CN104815696A - Metal oxalate nanofiber and preparation method as well as application thereof - Google Patents
Metal oxalate nanofiber and preparation method as well as application thereof Download PDFInfo
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 34
- 239000002184 metal Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002121 nanofiber Substances 0.000 title claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 36
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 11
- 239000010941 cobalt Substances 0.000 claims abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 4
- 239000000725 suspension Substances 0.000 claims abstract description 4
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- 239000000975 dye Substances 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000003344 environmental pollutant Substances 0.000 claims description 5
- 231100000719 pollutant Toxicity 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 2
- 229940012189 methyl orange Drugs 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 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 description 2
- 229940043267 rhodamine b Drugs 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 238000004448 titration Methods 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 23
- 238000006731 degradation reaction Methods 0.000 abstract description 23
- 239000003054 catalyst Substances 0.000 abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 12
- 239000001044 red dye Substances 0.000 abstract description 11
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000012467 final product Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 10
- JZVQPKHCUUWSIQ-UHFFFAOYSA-J copper cobalt(2+) oxalate Chemical compound [Co++].[Cu++].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O JZVQPKHCUUWSIQ-UHFFFAOYSA-J 0.000 description 10
- 239000002351 wastewater Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 206010064571 Gene mutation Diseases 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 208000010501 heavy metal poisoning Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- -1 oxalate metal compound Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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Abstract
本发明公开了一种金属草酸盐纳米纤维的制备方法，包括以下步骤：将金属盐溶液溶于乙醇溶液中，配成A溶液，作为金属前驱体，所述金属盐至少含钴一种金属元素；再将草酸溶于乙醇溶液中，配成B溶液，然后将B溶液在磁力搅拌下滴定在A溶液中，搅拌20-50min，所得的悬浮液转移到高压灭菌器中，100-200℃保存12-48h，冷却至室温，最后得到的产物用去离子水冲洗干净，50-100℃干燥得到金属草酸盐纳米纤维。本发明制备工艺简单、成本低、制备条件易于控制、合成周期短等优点。制备的金属草酸盐纳米纤维作为催化剂在过氧化氢体系中对刚果红染料有着优异的降解效果，可显著提高水质净化效果。
The invention discloses a method for preparing metal oxalate nanofibers, which comprises the following steps: dissolving a metal salt solution in an ethanol solution to prepare a solution A as a metal precursor, and the metal salt contains at least one metal of cobalt element; then dissolve oxalic acid in ethanol solution to form B solution, then titrate B solution in A solution under magnetic stirring, stir for 20-50min, and transfer the resulting suspension to an autoclave, 100-200 Store at °C for 12-48 hours, cool to room temperature, rinse the final product with deionized water, and dry at 50-100 °C to obtain metal oxalate nanofibers. The invention has the advantages of simple preparation process, low cost, easy control of preparation conditions, short synthesis cycle and the like. As a catalyst, the prepared metal oxalate nanofibers have an excellent degradation effect on Congo red dye in a hydrogen peroxide system, which can significantly improve the water purification effect.
Description
技术领域technical field
本发明涉及一种新型金属草酸盐材料的制备方法及其降解水中刚果红染料的研究，属于水处理领域。The invention relates to a preparation method of a novel metal oxalate material and research on degrading Congo red dye in water, belonging to the field of water treatment.
背景技术Background technique
染料废水是印刷纺织化工工业废水的主要组成部分，近些年来，随着染料和印染工业的迅速发展，新的添加剂、染料在印染化工工业的广泛应用，其产生的废水对环境危害日趋严重，在废水中人们发现了越来越多的有毒有机物，有些有机物甚至会引起基因突变、癌变、重金属慢性中毒，而且染料废水被排到江河、海洋和地表水，其中的染料成分即使浓度很低，也会造成被排入水体的透光率降低，造成水体生态系统破坏，对环境造成严重污染，进而影响人类的健康和生活。而刚果红是用途比较广泛的染料之一，它在生产和使用过程中流失率高，并且比较容易进入水体，对环境造成破坏；刚果红是联苯胺类偶氮染料，化学名是二苯基-4，4’-二(偶氮-2-)-1-氨基萘-4-磺酸钠，由于其结构的稳定性，其产生的染料废水是很难通过传统的物理、化学、生物方法降解，这些方法尽管可以使刚果红染料废水颜色褪去，但是其产生的中间产物不能有效地得到降解，其对环境污染更大。Dye wastewater is the main component of printing and textile chemical industry wastewater. In recent years, with the rapid development of dyes and printing and dyeing industries, new additives and dyes have been widely used in printing and dyeing chemical industry, and the wastewater produced by them has become more and more harmful to the environment. People have found more and more toxic organic substances in wastewater. Some organic substances can even cause gene mutation, cancer, and chronic heavy metal poisoning. Moreover, dye wastewater is discharged into rivers, oceans, and surface water. Even if the concentration of dye components is very low, It will also reduce the light transmittance discharged into the water body, cause damage to the water body ecosystem, cause serious pollution to the environment, and then affect human health and life. Congo red is one of the dyes with a wide range of uses. It has a high loss rate during production and use, and it is relatively easy to enter the water body, causing damage to the environment; Congo red is a benzidine-type azo dye, and its chemical name is diphenyl -4,4'-bis(azo-2-)-1-aminonaphthalene-4-sodium sulfonate, due to the stability of its structure, the dye wastewater produced by it is difficult to pass through traditional physical, chemical and biological methods Degradation, although these methods can make the color of Congo red dye wastewater fade, the intermediate products it produces cannot be degraded effectively, and it is more polluting to the environment.
发明内容Contents of the invention
本发明的目的在于提供一种高降解率、降解时间快的草酸盐复合金属催化剂材料及其在处理染料废水的过程方法，该材料在降解刚果红染料废水时表现出良好的效果。The object of the present invention is to provide a kind of oxalate composite metal catalyst material with high degradation rate and fast degradation time and its process method for treating dye wastewater. The material shows good effect when degrading Congo red dye wastewater.
本发明的目的通过以下技术方案实现：The object of the present invention is achieved through the following technical solutions:
一种金属草酸盐纳米纤维的制备方法，包括以下步骤：A preparation method of metal oxalate nanofibers, comprising the following steps:
将金属盐溶液溶于乙醇溶液中，配成A溶液，作为金属前驱体，所述金属盐至少含钴一种金属元素；再将草酸溶于乙醇溶液中，配成B溶液，然后将B溶液在磁力搅拌下滴定在A溶液中，搅拌20-50min，所得的悬浮液转移到高压灭菌器中，100-200℃保存12-48h，冷却至室温，最后得到的产物用去离子水冲洗干净，50-100℃干燥得到金属草酸盐纳米纤维。Dissolving the metal salt solution in the ethanol solution to make solution A, as a metal precursor, the metal salt contains at least one metal element of cobalt; then dissolving oxalic acid in the ethanol solution to make solution B, and then making solution B Titrate in solution A under magnetic stirring, stir for 20-50min, transfer the resulting suspension to an autoclave, store at 100-200°C for 12-48h, cool to room temperature, and rinse the final product with deionized water , and dried at 50-100°C to obtain metal oxalate nanofibers.
所述金属盐为钴、铜、镍和铁的硝酸盐或硫酸盐中的一种或两种以上的混合物。The metal salt is one or a mixture of two or more nitrates or sulfates of cobalt, copper, nickel and iron.
所述金属盐为钴和铜两种金属的硝酸盐或硫酸盐。The metal salt is nitrate or sulfate of cobalt and copper.
所述钴和铜的摩尔比为(1～10):1。The molar ratio of cobalt and copper is (1-10):1.
所述钴和草酸的摩尔比为1:1。The molar ratio of cobalt and oxalic acid is 1:1.
所述A溶液中钴离子的浓度为0.1～0.3mol/L，所述B溶液的浓度为0.1-1.0mol/L。The concentration of cobalt ions in the A solution is 0.1-0.3 mol/L, and the concentration of the B solution is 0.1-1.0 mol/L.
所述金属草酸盐纳米材料在过氧化氢体系中用于去除水中的污染物。The metal oxalate nanomaterial is used in a hydrogen peroxide system to remove pollutants in water.
所述的污染物为苯类有机染料。The pollutants are benzene organic dyes.
所述有机染料为刚果红、甲基橙、罗丹明B。The organic dyes are Congo red, methyl orange and rhodamine B.
与现有技术相比，本发明具有如下优点：Compared with prior art, the present invention has following advantage:
(1)本发明通过化学共沉淀法制备高反应活性的钴铜草酸盐纳米纤维和草酸钴纳米纤维，该制备工艺简单、成本低、制备条件易于控制、合成周期短等优点。制备的金属草酸盐纳米材料作为催化剂在过氧化氢体系中对刚果红染料有着优异的降解效果。可显著提高水质净化效果。(1) The present invention prepares highly reactive cobalt-copper oxalate nanofibers and cobalt oxalate nanofibers by a chemical co-precipitation method, which has the advantages of simple preparation process, low cost, easy control of preparation conditions, and short synthesis cycle. The prepared metal oxalate nanomaterials have excellent degradation effect on Congo red dye as catalyst in hydrogen peroxide system. Can significantly improve the water purification effect.
(2)草酸盐的金属复合催化剂和金属氧化物催化剂相比，其催化降解效果更加优异。而且复合金属在其反应过程中有一定的协同作用。复合的草酸盐表现出比较优越的催化性能。(2) Compared with the metal oxide catalyst, the metal composite catalyst of oxalate has a better catalytic degradation effect. Moreover, the composite metal has a certain synergistic effect in the reaction process. Composite oxalate showed superior catalytic performance.
附图说明Description of drawings
图1(a)、(c)为草酸钴的扫描电镜和透射电镜图片，(b)、(d)为钴铜草酸盐的扫描电镜和投射电镜图片。Fig. 1(a), (c) are scanning electron microscope and transmission electron microscope pictures of cobalt oxalate, (b), (d) are scanning electron microscope and transmission electron microscope pictures of cobalt copper oxalate.
图2为不同压力下制备得到的钴铜草酸盐(a)和草酸钴(b)的N2吸附-脱附曲线。Figure 2 is the N adsorption-desorption curves of cobalt copper oxalate (a) and cobalt oxalate (b) prepared under different pressures.
图3为不同催化剂降解刚果红染料的对比图。Fig. 3 is a comparison chart of the degradation of Congo red dye by different catalysts.
图4为材料对刚果红染料的催化降解效果图。Figure 4 is a diagram of the catalytic degradation effect of the material on Congo red dye.
图5为不同温度下对刚果红染料的催化降解效果图。Figure 5 is a diagram showing the catalytic degradation effect of Congo red dye at different temperatures.
具体实施方式Detailed ways
以下结合附图对本发明事例作进一步具体的描述，但是本发明的实施方式不限于此。The examples of the present invention will be further specifically described below in conjunction with the accompanying drawings, but the embodiments of the present invention are not limited thereto.
实施例1Example 1
取2.5mmol三水合硝酸铜和7.5mmol硝酸钴六水合物，溶于40ml乙醇中，所得溶液制备成金属前驱体A，再取7.5mmol草酸，溶于40ml乙醇中，所配成的溶液为B,然后将溶液B在磁力搅拌下滴定在溶液A中，搅拌30min,所得的悬浮液转移到高压灭菌器中，120℃保存12h，冷却至室温，最后得到的产物用去离子水冲洗干净，80℃干燥得到钴铜草酸盐。草酸钴的制备方法相同，只是前驱体溶液中不加入三水合硝酸铜。其电镜图片如图1所示：(a)、(c)和(b)、(d)分别为草酸钴和钴铜草酸盐的扫描电镜和透射电镜图片，所制备的草酸盐材料都具有纳米纤维状。图2中(a)和(b)分别为钴铜草酸盐和草酸钴的N2吸附-脱附曲线。BET表面积分别为76m2/g和74m2/g。Take 2.5mmol copper nitrate trihydrate and 7.5mmol cobalt nitrate hexahydrate, dissolve in 40ml ethanol, the resulting solution is prepared as metal precursor A, then take 7.5mmol oxalic acid, dissolve it in 40ml ethanol, the resulting solution is B , then titrate solution B in solution A under magnetic stirring, stir for 30 minutes, transfer the resulting suspension to an autoclave, store at 120°C for 12 hours, cool to room temperature, and rinse the final product with deionized water. Dry at 80°C to obtain cobalt copper oxalate. Cobalt oxalate was prepared in the same way, except that copper nitrate trihydrate was not added to the precursor solution. Its electron microscope picture is shown in Figure 1: (a), (c) and (b), (d) are scanning electron microscope and transmission electron microscope picture of cobalt oxalate and cobalt copper oxalate respectively, prepared oxalate material all Has a nanofibrous shape. (a) and (b) in Fig. 2 are the N2 adsorption-desorption curves of cobalt-copper oxalate and cobalt oxalate, respectively. The BET surface areas are 76 m 2 /g and 74 m 2 /g, respectively.
上述制得的金属草酸盐催化材料对染料废水的处理：The metal oxalate catalyst material that above-mentioned makes is to the treatment of dye wastewater:
刚果红是联苯胺类偶氮染料，是一种重要的染料，钴铜草酸盐在过氧化氢体系中，能产生大量的强氧化剂羟基自由基(HO·)，可以有效地降解刚果红等染料。其作为催化剂可以被应用于水处理中。Congo red is a benzidine-type azo dye, which is an important dye. Cobalt copper oxalate can generate a large number of strong oxidant hydroxyl radicals (HO ) in a hydrogen peroxide system, which can effectively degrade Congo red, etc. dye. It can be used as a catalyst in water treatment.
在100ml质量浓度100mg/L的刚果红溶液中加入100mg的钴铜草酸盐(或草酸钴)，再加入3％质量分数的过氧化氢溶液，搅拌，用硫酸和氢氧化钠调节初始溶液PH为7，温度30℃，取一定量的溶液，离心，过滤，然后采用分光光度计测定其浓度，从而计算该催化剂材料对刚果红的降解率，图3为不同催化剂对刚果红的降解曲线，钴铜草酸盐表现最好，达到96.20％。图4是钴铜草酸盐催化降解刚果红染料的效果图。Add 100 mg of cobalt copper oxalate (or cobalt oxalate) to 100 ml of Congo red solution with a mass concentration of 100 mg/L, then add 3% mass fraction of hydrogen peroxide solution, stir, and adjust the pH of the initial solution with sulfuric acid and sodium hydroxide 7, the temperature is 30°C, take a certain amount of solution, centrifuge, filter, and then use a spectrophotometer to measure its concentration, thereby calculating the degradation rate of the catalyst material to Congo red. Figure 3 is the degradation curve of different catalysts to Congo red. Cobalt-copper oxalate performed best at 96.20%. Figure 4 is an effect diagram of cobalt copper oxalate catalyzed degradation of Congo red dye.
实施例2Example 2
在催化降解刚果红溶液中，改变温度20℃，制备方法和其它催化条件同实施例1。In the catalytic degradation Congo red solution, the temperature was changed by 20° C., and the preparation method and other catalytic conditions were the same as in Example 1.
实施例3Example 3
在催化降解刚果红溶液中，改变温度40℃，制备方法和其它催化条件同实施例1。In the catalytic degradation solution of Congo red, the temperature was changed to 40° C., and the preparation method and other catalytic conditions were the same as in Example 1.
实施例4Example 4
在催化降解刚果红溶液中，改变温度50℃，制备方法和其它催化条件同实施例1。In the catalytic degradation Congo red solution, the temperature was changed by 50°C, and the preparation method and other catalytic conditions were the same as in Example 1.
实施例1、2、3、4中，考察了不同反应温度对催化降解刚果红的影响，结果如图5所示：四个温度所对应的降解率分别为96.20％、63.70％、96.33％、97.60％。随着反应温度的增加，降解效果越好，是因为温度升高，是过氧化氢的分解显著增强，产生了更多的强氧化剂羟基自由基(HO·)，使其降解更多的刚果红及其中间产物，在100min后，降解速度变慢，可能是因为溶液含有大量的N、S等元素，而产生的强氧化剂不能有效地降解它们，所以随着时间的进行溶液中污染物降解的比较缓慢。In Examples 1, 2, 3, and 4, the effects of different reaction temperatures on the catalytic degradation of Congo red were investigated, and the results are shown in Figure 5: the degradation rates corresponding to the four temperatures were 96.20%, 63.70%, 96.33%, respectively. 97.60%. As the reaction temperature increases, the degradation effect is better, because the temperature increases, the decomposition of hydrogen peroxide is significantly enhanced, and more strong oxidant hydroxyl radicals (HO ) are produced, which degrades more Congo red And its intermediate products, after 100min, the degradation rate slows down, probably because the solution contains a large amount of N, S and other elements, and the strong oxidant produced cannot degrade them effectively, so the pollutants in the solution degrade as time goes on. relatively slow.
比较例1Comparative example 1
采用不同方法制备的钴的草酸盐，其和传统的铁的氧化物对比，检测该草酸盐材料对刚果红染料的降解效果。The cobalt oxalate prepared by different methods was compared with the traditional iron oxide, and the degradation effect of the oxalate material on Congo red dye was tested.
由图3可知，草酸盐金属化合物作为催化剂，该材料表现出对刚果红染料良好的催化效果。It can be seen from Figure 3 that the oxalate metal compound is used as a catalyst, and this material shows a good catalytic effect on Congo red dye.
本发明是对类芬顿反应的进一步改进，制得了钴的草酸盐系列产品作为催化剂，其催化降解材料不仅仅局限在金属氧化物方面，拓宽了材料的选择；而且，重要的是该材料在用于水处理方面，表现出对水中染料优异的降解性能。The present invention is a further improvement to the Fenton-like reaction, and has produced cobalt oxalate series products as catalysts, and its catalytic degradation materials are not limited to metal oxides, which broadens the selection of materials; moreover, the important thing is that the materials In terms of water treatment, it exhibits excellent degradation performance for dyes in water.
以上内容是结合具体的优选实施方式进行的说明，其材料不只仅局限在钴的草酸盐系列，在不脱离本方面构思的前提下，草酸盐系列的金属催化剂以及金属草酸盐催化降解染料都应当视为属于本发明保护的范围。The above content is an explanation in conjunction with specific preferred embodiments. Its materials are not limited to cobalt oxalate series. On the premise of not departing from the concept of this aspect, metal catalysts of oxalate series and metal oxalate catalytic degradation All dyes should be regarded as belonging to the protection scope of the present invention.
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