CN108940317A - A kind of Fe3O4@C-CoS-TiO2Composite photo-catalyst and preparation method thereof - Google Patents
A kind of Fe3O4@C-CoS-TiO2Composite photo-catalyst and preparation method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 48
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 24
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 239000002105 nanoparticle Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 150000001868 cobalt Chemical class 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 88
- 150000002505 iron Chemical class 0.000 claims description 12
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 7
- 235000017281 sodium acetate Nutrition 0.000 claims description 7
- 239000001632 sodium acetate Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 238000002525 ultrasonication Methods 0.000 claims description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 7
- 238000005352 clarification Methods 0.000 description 5
- 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 5
- 239000000463 material Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 239000006249 magnetic particle Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical class [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
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Abstract
本发明提供一种Fe3O4@C‑CoS‑TiO2复合光催化剂及其制备方法，涉及光催化技术领域。该制备方法包括：S1，制备Fe3O4。S2，将碳源与Fe3O4分散在水中，超声搅拌后在150～200℃条件下反应4～8h，离心、洗涤、干燥后得到Fe3O4@C纳米颗粒。S3，将Fe3O4@C纳米颗粒、钴盐、硫脲、水、乙二醇、钛酸四丁酯和无水乙醇混合后，在150～200℃条件下反应12～16h，离心、洗涤、干燥后得到Fe3O4@C‑CoS‑TiO2复合光催化剂。Fe3O4@C‑CoS‑TiO2复合光催化剂整合了磁性复合材料的超顺磁性，也可响应可见光，可用于光催化降解水制氢或光催化分解水中的污染物。且其制备工艺简单、易于操作、重复性强、成本低。The invention provides a Fe 3 O 4 @C-CoS-TiO 2 composite photocatalyst and a preparation method thereof, which relate to the technical field of photocatalysis. The preparation method includes: S1, preparing Fe 3 O 4 . S2, disperse the carbon source and Fe 3 O 4 in water, and react at 150-200° C. for 4-8 hours after ultrasonic stirring, centrifuge, wash and dry to obtain Fe 3 O 4 @C nanoparticles. S3, mix Fe 3 O 4 @C nanoparticles, cobalt salt, thiourea, water, ethylene glycol, tetrabutyl titanate and absolute ethanol, react at 150-200°C for 12-16 hours, centrifuge, After washing and drying, Fe 3 O 4 @C-CoS-TiO 2 composite photocatalyst was obtained. The Fe3O4@C‑CoS‑TiO2 composite photocatalyst integrates the superparamagnetism of the magnetic composite material and can also respond to visible light. It can be used for photocatalytic degradation of water to produce hydrogen or photocatalytic decomposition of pollutants in water. Moreover, the preparation process is simple, easy to operate, strong in repeatability and low in cost.
Description
技术领域technical field
本发明涉及光催化技术领域，且特别涉及一种Fe3O4@C-CoS-TiO2复合光催化剂及其制备方法。The invention relates to the technical field of photocatalysis, and in particular to a Fe3O4 @C - CoS- TiO2 composite photocatalyst and a preparation method thereof.
背景技术Background technique
能源短缺和环境恶化是目前人类面临的两大问题。目前研究热点是利用光催化材料将水分解制氢。一方面能够利用光降解有机污染物，另一方面可产生清洁能源-氢能。因此，光催化材料在解决能源和环境问题方面有着双重的应用前景。Energy shortage and environmental degradation are two major problems facing mankind at present. The current research hotspot is the use of photocatalytic materials to split water into hydrogen. On the one hand, it can use light to degrade organic pollutants, and on the other hand, it can generate clean energy-hydrogen energy. Therefore, photocatalytic materials have dual application prospects in solving energy and environmental problems.
光催化技术是以n型半导体的能带理论而建立，利用光能激发半导体的价带电子发生跃迁,从而生成光生电子和空穴，形成光生载流子，载流子具有很强的氧化性，可将绝大部分的有机物氧化为CO2和H2O，甚至对部分无机物也能完全氧化分解。寻找到一种高效、绿色、廉价的催化剂是目前光催化技术急需攻克的一大难题。Photocatalytic technology is established based on the energy band theory of n-type semiconductors, using light energy to excite semiconductor valence band electrons to transition, thereby generating photogenerated electrons and holes, forming photogenerated carriers, which have strong oxidative properties , can oxidize most of the organic matter into CO 2 and H 2 O, and even completely oxidize and decompose some inorganic matter. Finding an efficient, green, and cheap catalyst is a major problem that photocatalytic technology urgently needs to overcome.
TiO2是一种常见的n型半导体，具有良好的化学稳定性和生物相容性。纳米TiO2因其较高的光催化活性在光催化领域得到广泛的应用。但是纳米TiO2在处理污水时很容易分散开来，难以在污水处理过后进行回收再利用，容易对环境造成二次污染，另外其不能响应可见光的缺点也导致纳米TiO2在污水处理方面无法得到深入的应用。 TiO2 is a common n-type semiconductor with good chemical stability and biocompatibility. Nano-TiO 2 has been widely used in the field of photocatalysis because of its high photocatalytic activity. However, nano - TiO2 is easy to disperse when treating sewage, and it is difficult to recycle and reuse after sewage treatment. in-depth application.
磁性复合材料作为一种新兴材料，它为多功能材料提供了一个绝佳的载体平台，可以将多种功能材料进行整合，从而发挥出材料的多重特性。可将磁性复合材料应用于光催化领域，制备具有催化活性的磁性催化剂，再利用磁性粒子本身的超顺磁性，在外加磁场的作用下可以将催化剂简单快速地分离出来，使得催化剂重复使用。As an emerging material, magnetic composite materials provide an excellent carrier platform for multifunctional materials, which can integrate a variety of functional materials to exert the multiple characteristics of materials. The magnetic composite material can be applied in the field of photocatalysis to prepare a magnetic catalyst with catalytic activity, and then use the superparamagnetism of the magnetic particle itself to separate the catalyst simply and quickly under the action of an external magnetic field, so that the catalyst can be reused.
基于上述理由，设计一种可见光响应磁性光催化剂，该催化剂具有被可见光驱动降解环境有机污染物和解决能源短缺的能力，具有较大的意义。Based on the above reasons, it is of great significance to design a visible light-responsive magnetic photocatalyst, which has the ability to degrade environmental organic pollutants and solve energy shortages driven by visible light.
发明内容Contents of the invention
本发明的目的在于提供一种Fe3O4@C-CoS-TiO2复合光催化剂，此光催化剂整合了磁性复合材料的超顺磁性，也可响应可见光，可用于光催化降解水制氢或光催化分解水中的污染物。The purpose of the present invention is to provide a Fe 3 O 4 @C-CoS-TiO 2 composite photocatalyst, which integrates the superparamagnetism of the magnetic composite material, can also respond to visible light, and can be used for photocatalytic degradation of water to produce hydrogen or Photocatalytic decomposition of pollutants in water.
本发明的目的在于提供一种Fe3O4@C-CoS-TiO2复合光催化剂的制备方法，制备工艺简单、易于操作、重复性强、成本低。The purpose of the present invention is to provide a preparation method of Fe 3 O 4 @C-CoS-TiO 2 composite photocatalyst, which has simple preparation process, easy operation, strong repeatability and low cost.
本发明解决其技术问题是采用以下技术方案来实现的。The present invention solves its technical problems by adopting the following technical solutions.
本发明提出一种Fe3O4@C-CoS-TiO2复合光催化剂的制备方法，包括以下步骤：The present invention proposes a preparation method of Fe 3 O 4 @C-CoS-TiO 2 composite photocatalyst, comprising the following steps:
S1，制备Fe3O4；S1, preparing Fe 3 O 4 ;
S2，制备Fe3O4@C：将碳源与所述Fe3O4分散在水中，超声搅拌后在150～200℃条件下反应4～8h，离心、洗涤、干燥后得到Fe3O4@C纳米颗粒；S2, preparation of Fe3O 4 @C: disperse the carbon source and the Fe 3 O 4 in water, after ultrasonic stirring, react at 150-200°C for 4-8 hours, centrifuge, wash and dry to obtain Fe 3 O 4 @C nanoparticles;
S3，制备Fe3O4@C-CoS-TiO2：将所述Fe3O4@C纳米颗粒、钴盐、硫脲、水、乙二醇、钛酸四丁酯和无水乙醇混合后，在150～200℃条件下反应12～16h，离心、洗涤、干燥后得到所述Fe3O4@C-CoS-TiO2复合光催化剂。S3, preparation of Fe 3 O 4 @C-CoS-TiO 2 : after mixing the Fe 3 O 4 @C nanoparticles, cobalt salt, thiourea, water, ethylene glycol, tetrabutyl titanate and absolute ethanol , react at 150-200° C. for 12-16 hours, centrifuge, wash and dry to obtain the Fe 3 O 4 @C-CoS-TiO 2 composite photocatalyst.
本发明还提出了一种Fe3O4@C-CoS-TiO2复合光催化剂，其根据上述的制备方法制得。The present invention also proposes a Fe 3 O 4 @C-CoS-TiO 2 composite photocatalyst, which is prepared according to the above-mentioned preparation method.
本发明实施例的Fe3O4@C-CoS-TiO2复合光催化剂及其制备方法的有益效果是：The beneficial effects of the Fe 3 O 4 @C-CoS-TiO 2 composite photocatalyst and its preparation method in the embodiment of the present invention are:
TiO2具有良好的化学稳定性和生物相容性，不能响应可见光。而CoS的能带比TiO2窄，但可以吸收可见光并被激发。将两者进行结合，一方面拓宽了复合光催化剂吸收光谱，使得复合光催化剂可吸收可见光并被激发，另一方面复合光催化剂可以使光生电子和空穴有效并快速的分离，提高光催化活性。 TiO2 has good chemical stability and biocompatibility, and cannot respond to visible light. While CoS has a narrower energy band than TiO2 , but it can absorb visible light and be excited. Combining the two, on the one hand, broadens the absorption spectrum of the composite photocatalyst, so that the composite photocatalyst can absorb visible light and be excited; on the other hand, the composite photocatalyst can effectively and quickly separate the photogenerated electrons and holes, improving the photocatalytic activity. .
Fe3O4是最为常见的一种磁性材料，处在纳米量级的Fe3O4在室温下可表现出超顺磁性，制备过程简单成本低廉，化学性质稳定且环保无毒。将磁性粒子本身的超顺磁性附加到复合光催化剂上，在外加磁场的作用下可以将复合催化剂简单快速地分离出来，使得复合光催化剂可重复使用，对环境友好。Fe 3 O 4 is the most common magnetic material. Nanoscale Fe 3 O 4 can exhibit superparamagnetism at room temperature. The preparation process is simple and cost-effective, and its chemical properties are stable and environmentally friendly and non-toxic. The superparamagnetism of the magnetic particle itself is added to the composite photocatalyst, and the composite catalyst can be separated simply and quickly under the action of an external magnetic field, making the composite photocatalyst reusable and environmentally friendly.
本发明制备的Fe3O4@C-CoS-TiO2复合光催化剂整合了磁性复合材料的超顺磁性，也可响应可见光，可用于光催化降解水制氢或光催化分解水中的污染物。且其制备工艺简单、易于操作、重复性强、成本低。The Fe 3 O 4 @C-CoS-TiO 2 composite photocatalyst prepared by the invention integrates the superparamagnetism of the magnetic composite material, can also respond to visible light, and can be used for photocatalytic degradation of water to produce hydrogen or photocatalytic decomposition of pollutants in water. Moreover, the preparation process is simple, easy to operate, strong in repeatability and low in cost.
具体实施方式Detailed ways
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Those who do not indicate the specific conditions in the examples are carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used were not indicated by the manufacturer, and they were all conventional products that could be purchased from the market.
下面对本发明实施例的一种Fe3O4@C-CoS-TiO2复合光催化剂及其制备方法进行具体说明。A Fe 3 O 4 @C-CoS-TiO 2 composite photocatalyst according to an embodiment of the present invention and a preparation method thereof are specifically described below.
本发明提出一种Fe3O4@C-CoS-TiO2复合光催化剂的制备方法，包括以下步骤：The present invention proposes a preparation method of Fe 3 O 4 @C-CoS-TiO 2 composite photocatalyst, comprising the following steps:
S1，制备Fe3O4。S1, preparing Fe 3 O 4 .
进一步地，所述制备Fe3O4的步骤为:在乙二醇中加入表面活性剂，搅拌至形成澄清液体，再加入铁盐、乙酸钠，溶解后在160～200℃条件下反应10～14h，洗涤、干燥得到Fe3O4。优选地，在本发明的较佳实施例中，选用十二烷基苯磺酸钠作为表面活性剂，可以将制备得的Fe3O4颗粒进行包裹防止团聚，另一个则是起到分散作用。Fe3O4纳米级粒子结构具有较大的比表面积，与其它吸附材料复合后，使其具有强的吸附能力和良好的分离特性。Further, the step of preparing Fe 3 O 4 is as follows: add a surfactant to ethylene glycol, stir until a clear liquid is formed, then add iron salt and sodium acetate, dissolve and react at 160-200°C for 10-20°C 14h, washed and dried to obtain Fe 3 O 4 . Preferably, in a preferred embodiment of the present invention, sodium dodecylbenzenesulfonate is selected as the surfactant, which can wrap the prepared Fe3O4 particles to prevent agglomeration, and the other is to disperse . The Fe 3 O 4 nano-scale particle structure has a large specific surface area, and when combined with other adsorption materials, it has strong adsorption capacity and good separation characteristics.
进一步地，所述铁盐选自硝酸铁、硫酸铁、氯化铁中的一种或多种，铁盐的量浓度为0.1～0.3mmol/ml。优选地，选用FeCl3·6H2O作为铁盐，其中铁盐的量浓度为0.1～0.2mmol/ml。FeCl3·6H2O价格低，易于购买。制备得到的Fe3O4的铁的化合价含有Fe3+和Fe2+。铁盐的量浓度维持在0.1～0.2mmol/ml之间，乙二醇可以将FeCl3·6H2O的Fe3+部分还原成Fe2+，但又不至于全部都进行还原。Further, the iron salt is selected from one or more of iron nitrate, iron sulfate, and iron chloride, and the concentration of the iron salt is 0.1-0.3 mmol/ml. Preferably, FeCl 3 ·6H 2 O is selected as the iron salt, wherein the concentration of the iron salt is 0.1-0.2 mmol/ml. FeCl 3 ·6H 2 O is cheap and easy to purchase. The iron valence of the prepared Fe 3 O 4 contains Fe 3+ and Fe 2+ . The concentration of iron salt is maintained between 0.1-0.2mmol/ml, and ethylene glycol can partially reduce Fe 3+ in FeCl 3 ·6H 2 O to Fe 2+ , but not completely.
进一步地，所述铁盐与乙酸钠的摩尔比为1:3～5。优选地，在本发明较佳实施例中，铁盐与乙酸钠的摩尔比为1:4，乙酸钠提供碱性环境。Further, the molar ratio of the iron salt to sodium acetate is 1:3-5. Preferably, in a preferred embodiment of the present invention, the molar ratio of iron salt to sodium acetate is 1:4, and sodium acetate provides an alkaline environment.
S2，制备Fe3O4@C：将碳源与所述Fe3O4分散在水中，超声搅拌后在150～200℃条件下反应4～8h，离心、洗涤、干燥后得到Fe3O4@C纳米颗粒。制备得到的Fe3O4@C具有超顺磁性，可以直接分散在水溶液中，在磁场下就可达到快速的固-液分离。S2, preparation of Fe 3 O 4 @C: disperse the carbon source and the Fe 3 O 4 in water, and after ultrasonic stirring, react at 150-200°C for 4-8 hours, centrifuge, wash and dry to obtain Fe 3 O 4 @C nanoparticles. The prepared Fe 3 O 4 @C has superparamagnetism, can be directly dispersed in aqueous solution, and can achieve rapid solid-liquid separation under a magnetic field.
进一步地，所述碳源与Fe3O4的质量比为5～15:1。优选地，在本发明较佳实施例中，所述碳源选用葡萄糖，葡萄糖价格便宜，易于取得，且碳元素含量多，是优质的碳源选择。Further, the mass ratio of the carbon source to Fe 3 O 4 is 5˜15:1. Preferably, in a preferred embodiment of the present invention, the carbon source is glucose. Glucose is cheap, easy to obtain, and has a high carbon content, so it is a high-quality carbon source choice.
更进一步地，所述碳源与Fe3O4的质量比为8～12:1。保证有足够的碳源复合到Fe3O4上，并对Fe3O4进行包裹。Furthermore, the mass ratio of the carbon source to Fe 3 O 4 is 8˜12:1. Ensure that there is enough carbon source to recombine on Fe 3 O 4 and wrap Fe 3 O 4 .
进一步地，所述洗涤、干燥步骤包括：用水和无水乙醇进行多次洗涤，最后一次用无水乙醇洗涤时先超声3～8min后再除去所述无水乙醇，然后在80℃条件下干燥6～10h。用无水乙醇进行最后一步清洗，可以使Fe3O4@C更为快速干燥。优选地，超声时间为5min，为了将附着在Fe3O4@C的细小杂质进行分离，而后去除。Further, the washing and drying steps include: washing with water and absolute ethanol for several times, the last time washing with absolute ethanol, ultrasonication is performed for 3-8 minutes, and then the absolute ethanol is removed, and then dried at 80°C 6～10h. The last step of cleaning with absolute ethanol can make Fe 3 O 4 @C dry more quickly. Preferably, the ultrasonic time is 5 minutes, in order to separate and remove the fine impurities attached to Fe 3 O 4 @C.
S3，制备Fe3O4@C-CoS-TiO2：将所述Fe3O4@C纳米颗粒、钴盐、硫脲、水、乙二醇、钛酸四丁酯和无水乙醇混合后，在150～200℃条件下反应12～16h，离心、洗涤、干燥后得到所述Fe3O4@C-CoS-TiO2复合光催化剂。S3, preparation of Fe 3 O 4 @C-CoS-TiO 2 : after mixing the Fe 3 O 4 @C nanoparticles, cobalt salt, thiourea, water, ethylene glycol, tetrabutyl titanate and absolute ethanol , react at 150-200° C. for 12-16 hours, centrifuge, wash and dry to obtain the Fe 3 O 4 @C-CoS-TiO 2 composite photocatalyst.
进一步地，所述钴盐溶液选自钴的硝酸盐、硫酸盐、卤化物、甲酸盐的一种或多种。在本发明较佳实施例中，优选六水合硝酸钴。Further, the cobalt salt solution is selected from one or more of cobalt nitrates, sulfates, halides, and formates. In preferred embodiments of the present invention, cobalt nitrate hexahydrate is preferred.
进一步地，所述钴盐和硫脲的质量比为1:0.5～2.5。优选地，所述钴盐和硫脲的质量比为1:0.5～1.5，使得钴盐和硫脲充分反应形成CoS。Further, the mass ratio of the cobalt salt to thiourea is 1:0.5-2.5. Preferably, the mass ratio of the cobalt salt and thiourea is 1:0.5-1.5, so that the cobalt salt and thiourea fully react to form CoS.
进一步地，钛酸四丁酯和水的体积用量比为1:10～30。优选地，在本发明的较佳实施例中，钛酸四丁酯和水的体积用量比为1:15～25。钛酸四丁酯和水反应生成TiO2，确保有足量的水与钛酸四丁酯反应生成TiO2。Further, the volume ratio of tetrabutyl titanate to water is 1:10-30. Preferably, in a preferred embodiment of the present invention, the volume ratio of tetrabutyl titanate to water is 1:15-25. Tetrabutyl titanate reacts with water to generate TiO 2 , ensuring sufficient water reacts with tetrabutyl titanate to generate TiO 2 .
进一步地，所述Fe3O4@C和所述钛酸四丁酯的投料比为0.05～0.25g/L。确保Fe3O4@C都能复合上TiO2。Further, the feed ratio of the Fe 3 O 4 @C to the tetrabutyl titanate is 0.05˜0.25 g/L. Make sure that Fe 3 O 4 @C can be compounded with TiO 2 .
本发明实施例还提供了一种Fe3O4@C-CoS-TiO2复合光催化剂，根据上述的制备方法制得。Fe3O4@C-CoS-TiO2复合光催化剂将CoS能带结构与TiO2的能带结构结合，从而吸收利用可见光。以Fe3O4@C作为磁性核心并起到稳定催化剂并保持活性的作用，所得到的Fe3O4@C-CoS-TiO2复合光催化剂在可见光响应条件下对环境中有机污染物的降解表现出很好的催化活性和稳定性，可重复使用，对环境友好。The embodiment of the present invention also provides a Fe 3 O 4 @C-CoS-TiO 2 composite photocatalyst, which is prepared according to the above-mentioned preparation method. The Fe 3 O 4 @C-CoS-TiO 2 composite photocatalyst combines the energy band structure of CoS with that of TiO 2 to absorb and utilize visible light. Using Fe 3 O 4 @C as the magnetic core to stabilize the catalyst and maintain its activity, the obtained Fe 3 O 4 @C-CoS-TiO 2 composite photocatalyst can resist the organic pollutants in the environment under the condition of visible light response. The degradation exhibits good catalytic activity and stability, is reusable and environmentally friendly.
以下结合实施例对本发明的特征和性能作进一步的详细描述。The characteristics and performance of the present invention will be described in further detail below in conjunction with the examples.
实施例1Example 1
本实施例提供的一种Fe3O4@C-CoS-TiO2复合光催化剂，包括以下步骤：A Fe 3 O 4 @C-CoS-TiO 2 composite photocatalyst provided in this embodiment comprises the following steps:
(1)制备Fe3O4：取30ml的乙二醇加入1mmol的十二烷基苯磺酸钠，搅拌1h至形成澄清液体，再加入4mmolFeCl3·6H2O和13mmol乙酸钠，搅拌0.5h后在180℃条件下保温12小时。产物先用去离子水和乙醇洗涤多次至澄清，最后一遍用无水乙醇洗涤，将洗涤后的产物干在60℃条件下干燥12h，最终黑色的Fe3O4。(1) Preparation of Fe 3 O 4 : Take 30ml of ethylene glycol and add 1mmol of sodium dodecylbenzenesulfonate, stir for 1h until a clear liquid is formed, then add 4mmol of FeCl 3 6H 2 O and 13mmol of sodium acetate, and stir for 0.5h Afterwards, it was incubated at 180° C. for 12 hours. The product was first washed with deionized water and ethanol several times until clarified, and finally washed with absolute ethanol. The washed product was dried at 60°C for 12 hours, and finally black Fe 3 O 4 was formed.
(2)制备Fe3O4@C：取1.0g葡萄糖、20ml去离子水于和0.1g的Fe3O4进行混合，超声搅拌30min，在180℃条件下反应6h。产物先用去离子水和乙醇洗涤多次至澄清，最后一遍用无水乙醇洗涤，超声5min，然后进行外加磁场分离，得到黑色产物，置入60℃条件下干燥8h得到Fe3O4@C纳米颗粒。(2) Preparation of Fe 3 O 4 @C: Mix 1.0 g of glucose, 20 ml of deionized water and 0.1 g of Fe 3 O 4 , stir ultrasonically for 30 min, and react at 180° C. for 6 h. The product was first washed with deionized water and ethanol several times until clarified, and finally washed with absolute ethanol, ultrasonicated for 5 minutes, and then separated by an external magnetic field to obtain a black product, which was dried at 60°C for 8 hours to obtain Fe 3 O 4 @C nanoparticles.
(3)制备Fe3O4@C-CoS-TiO2：将0.1g Fe3O4@C粉末、5ml无水乙醇、1.5g六水合硝酸钴、1.5g硫脲、5mL乙二醇、20mL去离子水和1ml钛酸四丁酯混合，磁力搅拌1h至均匀。而后在180℃条件下反应14h。产物先用去离子水和乙醇洗涤多次至澄清，最后一遍用无水乙醇洗涤，外加离心和磁场分离，然后在60℃下干燥12小时，研磨后得到Fe3O4@C-CoS-TiO2复合光催化剂。(3) Preparation of Fe 3 O 4 @C-CoS-TiO2: 0.1g Fe 3 O 4 @C powder, 5ml absolute ethanol, 1.5g cobalt nitrate hexahydrate, 1.5g thiourea, 5mL ethylene glycol, 20mL Ionized water and 1ml tetrabutyl titanate were mixed, and magnetically stirred for 1 hour until uniform. Then react at 180°C for 14h. The product was first washed with deionized water and ethanol several times until clarification, and finally washed with absolute ethanol, separated by centrifugation and magnetic field, and then dried at 60°C for 12 hours. Fe 3 O 4 @C-CoS-TiO was obtained after grinding 2 composite photocatalyst.
实施例2Example 2
本实施例提供的一种Fe3O4@C-CoS-TiO2复合光催化剂，与实施例1的区别之处在于：A Fe 3 O 4 @C-CoS-TiO 2 composite photocatalyst provided in this example differs from Example 1 in that:
步骤(3)制备Fe3O4@C-CoS-TiO2中，将0.1g Fe3O4@C粉末、5ml无水乙醇、1g六水合硝酸钴、1.5g硫脲、5mL乙二醇、20mL去离子水和1ml钛酸四丁酯混合，磁力搅拌1h至均匀。而后在180℃条件下反应14h。产物先用去离子水和乙醇洗涤多次至澄清，最后一遍用无水乙醇洗涤，外加离心和磁场分离，然后在60℃下干燥12小时，研磨后得到Fe3O4@C-CoS-TiO2复合光催化剂。Step (3) In the preparation of Fe 3 O 4 @C-CoS-TiO 2 , 0.1g of Fe 3 O 4 @C powder, 5ml of absolute ethanol, 1g of cobalt nitrate hexahydrate, 1.5g of thiourea, 5mL of ethylene glycol, 20mL of deionized water and 1ml of tetrabutyl titanate were mixed, and magnetically stirred for 1h until uniform. Then react at 180°C for 14h. The product was first washed with deionized water and ethanol several times until clarification, and finally washed with absolute ethanol, separated by centrifugation and magnetic field, and then dried at 60°C for 12 hours. Fe 3 O 4 @C-CoS-TiO was obtained after grinding 2 composite photocatalyst.
实施例3Example 3
本实施例提供的一种Fe3O4@C-CoS-TiO2复合光催化剂，与实施例1的区别之处在于：A Fe 3 O 4 @C-CoS-TiO 2 composite photocatalyst provided in this example differs from Example 1 in that:
步骤(3)制备Fe3O4@C-CoS-TiO2中，将0.1g Fe3O4@C粉末、5ml无水乙醇、1.5g六水合硝酸钴、1.5g硫脲、5mL乙二醇、25ml的去离子水和1ml钛酸四丁酯混合，磁力搅拌1h至均匀。而后在180℃条件下反应14h。产物先用去离子水和乙醇洗涤多次至澄清，最后一遍用无水乙醇洗涤，外加离心和磁场分离，然后在60℃下干燥12小时，研磨后得到Fe3O4@C-CoS-TiO2复合光催化剂。Step (3) In the preparation of Fe 3 O 4 @C-CoS-TiO 2 , 0.1g Fe 3 O 4 @C powder, 5ml absolute ethanol, 1.5g cobalt nitrate hexahydrate, 1.5g thiourea, 5mL ethylene glycol , 25ml of deionized water and 1ml of tetrabutyl titanate were mixed, and magnetically stirred for 1h until uniform. Then react at 180°C for 14h. The product was first washed with deionized water and ethanol several times until clarification, and finally washed with absolute ethanol, separated by centrifugation and magnetic field, and then dried at 60°C for 12 hours. Fe 3 O 4 @C-CoS-TiO was obtained after grinding 2 composite photocatalyst.
实施例4Example 4
本实施例提供的一种Fe3O4@C-CoS-TiO2复合光催化剂，与实施例1的区别之处在于：A Fe 3 O 4 @C-CoS-TiO 2 composite photocatalyst provided in this example differs from Example 1 in that:
步骤(3)制备Fe3O4@C-CoS-TiO2中，将0.2g Fe3O4@C粉末、5ml无水乙醇、1.5g六水合硝酸钴、1.5g硫脲、5mL乙二醇、20mL去离子水和1ml钛酸四丁酯混合，磁力搅拌1h至均匀。而后在180℃条件下反应14h。产物先用去离子水和乙醇洗涤多次至澄清，最后一遍用无水乙醇洗涤，外加离心和磁场分离，然后在60℃下干燥12小时，研磨后得到Fe3O4@C-CoS-TiO2复合光催化剂。Step (3) In the preparation of Fe 3 O 4 @C-CoS-TiO 2 , 0.2g Fe 3 O 4 @C powder, 5ml absolute ethanol, 1.5g cobalt nitrate hexahydrate, 1.5g thiourea, 5mL ethylene glycol , 20mL of deionized water and 1ml of tetrabutyl titanate were mixed, and magnetically stirred for 1h until uniform. Then react at 180°C for 14h. The product was first washed with deionized water and ethanol several times until clarification, and finally washed with absolute ethanol, separated by centrifugation and magnetic field, and then dried at 60°C for 12 hours. Fe 3 O 4 @C-CoS-TiO was obtained after grinding 2 composite photocatalyst.
对比例1Comparative example 1
本对比例提供的一种TiO2光催化剂，其制备步骤包括：A kind of TiO photocatalyst that this comparative example provides, its preparation step comprises:
将20mL去离子水和1ml钛酸四丁酯混合，磁力搅拌1h至均匀。而后在180℃条件下反应14h。产物先用去离子水和乙醇洗涤多次至澄清，最后一遍用无水乙醇洗涤，然后在60℃下干燥12小时，研磨后得到TiO2光催化剂。Mix 20mL of deionized water and 1ml of tetrabutyl titanate, and magnetically stir for 1h until uniform. Then react at 180°C for 14h. The product was first washed with deionized water and ethanol several times until clarification, and finally washed with absolute ethanol, then dried at 60 °C for 12 hours, and ground to obtain a TiO2 photocatalyst.
试验例1Test example 1
分别测定实施例1以及对比例1提供的可见光催化剂的光催化活性。在300W氙灯照射下，以甲醇水溶液为反应体系，实施例1光催化剂的氢气产率为4.9-5.9mmol/g/h。而相同条件下，实施例1比对比例1作为光催化剂时高出近70倍。The photocatalytic activities of the visible light catalysts provided in Example 1 and Comparative Example 1 were measured respectively. Under the irradiation of a 300W xenon lamp, using methanol aqueous solution as the reaction system, the hydrogen production rate of the photocatalyst in Example 1 was 4.9-5.9 mmol/g/h. And under the same conditions, Example 1 is nearly 70 times higher than that of Comparative Example 1 when it is used as a photocatalyst.
综上所述，本发明实施例提供的Fe3O4@C-CoS-TiO2复合光催化剂在可见光响应条件下，表现出很好的催化活性，并具有较强的制氢能力。In summary, the Fe 3 O 4 @C-CoS-TiO 2 composite photocatalyst provided by the embodiment of the present invention exhibits good catalytic activity and strong hydrogen production capacity under the condition of visible light response.
以上所描述的实施例是本发明一部分实施例，而不是全部的实施例。本发明的实施例的详细描述并非旨在限制要求保护的本发明的范围，而是仅仅表示本发明的选定实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The embodiments described above are some, not all, embodiments of the present invention. The detailed description of the embodiments of the invention is not intended to limit the scope of the claimed invention but to represent only selected embodiments of the invention. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.
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