBFUTMA-UHFFFAOYSA-K tripotassium;phosphate;trihydrate Chemical compound O.O.O.[K+].[K+].[K+].[O-]P([O-])([O-])=O KPZYAGQLBFUTMA-UHFFFAOYSA-K 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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Abstract
本发明涉及一种Ag3PO4/Mg-Al LDO可见光复合光催化剂及其制备与应用，光催化剂包括：质量比为1∶10～5∶1的Ag3PO4纳米颗粒和镁铝双金属氧化物Mg-Al LDO；制备方法包括：将共沉淀法制备得到的镁铝层状双氢氧化物分散到可溶性磷酸盐的溶液中，加入硝酸银溶液，搅拌4～24h，再经洗涤和煅烧后，得到Ag3PO4/Mg-Al LDO可见光复合光催化剂；光催化剂应用于染料废水中阴离子污染物的降解和去除。本发明保留了吸附剂本身吸附性能强的特点，同时具备了较高的可见光催化活性，在染料废水的净化处理领域具有良好的应用前景；该制备工艺和生产设备简单，对环境友好，易于工业化生产。
The invention relates to an Ag 3 PO 4 /Mg-Al LDO visible light composite photocatalyst and its preparation and application. The photocatalyst includes: Ag 3 PO 4 nanoparticles and magnesium-aluminum bimetallic with a mass ratio of 1:10 to 5:1 Oxide Mg-Al LDO; the preparation method includes: dispersing the magnesium-aluminum layered double hydroxide prepared by the co-precipitation method into the soluble phosphate solution, adding silver nitrate solution, stirring for 4 to 24 hours, and then washing and calcining Finally, Ag 3 PO 4 /Mg-Al LDO visible light composite photocatalyst was obtained; the photocatalyst was applied to the degradation and removal of anion pollutants in dye wastewater. The present invention retains the strong adsorption performance of the adsorbent itself, and at the same time possesses high visible light catalytic activity, and has a good application prospect in the field of purification and treatment of dye wastewater; the preparation process and production equipment are simple, friendly to the environment, and easy to industrialize Production.
Description
技术领域technical field
本发明属于可见光复合光催化剂的领域，特别涉及一种Ag3PO4/Mg-Al LDO可见光复合光催化剂及其制备与应用。The invention belongs to the field of visible light composite photocatalyst, in particular to an Ag 3 PO 4 /Mg-Al LDO visible light composite photocatalyst and its preparation and application.
背景技术Background technique
1972年，Fujishima和Honda发现以TiO2作为光阳极在紫外光下具有催化分解H2O产生H2和O2的现象，标志着多相光催化研究开始了一个新时代。30多年来，光催化一直是研究领域比较热门的一门科学。但是由于TiO2本身带隙宽度的限制，使其只能吸收仅占太阳光小部分的紫外光，而对占太阳光大部分的可见光无响应。所以其后的二十年中，研究对象主要集中在对TiO2的改性方面，如过渡金属掺杂、非金属掺杂和金属非金属共掺杂等，以此来实现TiO2的可见光响应。通过对TiO2改性，尽管能提高其光谱响应范围，使其具有一定的可见光活性，但是量子效率较低，且改性本身存在诸多不足。因此，开发新型可见光催化剂成为近年来光催化研究的热点方向。In 1972, Fujishima and Honda discovered that using TiO 2 as a photoanode can catalyze the decomposition of H 2 O to generate H 2 and O 2 under ultraviolet light, marking the beginning of a new era in the research of heterogeneous photocatalysis. For more than 30 years, photocatalysis has been a popular science in the research field. However, due to the limitation of the bandgap width of TiO 2 itself, it can only absorb ultraviolet light which accounts for only a small part of sunlight, and has no response to visible light which accounts for most of sunlight. Therefore, in the following two decades, the research objects mainly focused on the modification of TiO 2 , such as transition metal doping, non-metal doping and metal-nonmetal co-doping, etc., so as to realize the visible light response of TiO 2 . Although the modification of TiO 2 can improve its spectral response range and make it have a certain visible light activity, the quantum efficiency is low, and the modification itself has many shortcomings. Therefore, the development of new visible light catalysts has become a hot topic in photocatalysis research in recent years.
与TiO2相比，Ag3PO4禁带宽度较窄，约为2.45eV，因而可以有效的吸收可见光。Ag3PO4作为一种新型可见光催化剂，与目前光催化活性较好的可见光催化剂，如BiVO4、WO3、TiO2-xNx等相比，具有更高的可见光催化效率。[Zhiguo Yi，Jinhua Ye，Naoki Kikugawa et al.，An orthophosphate semiconductor with photooxidation properties under visible-light irradiation，Nature Mater.，2010，9：559-564]但是，通过一般的化学方法制备得到的Ag3PO4晶粒尺寸大，分布宽，比表面积低，从而在很大程度上影响着其光催化活性的进一步提高。Compared with TiO 2 , Ag 3 PO 4 has a narrower band gap of about 2.45eV, so it can effectively absorb visible light. As a new type of visible light catalyst, Ag 3 PO 4 has higher visible light catalytic efficiency compared with current visible light catalysts with better photocatalytic activity, such as BiVO 4 , WO 3 , TiO 2-x N x , etc. [Zhiguo Yi, Jinhua Ye, Naoki Kikugawa et al., An orthophosphate semiconductor with photooxidation properties under visible-light irradiation, Nature Mater., 2010, 9: 559-564] However, Ag 3 PO prepared by general chemical methods 4 The grain size is large, the distribution is wide, and the specific surface area is low, which greatly affects the further improvement of its photocatalytic activity.
层状双氢氧化物(layered double hydroxides，简称LDH)，又称为阴离子粘土，是一种结构非常类似水镁石的层状双金属氢氧化物。基本结构式为：[M2+ 1-xM3+ x(OH)2]x+Am- x/m·nH2O，其中：M2+为Mg2+、Zn2+和Fe2+等二价金属阳离子；M3+为Al3+和Fe3+等三价金属阳离子；Am为CO3 2-、Cl-、NO3 -和SO4 2-等阴离子。LDH经焙烧后，结构羟基和层间离子逸出，从而转化为复合双金属氧化物(LDO)。LDH及其焙烧衍生物均具备较高的比表面积，常被用作催化剂载体。载体的引入，使其担载的催化材料具有更高的催化活性和选择性，一方面有助于催化剂热稳定性的提高，避免组分的聚集和烧结，从而得到晶粒较小，尺寸分布较窄的催化剂；另一方面LDH及其焙烧衍生物可以将有机染料吸附于复合催化剂的表面，更大程度地提高催化剂的活性。Layered double hydroxides (LDH for short), also known as anionic clay, is a layered double metal hydroxide with a structure very similar to brucite. The basic structural formula is: [M 2+ 1-x M 3+ x (OH) 2 ] x+ A m- x/m nH 2 O, where: M 2+ is Mg 2+ , Zn 2+ and Fe 2+ etc. Divalent metal cations; M 3+ is trivalent metal cations such as Al 3+ and Fe 3+ ; A m is anions such as CO 3 2- , Cl - , NO 3 - and SO 4 2- . After LDH is calcined, structural hydroxyl groups and interlayer ions escape, thus transforming into composite double metal oxide (LDO). LDH and its calcined derivatives have high specific surface area and are often used as catalyst supports. The introduction of the carrier makes the catalytic material carried by it have higher catalytic activity and selectivity. On the one hand, it helps to improve the thermal stability of the catalyst and avoid the aggregation and sintering of components, so as to obtain smaller grains and better size distribution. Narrower catalyst; on the other hand, LDH and its calcined derivatives can adsorb organic dyes on the surface of the composite catalyst, thereby improving the activity of the catalyst to a greater extent.
但迄今为止，关于将Ag3PO4纳米颗粒对Mg-Al LDO进行改性处理的文献和专利尚未见相关报道。But so far, there have been no relevant reports in the literature and patents on the modification of Mg-Al LDO by Ag 3 PO 4 nanoparticles.
发明内容Contents of the invention
本发明所要解决的技术问题是提供一种Ag3PO4/Mg-Al LDO可见光复合光催化剂及其制备与应用，该催化剂保留了吸附剂本身吸附性能强的特点，同时具备了较高的可见光催化活性，，在染料废水的净化处理领域具有良好的应用前景；该制备工艺和生产设备简单，对环境友好，易于工业化生产。The technical problem to be solved by the present invention is to provide a Ag 3 PO 4 /Mg-Al LDO visible light composite photocatalyst and its preparation and application. The catalytic activity has good application prospect in the field of purification and treatment of dye wastewater; the preparation process and production equipment are simple, environmentally friendly and easy for industrial production.
本发明的一种Ag3PO4/Mg-Al LDO可见光复合光催化剂，其组分包括：质量比为1∶10～5∶1的Ag3PO4纳米颗粒和镁铝双金属氧化物Mg-Al LDO。A Ag 3 PO 4 /Mg-Al LDO visible light composite photocatalyst of the present invention, its components include: Ag 3 PO 4 nanoparticles with a mass ratio of 1:10 to 5:1 and magnesium aluminum double metal oxide Mg- Al LDO.
该负载Ag3PO4的Mg-Al LDO中，所述Ag3PO4纳米颗粒尺寸为15～250nm，镁铝双金属氧化物厚度为4～15nm，复合光催化剂的比表面积40～220m2/g。In the Mg-Al LDO loaded with Ag 3 PO 4 , the size of the Ag 3 PO 4 nanoparticles is 15-250 nm, the thickness of the magnesium-aluminum double metal oxide is 4-15 nm, and the specific surface area of the composite photocatalyst is 40-220 m 2 / g.
本发明的一种Ag3PO4/Mg-Al LDO可见光复合光催化剂的制备方法，包括：A preparation method of Ag 3 PO 4 /Mg-Al LDO visible light composite photocatalyst of the present invention comprises:
(1)室温下，将摩尔比为2∶1～4∶1的可溶性的镁盐和铝盐溶于水中，得混合盐溶液；再将摩尔比为：1∶1～1∶6的可溶性的碳酸盐和无机碱溶于水中，得混合碱溶液；于0～50℃将混合盐溶液逐滴加入混合碱溶液中，升温至70～100℃反应2～24h，洗涤，干燥，得Mg-Al-CO3LDH；(1) At room temperature, dissolve soluble magnesium salt and aluminum salt with a molar ratio of 2:1 to 4:1 in water to obtain a mixed salt solution; Dissolve carbonates and inorganic alkalis in water to obtain a mixed alkali solution; add the mixed salt solution dropwise to the mixed alkali solution at 0-50°C, raise the temperature to 70-100°C for 2-24 hours, wash and dry to obtain Mg- Al-CO 3 LDH;
(2)室温下，将上述Mg-Al-CO3LDH加入可溶性磷酸盐溶液中，搅拌形成悬浮液，再加入硝酸银溶液于室温下搅拌4～24h，洗涤，干燥，得Ag3PO4/Mg-Al-CO3LDH的复合物，其中，Mg-Al-CO3LDH和可溶性磷酸盐的质量比为1∶5～10∶1，可溶性磷酸盐和硝酸银的摩尔比为1∶3～3∶1；(2) At room temperature, add the above Mg-Al-CO 3 LDH into the soluble phosphate solution, stir to form a suspension, then add silver nitrate solution, stir at room temperature for 4-24 hours, wash and dry to obtain Ag 3 PO 4 / The composite of Mg-Al-CO 3 LDH, wherein, the mass ratio of Mg-Al-CO 3 LDH and soluble phosphate is 1:5～10:1, and the molar ratio of soluble phosphate and silver nitrate is 1:3～ 3:1;
(3)将上述Ag3PO4/Mg-Al-CO3LDH的复合物于400～600℃煅烧2～4h得到Ag3PO4/Mg-AlLDO可见光复合光催化剂。(3) Calcining the above Ag 3 PO 4 /Mg-Al-CO 3 LDH composite at 400-600° C. for 2-4 hours to obtain Ag 3 PO 4 /Mg-Al-AlDO visible light composite photocatalyst.
所述步骤(1)中的镁盐为硝酸镁或氯化镁，铝盐为硝酸铝或氯化铝。The magnesium salt in the step (1) is magnesium nitrate or magnesium chloride, and the aluminum salt is aluminum nitrate or aluminum chloride.
所述步骤(1)中的碳酸盐为碳酸钾、碳酸钠或碳酸铵，无机碱为氢氧化钾或氢氧化钠。The carbonate in the step (1) is potassium carbonate, sodium carbonate or ammonium carbonate, and the inorganic base is potassium hydroxide or sodium hydroxide.
所述步骤(2)中的可溶性磷酸盐为磷酸钾、磷酸氢二钾、磷酸二氢钾、磷酸钠、磷酸氢二钠或磷酸二氢钠。The soluble phosphate in the step (2) is potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium phosphate, disodium hydrogen phosphate or sodium dihydrogen phosphate.
所述步骤(1)和(2)中的洗涤为分别用去离子水和无水乙醇洗涤。The washing in the steps (1) and (2) is washing with deionized water and absolute ethanol respectively.
本发明的一种Ag3PO4/Mg-Al LDO可见光复合光催化剂应用于染料废水中阴离子污染物的降解和去除。An Ag 3 PO 4 /Mg-Al LDO visible light composite photocatalyst of the present invention is applied to the degradation and removal of anion pollutants in dye wastewater.
本发明在混合盐溶液滴加至混合碱溶液这一过程中，晶体成核和生长同时发生，加料时间越长，粒径分布越宽。采用多管同时加料，缩短了这一过程的时间，有利于晶粒尺寸的均匀分布。加料过程在一个较低的温度(0～50℃)下进行，使得晶体成核速率更快，生长速率更慢，从而使得晶粒尺寸分布更加均匀。经焙烧，Ag3PO4/Mg-Al-CO3LDH的复合物中Mg-Al-CO3LDH的结构羟基和层间CO3 2-离子逸出，原Mg-Al-CO3LDH结构逐渐破坏，转化为复合氧化物，从而得到Ag3PO4/Mg-Al LDO。前驱体Mg-Al-CO3LDH的晶粒尺寸及分布决定了Mg-Al LDO的晶粒尺寸及分布，然而相对于前驱体Mg-Al-CO3LDH而言，Mg-Al LDO比表面积更大，吸附能力更强。经焙烧，将Ag3PO4/Mg-Al-CO3LDH转化为Ag3PO4/Mg-AlLDO，使复合催化剂具备较高的比表面积和较强的吸附性能。In the present invention, during the process of adding the mixed salt solution dropwise to the mixed alkali solution, crystal nucleation and growth occur simultaneously, and the longer the feeding time, the wider the particle size distribution. The simultaneous feeding of multiple tubes shortens the time of this process and is conducive to the uniform distribution of grain size. The feeding process is carried out at a lower temperature (0-50° C.), so that the crystal nucleation rate is faster and the growth rate is slower, so that the grain size distribution is more uniform. After calcination, the structural hydroxyl groups of Mg-Al-CO 3 LDH and interlayer CO 3 2- ions in the Ag 3 PO 4 /Mg-Al-CO 3 LDH composite escaped, and the original Mg-Al-CO 3 LDH structure gradually Destroyed, transformed into composite oxide, thus obtaining Ag 3 PO 4 /Mg-Al LDO. The grain size and distribution of the precursor Mg-Al-CO 3 LDH determine the grain size and distribution of the Mg-Al LDO, but compared with the precursor Mg-Al-CO 3 LDH, the specific surface area of the Mg-Al LDO is larger Larger, stronger adsorption capacity. After roasting, Ag 3 PO 4 /Mg-Al-CO 3 LDH is transformed into Ag 3 PO 4 /Mg-AlLDO, so that the composite catalyst has a higher specific surface area and stronger adsorption performance.
将Ag3PO4/Mg-Al LDO可见光复合光催化剂分散在酸性红1溶液中，以500W氙灯为光源，采用JZ-420滤光片将420nm以下的光滤掉，经可见光照射后，溶液很快由红色变为无色，复合物粉末先由黑色变为红色，表明复合光催化剂具有较强的吸附性能，再慢慢由红色变为黑色，表明吸附的染料已被降解。复合光催化剂在水中的浓度为0.4g/L～20g/L，光催化过程中可通入空气或氧气来加速光催化过程。Disperse the Ag 3 PO 4 /Mg-Al LDO visible light composite photocatalyst in the acid red 1 solution, use a 500W xenon lamp as the light source, and use a JZ-420 filter to filter out the light below 420nm. After being irradiated by visible light, the solution is very It quickly changed from red to colorless, and the composite powder first changed from black to red, indicating that the composite photocatalyst had strong adsorption performance, and then slowly changed from red to black, indicating that the adsorbed dye had been degraded. The concentration of the composite photocatalyst in water is 0.4g/L-20g/L, and air or oxygen can be introduced into the photocatalytic process to accelerate the photocatalytic process.
有益效果Beneficial effect
(1)本发明保留了吸附剂本身吸附性能强的特点，同时具备了较高的可见光催化活性，在染料废水的净化处理领域具有良好的应用前景；(1) The present invention retains the characteristics of strong adsorption performance of the adsorbent itself, and at the same time possesses high visible light catalytic activity, and has a good application prospect in the field of purification and treatment of dye wastewater;
(2)该制备工艺和生产设备简单，对环境友好，易于工业化生产。(2) The preparation process and production equipment are simple, environmentally friendly and easy for industrial production.
附图说明Description of drawings
图1为实施例2制备的Ag3PO4/Mg-Al LDO的X射线衍射图；Fig. 1 is the X-ray diffraction pattern of Ag 3 PO 4 /Mg-Al LDO prepared in Example 2;
图2为实施例2制备的Ag3PO4/Mg-Al LDO(Ag3PO4wt％＝50％)和实施例3制备的Ag3PO4/Mg-Al LDO(Ag3PO4wt％＝25％)的紫外-可见漫反射光谱；Figure 2 shows the Ag 3 PO 4 /Mg-Al LDO prepared in Example 2 (Ag 3 PO 4 wt% = 50%) and the Ag 3 PO 4 /Mg-Al LDO prepared in Example 3 (Ag 3 PO 4 wt% =25%) UV-Vis diffuse reflectance spectrum;
图3为实施例2制备的Ag3PO4/Mg-Al LDO作为光催化剂降解酸性红1浓度随时间的变化；Fig. 3 is the concentration of Ag 3 PO 4 /Mg-Al LDO prepared in Example 2 used as a photocatalyst to degrade Acid Red 1 over time;
图4为实施例2制备的Ag3PO4/Mg-Al LDO及其光催化酸性红1后的红外光谱，作为对比，给出了酸性红1的红外光谱。Fig. 4 is the infrared spectrum of Ag 3 PO 4 /Mg-Al LDO prepared in Example 2 and its photocatalyzed Acid Red 1. As a comparison, the infrared spectrum of Acid Red 1 is given.
具体实施方式Detailed ways
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art may make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
实施例1Example 1
室温下，称取76.24g六水氯化镁和45.27g六水氯化铝加入262.5ml水中，搅拌至完全溶解，得混合盐溶液。另称取52.5g氢氧化钠和66.38g碳酸钠加入375ml水中，搅拌至完全溶解，得混合碱溶液。将混合碱溶液倒入三口烧瓶中，置于油浴锅，将油浴锅加热至50℃，采用三个恒压滴管将混合盐溶液逐滴滴加到混合碱溶液中。滴加完毕后，将油浴锅加热到90℃，保温4h。保温结束后分别用去离子水和无水乙醇洗涤6次和2次，经90℃干燥24h，得到Mg-Al-CO3LDH。At room temperature, weigh 76.24g of magnesium chloride hexahydrate and 45.27g of aluminum chloride hexahydrate into 262.5ml of water, and stir until completely dissolved to obtain a mixed salt solution. Separately weigh 52.5g of sodium hydroxide and 66.38g of sodium carbonate into 375ml of water and stir until completely dissolved to obtain a mixed alkali solution. Pour the mixed alkali solution into a three-necked flask, place it in an oil bath, heat the oil bath to 50°C, and use three constant pressure droppers to add the mixed salt solution to the mixed alkali solution drop by drop. After the dropwise addition, the oil bath was heated to 90°C and kept for 4h. After the heat preservation was completed, it was washed 6 times and 2 times with deionized water and absolute ethanol, respectively, and dried at 90° C. for 24 hours to obtain Mg—Al—CO 3 LDH.
实施例2Example 2
室温下，称取4.8g十二水磷酸氢二钠加入到150ml水中，搅拌至完全溶解，再称取3g实施例1制备的Mg-Al-CO3LDH加入到上述溶液中，搅拌悬浮液10min。称取2.3g硝酸银加入50ml水中，避光搅拌至完全溶解后，加入到上述悬浮液中，在室温下避光搅拌24h。反应结束后，用蒸馏水洗涤6次，经过70℃烘干24h。将粉体于空气中400℃煅烧4h，得到Ag3PO4/Mg-Al LDO(Ag3PO4wt％＝50％)。At room temperature, weigh 4.8g of disodium hydrogen phosphate dodecahydrate and add it to 150ml of water, stir until completely dissolved, then weigh 3g of Mg-Al-CO 3 LDH prepared in Example 1 and add it to the above solution, and stir the suspension for 10min . Weigh 2.3g of silver nitrate and add it into 50ml of water, and stir until completely dissolved in the dark, then add it to the above suspension, and stir at room temperature for 24h in the dark. After the reaction, wash with distilled water 6 times, and dry at 70°C for 24 hours. The powder was calcined at 400° C. in air for 4 hours to obtain Ag 3 PO 4 /Mg-Al LDO (Ag 3 PO 4 wt%=50%).
图1为本实施例制备的Ag3PO4/Mg-Al LDO的X射线衍射图，图中所示的Ag3PO4特征峰十分明显，同时，还出现了单质Ag的特征峰，表明Ag3PO4/Mg-Al LDO的复合物中Ag的化学环境以Ag3PO4为主，含有部分单质Ag。而Mg-Al LDO以无定形的形式出现。图2为实施例2制备的Ag3PO4/Mg-Al LDO(Ag3PO4wt％＝50％)的紫外-可见光漫反射光谱见图2，复合催化剂在可见光区均有较强的吸收。Ag3PO4的吸收带边约为530nm，复合催化剂在大于530nm处的吸收主要是因为经400℃煅烧过后，样品中部分的Ag3PO4转化为单质Ag。Figure 1 is the X-ray diffraction pattern of the Ag 3 PO 4 /Mg-Al LDO prepared in this example. The characteristic peaks of Ag 3 PO 4 shown in the figure are very obvious, and at the same time, the characteristic peaks of elemental Ag also appear, indicating that Ag The chemical environment of Ag in the composite of 3 PO 4 /Mg-Al LDO is mainly Ag 3 PO 4 , and contains some elemental Ag. However, Mg-Al LDO appears in an amorphous form. Figure 2 is the ultraviolet-visible light diffuse reflectance spectrum of Ag 3 PO 4 /Mg-Al LDO (Ag 3 PO 4 wt%=50%) prepared in Example 2. See Figure 2. The composite catalyst has strong absorption in the visible light region . The absorption band edge of Ag 3 PO 4 is about 530nm, and the absorption of the composite catalyst at greater than 530nm is mainly due to the conversion of part of Ag 3 PO 4 in the sample to simple Ag after calcination at 400°C.
实施例3Example 3
室温下，称取1.6g十二水磷酸氢二钠加入到150ml水中，搅拌至完全溶解，再称取3g实施例1制备的Mg-Al-CO3LDH加入到上述溶液中，搅拌悬浮液10min。称取0.77g硝酸银加入50ml水中，避光搅拌至完全溶解后，加入到上述悬浮液中，在室温下避光搅拌24h。反应结束后，用蒸馏水洗涤6次，经过70℃烘干24h。将粉体于空气中400℃煅烧4h，得到Ag3PO4/Mg-Al LDO(Ag3PO4wt％＝25％)。At room temperature, weigh 1.6g of disodium hydrogen phosphate dodecahydrate and add it to 150ml of water, stir until completely dissolved, then weigh 3g of Mg-Al-CO 3 LDH prepared in Example 1 and add it to the above solution, and stir the suspension for 10min . Weigh 0.77g of silver nitrate and add it into 50ml of water, and stir until completely dissolved in the dark, then add it to the above suspension, and stir at room temperature for 24 hours in the dark. After the reaction, wash with distilled water 6 times, and dry at 70°C for 24 hours. The powder was calcined at 400° C. in air for 4 hours to obtain Ag 3 PO 4 /Mg-Al LDO (Ag 3 PO 4 wt%=25%).
图2给出了本实施例制备的Ag3PO4/Mg-Al LDO(Ag3PO4wt％＝25％)的紫外-可见光漫反射光谱，复合催化剂在可见光区均有较强的吸收。Figure 2 shows the ultraviolet-visible light diffuse reflectance spectrum of Ag 3 PO 4 /Mg-Al LDO (Ag 3 PO 4 wt%=25%) prepared in this example, and the composite catalyst has strong absorption in the visible light region.
实施例4Example 4
将实施例2制备的Ag3PO4/Mg-Al LDO用作可见光催化剂降解酸性红1，以500W氙灯为光源，采用JZ-420滤光片将420nm以下的光滤掉。称取0.2gAg3PO4/Mg-Al LDO加入100ml，浓度为50mg/L的酸性红1溶液中，黑暗搅拌30min，使酸性红1在催化剂表面达到吸附/脱附平衡。然后开启光源进行光催化反应，每隔10min取3ml反应液，经离心分离后取上层清液，然后利用紫外可见吸收光谱仪(型号为Lambda 35，Perkin Elmer，America)在波长505nm处测吸光度来确定降解过程中酸性红1浓度的变化。The Ag 3 PO 4 /Mg-Al LDO prepared in Example 2 was used as a visible light catalyst to degrade
图3为本实施例中Ag3PO4/Mg-Al LDO用作可见光催化剂降解酸性红1，从图中可以看出，Ag3PO4/Mg-Al LDO可见光复合光催化剂，保留了吸附剂本身吸附性能力强的特点，同时具备了较高的可见光催化活性。Figure 3 shows that Ag 3 PO 4 /Mg-Al LDO is used as a visible light catalyst to degrade
图4给出了Ag3PO4/Mg-Al LDO，以及催化酸性红1后复合物的红外光谱，其中还给出了酸性红1的红外光谱进行对比。从图中能看到该复合物在光催化降解酸性红1后，峰型几乎与催化前Ag3PO4/Mg-Al LDO一致，没有出现酸性红1的特征峰，从而证明酸性红1已被分解。Figure 4 shows the infrared spectrum of Ag 3 PO 4 /Mg-Al LDO, and the complex after catalyzing
实施例5Example 5
室温下，称取40.35g二水硝酸镁和20.56g九水硝酸铝加入262.5ml水中，搅拌至完全溶解，得混合盐溶液。另称取50.06g氢氧化钾和20.56g碳酸钾加入375ml水中，搅拌至完全溶解，得混合碱溶液。将混合碱溶液倒入三口烧瓶中，置于油浴锅，将油浴锅加热至50℃，采用三个恒压滴管将混合盐溶液逐滴滴加到混合碱溶液中。滴加完毕后，将油浴锅加热到90℃，保温4h。保温结束后分别用去离子水和无水乙醇洗涤6次和2次，经90℃干燥24h，得到Mg-Al-CO3LDH。At room temperature, weigh 40.35g of magnesium nitrate dihydrate and 20.56g of aluminum nitrate nonahydrate into 262.5ml of water, and stir until completely dissolved to obtain a mixed salt solution. Weigh 50.06g of potassium hydroxide and 20.56g of potassium carbonate into 375ml of water and stir until completely dissolved to obtain a mixed alkali solution. Pour the mixed alkali solution into a three-necked flask, place it in an oil bath, heat the oil bath to 50°C, and use three constant pressure droppers to add the mixed salt solution to the mixed alkali solution drop by drop. After the dropwise addition, the oil bath was heated to 90°C and kept for 4h. After the heat preservation was completed, it was washed 6 times and 2 times with deionized water and absolute ethanol, respectively, and dried at 90° C. for 24 hours to obtain Mg—Al—CO 3 LDH.
室温下，称取0.5g三水磷酸钾加入到150ml水中，搅拌至完全溶解，再称取5g上述制备的Mg-Al-CO3LDH加入到上述溶液中，搅拌悬浮液10min。称取1.5g硝酸银加入50ml水中，避光搅拌至完全溶解后，加入到上述悬浮液中，在室温下避光搅拌4h。反应结束后，用蒸馏水洗涤6次，经过70℃烘干24h。将粉体于空气中600℃煅烧2h，得到Ag3PO4/Mg-AlLDO。At room temperature, weigh 0.5g of potassium phosphate trihydrate and add it to 150ml of water, stir until completely dissolved, then weigh 5g of the above-prepared Mg-Al-CO 3 LDH and add it to the above solution, and stir the suspension for 10min. Weigh 1.5g of silver nitrate and add it into 50ml of water, and stir until completely dissolved in the dark, then add it to the above suspension, and stir at room temperature for 4h in the dark. After the reaction, wash with distilled water for 6 times, and dry at 70°C for 24 hours. The powder was calcined in air at 600°C for 2 hours to obtain Ag 3 PO 4 /Mg-AlLDO.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5188660A (en) * | 1991-10-16 | 1993-02-23 | E. I. Du Pont De Nemours And Company | Process for making finely divided particles of silver metals |
| CN1459474A (en) * | 2002-05-20 | 2003-12-03 | 中国科学院理化技术研究所 | Micro-mesoporous silica heterocomplex and preparation method and application thereof |
| JP2009078211A (en) * | 2007-09-26 | 2009-04-16 | National Institute For Materials Science | photocatalyst |
| CN101648139A (en) * | 2009-09-03 | 2010-02-17 | 福州大学 | Novel visible catalyst-silver phosphate and preparation method thereof |
| CN101940937A (en) * | 2010-10-21 | 2011-01-12 | 武汉理工大学 | High-efficiency visible light catalyst silver phosphate and preparation method thereof |
-
2011
- 2011-01-28 CN CN 201110031651 patent/CN102151577B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5188660A (en) * | 1991-10-16 | 1993-02-23 | E. I. Du Pont De Nemours And Company | Process for making finely divided particles of silver metals |
| CN1459474A (en) * | 2002-05-20 | 2003-12-03 | 中国科学院理化技术研究所 | Micro-mesoporous silica heterocomplex and preparation method and application thereof |
| JP2009078211A (en) * | 2007-09-26 | 2009-04-16 | National Institute For Materials Science | photocatalyst |
| CN101648139A (en) * | 2009-09-03 | 2010-02-17 | 福州大学 | Novel visible catalyst-silver phosphate and preparation method thereof |
| CN101940937A (en) * | 2010-10-21 | 2011-01-12 | 武汉理工大学 | High-efficiency visible light catalyst silver phosphate and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《nature materials》 20100731 Zhiguo Yi et al. An orthophosphate semiconductor with photooxidation properties under visible-light irradiation 第9卷, * |
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